Nanotechnology in the Life Sciences

Indu Bhushan
Vivek Kumar Singh
Durgesh Kumar Tripathi Editors

Nanomaterials and
Environmental
Biotechnology
Nanotechnology in the Life Sciences

Series Editor
Ram Prasad
School of Environmental Science and Engineering,
Sun Yat-sen University, Guangzhou, China
Amity Institute of Microbial Technology,
Amity University,  Noida, Uttar Pradesh, India
Nano and biotechnology are two of the 21st century’s most promising technologies.
Nanotechnology is demarcated as the design, development, and application of
materials and devices whose least functional make up is on a nanometer scale (1 to
100 nm). Meanwhile, biotechnology deals with metabolic and other physiological
developments of biological subjects including microorganisms. These microbial
processes have opened up new opportunities to explore novel applications, for
example, the biosynthesis of metal nanomaterials, with the implication that these
two technologies (i.e., thus nanobiotechnology) can play a vital role in developing
and executing many valuable tools in the study of life. Nanotechnology is very
diverse, ranging from extensions of conventional device physics to completely new
approaches based upon molecular self-assembly, from developing new materials
with dimensions on the nanoscale, to investigating whether we can directly control
matters on/in the atomic scale level. This idea entails its application to diverse fields
of science such as plant biology, organic chemistry, agriculture, the food industry,
and more.
Nanobiotechnology offers a wide range of uses in medicine, agriculture, and the
environment. Many diseases that do not have cures today may be cured by
nanotechnology in the future. Use of nanotechnology in medical therapeutics needs
adequate evaluation of its risk and safety factors. Scientists who are against the use
of nanotechnology also agree that advancement in nanotechnology should continue
because this field promises great benefits, but testing should be carried out to ensure
its safety in people. It is possible that nanomedicine in the future will play a crucial
role in the treatment of human and plant diseases, and also in the enhancement of
normal human physiology and plant systems, respectively. If everything proceeds as
expected, nanobiotechnology will, one day, become an inevitable part of our
everyday life and will help save many lives.

More information about this series at http://www.springer.com/series/15921

Indu Bhushan  •  Vivek Kumar Singh
Durgesh Kumar Tripathi
Editors

Nanomaterials
and Environmental
Biotechnology
Editors
Indu Bhushan Vivek Kumar Singh
School of Biotechnology School of Physics
Shri Mata Vaishno Devi University Shri Mata Vaishno Devi University
Katra, Jammu and Kashmir, India Katra, Jammu and Kashmir, India

Durgesh Kumar Tripathi

Amity Institute of Organic Agriculture
Amity University
Noida, Uttar Pradesh, India

ISSN 2523-8027     ISSN 2523-8035 (electronic)

Nanotechnology in the Life Sciences
ISBN 978-3-030-34543-3    ISBN 978-3-030-34544-0 (eBook)
https://doi.org/10.1007/978-3-030-34544-0

© Springer Nature Switzerland AG 2020

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Preface

Nanoscience is the science of small, i.e., nanoscale particles (1–100  nm), which
have a distinctive place not only because of their specific properties and reduced
dimensions but also due to their potential role as building blocks for the synthesis of
many nanostructure compounds. Nanoscience has added altogether another dimen-
sion of change in the direction of the revolutionary advancement in scientific under-
standing and it is applied across many other new technologies. From the time when
nanoscience was introduced several years ago, it has changed our lives signifi-
cantly – and will continue to do so! It all started in the field of physics “especially
in electronics” and later followed in pharmaceutical and chemical sciences.
Although the progress in the field of nanotechnology is a contemporary multidisci-
plinary science which involves the fields of chemistry, physics, engineering, and
biology, the production of nanoparticles (NPs), both by humans and in nature, dates
back to the pre-Christian era. In the present times, nanoscience and nanotechnology
have taken major roles in branches of research and industry which impact human
lives and yield unexpected results. However, the core aspect of nanoscience has
always been in the betterment of technological applications in various arenas, thus
making our daily lives easy and better. It enables quick advancements in a wide
array of fields, i.e., economical, environmental, pharmaceutical, industrial, and sev-
eral others. This book presents a fresh insight into the recent developments taking
place into various sectors, consolidating all the knowledge into one place. It is
aimed at an extensive array of book lovers with backgrounds in biology, chemistry,
medicine, and physics. This book emphasizes that nanotechnologies are now exten-
sively believed to have the capability to benefit diverse areas such as water decon-
tamination, drug development, communication technologies and information, and
manufacture lighter and stronger equipment. Each chapter in it gives an account of

v
vi Preface

the application of nanotechnology in basic sciences and manufacturing, along with

the commercial potential of nanomaterials in various industries and environment.

Katra, Jammu and Kashmir, India  Indu Bhushan

Katra, Jammu and Kashmir, India  Vivek Kumar Singh
Noida, Uttar Pradesh, India  Durgesh Kumar Tripathi
Contents

  1 Nanoparticles and Plant Interaction with Respect

to Stress Response������������������������������������������������������������������������������������    1
Mohammed Shariq Iqbal, Akhilesh Kumar Singh,
Satarudra Prakash Singh, and Mohammad Israil Ansari
  2 Nanoencapsulation Technology:
Boon to Food Packaging Industries��������������������������������������������������������   17
Somenath Das, Anand Kumar Chaudhari, Abhishek Kumar
Dwivedy, Neha Upadhyay, Vipin Kumar Singh, Akanksha Singh,
and Nawal Kishore Dubey
  3 Ecotoxicity of Metallic Nanoparticles and Possible
Strategies for Risk Assessment���������������������������������������������������������������   41
Ifra Zoomi, Harbans Kaur Kehri, Ovaid Akhtar, Dheeraj Pandey,
Pragya Srivastava, and Raghvendra Pratap Narayan
  4 Tripartite Interaction Among Nanoparticles, Symbiotic
Microbes, and Plants: Current Scenario and Future Perspectives ����   55
Ovaid Akhtar, Ifra Zoomi, Dheeraj Pandey, Harbans Kaur Kehri,
and Raghvendra Pratap Narayan
  5 Effect of Nanoparticles on Plant Growth and Physiology
and on Soil Microbes ������������������������������������������������������������������������������   65
Muhammad Nafees, Shafaqat Ali, Muhammad Rizwan,
Asma Aziz, Muhammad Adrees, Syed Makhdoom Hussain,
Qasim Ali, and Muhammad Junaid

vii
viii Contents

  6 Recent Trends and Advancement Toward Phyto-mediated

Fabrication of Noble Metallic Nanomaterials: Focus
on Silver, Gold, Platinum, and Palladium���������������������������������������������   87
Satarudra Prakash Singh, Mohammad Israil Ansari, Brijesh Pandey,
Janmejai Kumar Srivastava, Thakur Prasad Yadav, Humaira Rani,
Ashna Parveen, Jyoti Mala, and Akhilesh Kumar Singh
  7 Development of Environmental Biosensors for Detection,
Monitoring, and Assessment ������������������������������������������������������������������  107
Shagun Gupta and Vipan Kakkar
  8 Nano-Based Materials and Their Synthesis������������������������������������������  127
Shalini Chaudhary, Atin Kumar Pathak, and Shamshad Ahmad
  9 Nano-based Composites and Their Synthesis����������������������������������������  141
Shalok Bharti, Lalit Thakur, Sanjeev Anand, and Varun Dutta
10 Appraisal of Chitosan-Based Nanomaterials
in Enzyme Immobilization and Probiotics Encapsulation ������������������  163
Subham Rakshit, Suman Kumar Halder,
and Keshab Chandra Mondal
11 Nano-Based Drug Delivery Tools for Personalized Nanomedicine������  189
Shama Parveen, Neera Yadav, and Monisha Banerjee
12 Nanotechnology as Potential and Innovative Platform
Toward Wastewater Treatment: An Overview��������������������������������������  201
Akhilesh Kumar Singh and Paras Porwal
13 Solid Lipid Nanoparticles������������������������������������������������������������������������  221
Akhlesh Kumar Jain and Suresh Thareja
14 Nanotechnology Applications and Synthesis
of Graphene as Nanomaterial for Nanoelectronics������������������������������  251
Anil Bhardwaj, Gaurav Sharma, and Sumeet Gupta
15 Efficiency Enhancement of Renewable Energy Systems
Using Nanotechnology ����������������������������������������������������������������������������  271
Neelu Raina, Preeti Sharma, Parvez Singh Slathia,
Deepali Bhagat, and Atin Kumar Pathak
16 Wastewater and Industrial Effluent Treatment
by Using Nanotechnology������������������������������������������������������������������������  299
Sourav Maity, Debopriya Sinha, and Angana Sarkar
17 Biomolecular and Cellular Manipulation and Detection
(Nanofluidics and Micro- and Nanotechnologies
in Integrative Biology) ����������������������������������������������������������������������������  315
Shagun Gupta, Vijeshwar Verma, and Vipan Kakkar
Contents ix

18 Bio-Based Nano-Lubricants for Sustainable Manufacturing��������������  333

Rahul Anand, Mir Irfan Ul Haq, and Ankush Raina
19 Nanomaterials Used for Delivery of Bioactives ������������������������������������  381
Akhlesh Kumar Jain and Umesh Gupta
20 Efficacy of Nano-phytochemicals Over Pure
Phytochemicals Against Various Cancers: Current
Trends and Future Prospects������������������������������������������������������������������  407
Asif Jafri, Saima Amjad, Shabana Bano, Sudhir Kumar,
M. Serajuddin, and Md Arshad

Index������������������������������������������������������������������������������������������������������������������  425
Chapter 1
Nanoparticles and Plant Interaction
with Respect to Stress Response

Mohammed Shariq Iqbal, Akhilesh Kumar Singh, Satarudra Prakash Singh,

and Mohammad Israil Ansari

1.1  Introduction

Nanotechnology is an incipient multidirectional technique with extensive applica-

tions in cancer remedies, drug delivery, microelectronics, biosensors, and cosmetic
production, and also in agricultural fields (Nel et al. 2006; Singh et al. 2016, 2019;
Arif et al. 2018; Shweta et al. 2018, 2017; Vishwakarma et al. 2018; Rastogi et al.
2019a, b). However, unspecified discharge of nanoparticles (metallic) into ecologi-
cal communities has increased worldwide apprehension about their probable toxicity.
The length of nanoparticles generally ranges from 1 to 100 nm in at least two dimen-
sions, so that these are extremely fine particles with more surface area (Nowack and
Bucheli 2007). Compared to molecules and bulk materials, nanoparticles are inter-
mediate in size. The distinctive physical as well as chemical properties of nanopar-
ticles result from their detachment in bulk material into reduced and smaller pieces
(Jefferson 2000). However, because of their nanoscale size, their surface area thus
increases, which makes them extremely catalytic or reactive.
The haphazard release of nanoparticles into natural environments from industrial
effluents leads to their bulk production (Brunner et  al. 2006; Owen and Handy
2007). Thus, most produced nanoparticles consist of heavy metals, toxifying water
and soil with metallic nanoparticles, now a concern in environmental degradation.
Plant interaction with excess nanoparticles in water and soil may cause the uptake
and accumulation of the nanoparticles in the plant, leading to their ultimate convey-
ance to the ecosystem. However, nanoparticles may persist and be accumulated

M. S. Iqbal · A. K. Singh · S. P. Singh

Amity Institute of Biotechnology, Amity University Uttar Pradesh, Lucknow Campus,
Lucknow, India
M. I. Ansari (*)
Department of Botany, University of Lucknow, Lucknow, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 1

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_1
2 M. S. Iqbal et al.

within the plant, thus causing physical as well as chemical damage to various parts
of the plant. Generally, nanoparticles pass into the plant root system through junc-
tions of the lateral roots, thereby reaching the xylem tissue through the pericycle
and the cortex (Dietz and Herth 2011). Moreover, although the cell wall restricts the
entrance of nanoparticles into the plant body, cell walls have a definite pore size,
allowing the transference of nanoparticles smaller than the pore size of the cell wall
(Fleischer et al. 1999; Navarro et al. 2008). The degree of penetration is subject to
the surface characteristics and dimensions of the nanoparticles. Undeniably, the
smaller nanoparticles can pass through the cell wall easily. Larger nanoparticles are
unable to pass through the cell wall and thus cannot disturb the metabolic pathways
of the cell (Verano-Braga et al. 2014). However, flower stigmas, hydathodes, and
stomata possess larger cell-wall openings, so that larger-size nanoparticles can pass
through and possibly affect the plant. Chemical and physical interactions of
nanoparticles with plants could be a natural or induced phenomenon. Chemical
interfaces encompass the production of reactive oxygen or nitrogen species (ROS/
RNS) (Nel et  al. 2006), disruption in cell membrane transport activity of ions
(Auffan et al. 2008), injury from oxidative stress (Foley et al. 2002; Jalil et al. 2017),
and peroxidation of lipids present in the cells of the plant (Kamat et al. 2000). The
ensuing admittance into the body of the plant through the cell wall subsequently
allows nanoparticles to associate and work as metallic ions, reacting with carboxyl
and sulfhydryl groups and eventually modifying protein activity. The effect of
nanoparticle applications in shown in Fig. 1.1.
However, while studying engineered nanomaterials that arbitrate ecotoxicity,
several artifacts that often lead to misconceptions of outcomes should be considered
(Petersen et  al. 2014). These probable aspects consist of noxious scum in engi-
neered nanomaterials, their apposite storage and dissemination in a particular
medium. Furthermore, engineered nanomaterials imply unintended effects on plant

Fig. 1.1  Effect of nanoparticles on plants, leading to stress conditions

1  Nanoparticles and Plant Interaction with Respect to Stress Response 3

growth and development by depletion of nutrients with time and the diffusion of the
engineered nanomaterials in organisms. Additionally, the dissolution, settling, and
agglomeration properties of engineered nanomaterials cause diverse variations all
through the study period that are difficult to evaluate accurately. Characteristics
such as greater superficial area with distinct physical as well as chemical properties
allow engineered nanomaterials to freely interact with ions physicochemically
within the nutrient medium, thereby causing unintended toxic reactions such as
wilting and chlorosis (Slomberg and Schoenfisch 2012; Begum and Fugetsu 2012;
Jalil et al. 2018). Furthermore, as engineered nanomaterials interact with organic
acids in the roots of the plant, the pH of the media falls, thereby modifying the nutri-
ent quantity and properties of the engineered materials (Marschner 1995). The inef-
fectiveness of such interactions and their effects can be observed as an incongruous
elucidation of phytotoxicity, and eventually a fictitious impression of engineered
nanomaterials is understood (Ma et al. 2010).

1.2  The Nanoparticle and Its Role in Plant Stress

It is been reported that nanoparticles generally possess desired and undesired out-
comes on various plant species because of their configuration, dissimilar size,
altered physicochemical properties, and the concentrations of different nanoparti-
cles used (Ma et al. 2010; Tripathi et al. 2017). It was reported that carbon nano-
tubes (multi-walled) substantially exaggerated the upregulation of stress-related
gene expression in tomato seed germination and further affected the progress of the
seedlings (Khodakovskaya et al. 2009; Singh et al. 2016; Koul et al. 2018). In a
finding by Lee et al. (2010), Al2O3 nanoparticles were found to be less toxic than
ZnO, SiO2, or Fe2O3 nanoparticles when used to treat Arabidopsis thaliana. Earlier
investigations on algae also underscored the noxious effects of nanoparticles
(Arouja et  al. 2009). Several nanoparticles such as CeO2, ZnO, TiO2, and Ag
nanoparticles were observed to be deposited on the cell-wall surface as well as on
the surface of the organelles, which causes stimulation in the form of stress response
from oxidative stress within the cell (Buzea et  al. 2007). In another study of
Cucurbita pepo, the outcome of showed that seed germination was not altered by
treatment with Cu, Si, Ag, and ZnO nanoparticles. On the other hand, their comple-
mentary bulk constituents and Cu nanoparticles cause alteration in root length when
estimated against the control and a powder of bulk copper (Stampoulis et al. 2009).
Treatment with ZnO nanoparticles affected root length in rice plants, but TiO2
nanoparticles had no effect on the roots (Boonyanitipong et al. 2011). In another
study, Riahi-Madvar et al. (2012) revealed effects on the roots of Triticum aestivum
by treating the plant withAl2O3 nanoparticles at different concentrations, although
the nanoparticles did not influence seed germination, shoot length, or fresh weight/dry
weight ratio. Treatment of rice seedlings with CuO nanoparticles had an effect on
enzymatic activity. Enzymatic antioxidant values were shown to be elicited (Shaw
and Hossain 2013). An analogous experiment was conducted by Shaw et al. (2014)
4 M. S. Iqbal et al.

wherein treatment of Hordeum vulgare with CuO nanoparticles caused an effect on

photosynthetic activity and also on the antioxidants. It was elucidated that the
decreased growth of shoot and root length caused poor photosynthetic activity.
Furthermore, Atha et al. (2012) showed CuO nanoparticles cause decreased growth
and DNA damage in Raphanus sativus, Lolium perenne, and Lolium rigidum plants.
Rico et  al. (2013) revealed effects on photosynthetic activity, enzymatic activity,
and ascorbate and thiol levels when CeO2 nanoparticles were used to treat rice seed-
lings. Formation of ROS/RNS and H2O2 when Spirodela punctata plants were
treated with Ag and ZnO nanoparticles showed the significant toxicity of these
nanoparticles (Thwala et  al. 2013). Among the numerous metallic nanoparticles,
ample consideration has been paid to Ag nanoparticles because of their distinctive
biological and physicochemical properties when compared to various other large-­
size nanoparticles (Sharma et al. 2009). The fungicidal and bactericidal properties
of Ag nanoparticles have widespread application as an indispensable constituent in
various products at domestic, nutritional, and industrial levels (Tran et al. 2013).
Silver nanoparticles when compared to silver-based compound nanoparticles pos-
sess an enlarged surface area accessible for microbe interface; further, it was
reported that such are more noxious to various fungi and bacteria and several viruses
as well. Similar to alternate metallic nanoparticles, Ag nanoparticles possess more
impact on prompt stress reactions (ROS/RNS) in various microorganisms, algae,
animals, and plants (Jiang et al. 2012). Conversely, the stimulus of Ag nanoparticles
on plants is basically governed by such factors as plant species, growth and devel-
opmental stage, type and concentration of nanoparticles used, and experimental
parameters such as period of treatment, humidity and temperature, and method of
nanoparticle treatment (Vannini et al. 2013). Ag nanoparticles are one of the most
widely examined nanoparticles whose toxic effects have been investigated in numer-
ous plant crops (Stampoulis et  al. 2009; Jiang et  al. 2012; Kumari et  al. 2009).
Several studies have revealed that Ag nanoparticles were disadvantageous for plant
growth as compared to the growth-enhancing possession of Ag nanoparticles in
wetland plants (Yin et  al. 2012), Proteus vulgaris and Zea mays (Salama 2012),
Brassica juncea (Sharma et al. 2012), and Eruca sativa (Vannini et al. 2013). Ag
nanoparticles showed a chromotoxic outcome on mitotic cell division in Allium
cepa (Kumari et al. 2009). Further, Ag nanoparticles intermingle with proteins (are
membrane bound) and stimulate various metabolic pathways, which restricts cell
propagation (Roh et al. 2012; Gopinath et al. 2010). Some of the numerous effects
of nanoparticles on plants are summarized in Table 1.1.

1.3  Mechanistic Interaction of Nanoparticles in Plant Stress

Recent studies showed that all the interactions of nanoparticles may be determined
and noted to be affected by plant species, nanoparticle type and size, and the chemi-
cal structure, constancy, and functional aspects of the nanoparticles. The interaction
of nanoparticles with plants leading to stress can be classified into different phases
of nanoparticle uptake, translocation within the plant, accumulation in different
1  Nanoparticles and Plant Interaction with Respect to Stress Response 5

Table 1.1  Response of different plants toward different kinds of nanoparticles

Types of
nanoparticles
Plants applied Response References
Boswellia Silver Improved germination Savithramma et al. (2012);
ovalifoliolata, rate; enhanced enzymatic Yuan et al. (2018b);
Egeria densa, Juncus antioxidants; no effect on Olchowik et al. (2017)
effusus, Quercus chlorophyll; no
robur phytotoxicity
Gloriosa superba, Cerium oxide Toxic; Increased plant Arumugama et al. (2015);
Arabidopsis thaliana growth Ma et al. (2013)
Gum karaya, Copper oxide Therapeutic applications; Jayalakshmi and
Phyllanthus amarus, Positive antimicrobial Yogamoorthi (2014);
Cassia alata activity Vellora et al. (2013);
Acharyulu et al. (2014)
Quercus robur Copper Positive antimicrobial Olchowik et al. (2017)
activity; no phytotoxicity
Euphorbia Palladium As a catalyst Nasrollahzadeha et al.
condylocarpa 2015
Oryza sativa, Titanium dioxide Phytocatalyst Ramimoghadam et al.
Triticum aestivum, Elicitation of chlorophyll (2014); Mahmoodzadeh
Lycopersicon et al. (2013); Qi et al.
esculentum (2013)
Glycine max, Vigna Iron oxide Improved productivity Dhoke et al. (2013);
radiata and quantity Sheykhbaglou et al. (2010)
Capsicum annuum Iron Promoted plant growth; Yuan et al. (2018a, b)
alleviated iron deficiency
Arachis hypogaea Zinc oxide Improved productivity Prasad et al. (2012)
Cucumis sativus Gold Improved germination Barrena et al. (2009)
rate
Lycopersiconm Carbon Improved germination Morla et al. (2011)
esculentum nanotubes rate
Solanum Nickel oxide Induced apoptosis in Faisal et al. (2013); Soares
lycopersicon roots; enhanced et al. (2016)
antioxidants
Lemna minor Alumina Enlarged plant growth; Juhel et al. (2011)
improved productivity
and quantity

cells and tissues, and desired or undesired outcomes. Some of the studies revealing
such conditions are discussed next.

1.3.1  Phytotoxicity Mechanism of Nanoparticles

Investigation related to phytotoxicity in higher plants is imperative for elucidating

the toxic effect of nanoparticles. Both undesirable and desirable or insignificant
effects have been elucidated concerning the potential noxiousness of nanoparticles
6 M. S. Iqbal et al.

to various plants (Bystrzejewska-Piotrowska et al. 2009; Sohaebuddin et al. 2010;

Muller et al. 2005; Jalil et al. 2018). Various studies point toward nanoparticle toxic-
ity (Ghodake et al. 2010; Stampoulis et al. 2009). A noticeable variation in germina-
tion rate and growth was detected in the seeds of rice when exposed to carbon
nanomaterials, mainly carbon nanotubes (Wang et al. 2012; Smirnova et al. 2012;
Tan and Fugetsu 2007). In the experiment, water content in carbon nanotube-treated
seeds was compared to that in control seeds, with better water content observed in
the treated seeds. The germinating seeds were supplemented with carbon nanotubes
to elucidate the effect on further developmental stages. The findings show signifi-
cant use of carbon nanotubes to improve the growth of rice seedlings (Smirnova
et al. 2012). In another example using Al2O3 nanoparticles, root length elongation
was hindered in soybean, carrot, cabbage, cucumber, and corn (Kollmeier et  al.
2000; Yamamoto et al. 2001; Tian et al. 2007; Ryan et al. 1992), whereas nanopar-
ticles of ZnO were found to be maximally toxic, impeding the growth rate of the
roots in various plants (Stella et  al. 2010; Ma et  al. 2009; Huang et  al. 2002).
Nanoparticles of ZnO were observed to be noxious in high concentrations when
used to treat Arabidopsis thaliana plants, where a decreased germination rate was
observed, with Al2O3, SiO2, and Fe (II, III) oxide nanoparticles showing a moderate
effect (Bin Hussein et al. 2002; Wang et al. 2004; Dwivedi and Randhawa 1974).
With consideration for the toxicological aspect, the ratio of particle size to surface
area is a vital physical property of a nanoparticle; the lesser the particle size, the
greater the surface area. Hence, more of its atoms or molecules are exhibited exter-
nally than internally (Fugetsu and Parvin 2011; Begum et al. 2011). Several studies
revealed surface properties of nanoparticles to be more toxic with a higher toxicity
level than finer particles of the same material (Clarke and Brennan 1989; Kashem
and Kawai 2007): this has been experimentally demonstrated by the use of diverse
types of nanoparticles, such as cobalt, nickel, titanium dioxide, and carbon black. It
was observed that TiO2 nanoparticles with a minimum size less than 30 nm conse-
quently are 43 fold more inflammatory than nanoparticles larger than 200 nm (Feizi
et  al. 2012; Castiglione et  al. 2011; Qiu et  al. 2013). Numerous investigations
revealed that nano-sized particles are somewhat more toxic than micro-sized parti-
cles (Currie and Perry 2007). It was elucidated that one of the important parameters
of noxiousness of nanoparticles is surface area. For instance, crystalline TiO2 did
not exhibited more severe toxicity than shown by TiO2 nanoparticles (Stephen et al.
2012; Han et al. 2010). Generally, the present phytotoxic outline of nanoparticles is
somewhat hypothetical; initially, the effects of nanoparticle properties are not well
understood and further investigation on toxic effects is necessary, particularly on
valuable food crops (Groppa et al. 2008). Thus, it can be concluded that various
investigations have revealed that direct exposure to a particular kind of n­ anoparticles
instigated a noteworthy phytotoxic effect, underscoring the necessity for environ-
mental accountability for discarding wastes containing nanoparticles. Further stud-
ies on the influence of nanoparticles on valuable food crops and on the environment
are required.
1  Nanoparticles and Plant Interaction with Respect to Stress Response 7

1.3.2  Uptake Mechanism of Nanoparticles

Investigations on the mechanism of uptake of nanoparticles in plants lack reliable

and widely acceptable information (Nevius et  al. 2012). Previous observations
showed that nanoparticles may adhere to the plant root system and cause physico-
chemical changes during uptake within the plant (Hartley and Lepp 2008; Taylor
and Foy 1985). Currently, various investigations emphasize revealing the interface
mechanism of nanoparticles toward plants (Besson-Bard et al. 2009; Zhang et al.
2017; Ma et al. 2018). Nanoparticle uptake and accumulation may differ depending
on the difference in size and type of nanoparticle within the plant. Undeniably, vali-
dation of the mechanism of nanoparticle uptake is very restricted, and it depends on
the concentration applied (Smirnova et al. 2012). Thus, most of the investigations
reported do not yield similar outcomes for diverse forms (shapes and sizes) of
nanoparticles (John et al. 1972). The majority of information is related to metal-­
based nanoparticles such as TiO2, ZnO, Ag, Au, or Fe that correspond to a particular
germination stage of the plant. Various possibilities have been suggested for
nanoparticle uptake by the cells of the plants. Studies have suggested that nanopar-
ticles move in plant cells by binding with protein biomolecules or ion channels, or
through the process of endocytosis by means of new pores formed, finally binding
to some organic molecule (Maine et al. 2001; Kurepa et al. 2010). For such investi-
gations, carbon nanotubes have been preferred over other nanoparticles (Smirnova
et al. 2012). However, it was reported that nanoparticles when compared to the bulk
metals cause more reactivity by the greater surface area to mass ratio (Yuan et al.
2011). Subsequently, the nanoparticles might align with membrane transporters to
form complexes as the root absorbs these and transports the particles into the plants.
Thus, nanoparticles have been identified that can recognize ion transporters and be
readily taken up by the plant (Tani and Barrington 2005). Selectivity among types
of plants and the uptake of nanoparticles, which is still not very clear, is an area of
further investigation.

1.3.3  Translocation Mechanism of Nanoparticles

Several investigations supported that the translocation of nanoparticles is deter-

mined by the quantity delivered and the species of plant (Yang and Ma 2010).
Specific nanoparticles move swiftly within the plant, forming interactions with
other biomolecules. Thus, the other nutrients are estimated according to the
­translocation of the nanoparticles applied (Zhu et  al. 2008). The mechanism of
translocation is instigated by the permeation of nanoparticles, into first the cell walls
and then the plasma membrane of the cells. Through conduction by the plant xylem,
the uptake mechanism and nanoparticle transferences take place in the shoot system
8 M. S. Iqbal et al.

(Pola et al. 2012; Birbaum et al. 2010). The pore size of the cell wall is a vital criterion
for the selection of nanoparticles, determining which nanoparticles can penetrate.
As was investigated in Allium porrum, nanoparticle penetration was swifter in
stomata than in the leaf (Birbaum et al. 2010).

1.3.4  I nteraction Mechanism of Nanoparticles Leading

to Stress

For the past few decades, the phytotoxicity of nanoparticles has been extensively
investigated in several plant species, mainly focusing morpho-physiologically and
biochemically. Nevertheless, only a few experiments have been focused on nanopar-
ticle interaction with biomolecules with consideration of proteomics and causes of
stress in the plant. Mirzajani et  al. (2014) revealed by proteomic technique (gel-­
based) that the interaction of Ag nanoparticles on Oryza sativa causes toxicity. This
investigation, based on root proteomics, elucidated that Ag nanoparticle-associated
proteins were mainly related to the oxidative stress pathway, transcription, cell-wall
synthesis, ion signaling and its regulation, division of cells, and degradation of pro-
tein. The effect of nanoparticles on the cell leading to such alterations is shown in
Fig. 1.2. It was further observed that elicitation of enzymatic antioxidants such as
peroxidases, glutathione-S-transferase, L-ascorbate, and superoxide dismutase
induces enhanced formation of ROS under Ag nanoparticle treatment stress (Vannini
et al. 2013). When Ag nanoparticles and AgNO3 compounds were applied to Erruca
sativa roots, both forms of silver produced alterations in the proteins associated
with cellular homeostasis and redox regulation. These outcomes showed that the
noxiousness of Ag nanoparticles mainly derives from its distinctive physicochemi-
cal characteristics (Vannini et al. 2013). Under flooding stress, the toxicity mecha-
nism of Ag nanoparticles was studied in early stages of Glycine max plants, showing
that proteins associated with signaling pathways, and the metabolism of cells and
stress response, were altered. Furthermore, glyoxalase, an enzyme related to the
detoxification pathway, was also degraded by Ag nanoparticle treatment (Mustafa
et al. 2015a, b). In another study by Mustafa et al. (2015a, b), wherein the effects of
Ag, ZnO, and Al2O3 nanoparticles were compared for treating Glycine max plant
under flooding stress, protein synthesis was degraded, and glycolysis and lipid
metabolism were also affected. Such investigations exhibit the interaction of
nanoparticles with plants, but more research is needed to fully elucidate such effects.
Thus, the desired as well as undesirable effects of nanoparticles can be observed on
plants depending upon the requirements. Future investigations on interaction of
nanoparticles with plants would help elucidate better understanding, implying
­specific nanoparticles can be applied to plants for desired outcomes, which may
lead to better agricultural yields.
1  Nanoparticles and Plant Interaction with Respect to Stress Response 9

Fig. 1.2  Systematic representation of effect of nanoparticles within the plant cell leading to stress
conditions

1.4  Conclusions and Future Prospects

The investigations conducted so far mostly concern plant reactions to a particular

nanoparticle stress displaying an abundance of proteins associated with ROS, sig-
naling caused by stress, pathways related to plant hormones, oxidation-reduction
within the cell, and detoxification. Investigations on nanoparticles causing phyto-
toxicity showed that nanoparticle size is an important aspect in the type and degree
of response within the plant cell. Further investigations are needed to fully elucidate
whether metallic nanoparticles wield their noxious effects because of their distinc-
tive characteristics or the loose metallic ions. Furthermore, exploration intended to
recognize and illustrate subcellular organelles for elucidating the detailed altera-
tions within the cell helps to understand the stress mechanism caused by nanopar-
ticles. Additionally, metabolomics and transcriptomics techniques can have great
prospects to fully elucidate the stress response toward nanoparticles. All this infor-
mation would give us a wide explanation of the response mechanism of plants to
stress caused by nanoparticles. Such investigations on plant stress tolerance mecha-
nisms toward nanoparticles can lead to better plant yields for the production of
specific valuable phytochemicals. These data, based on the interaction of
­nanoparticles with plants, would help elucidate improved understanding about the
plant responses, which would suggest particular nanoparticles for plants for anticipated
10 M. S. Iqbal et al.

outcomes. This information can be advantageous for the agricultural perspective

in improved yields and increased production of secondary metabolites that are
beneficial in the pharmaceutical and nutraceutical industries.

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Chapter 2
Nanoencapsulation Technology:
Boon to Food Packaging Industries

Somenath Das, Anand Kumar Chaudhari, Abhishek Kumar Dwivedy,

Neha Upadhyay, Vipin Kumar Singh, Akanksha Singh,
and Nawal Kishore Dubey

2.1  Introduction

Global food security is one of the biggest issues nowadays. Various food-borne
pathogens like bacteria, fungi, and insects not only invade the food but also alter
their nutritional profile by producing toxic metabolites (Scallan et al. 2011; Marin
et al. 2013; Kim et al. 2003; Park et al. 2003; in’t Veld 1996). Fungi, most impor-
tantly belonging to the species of Aspergillus, Penicillium, and Fusarium, are the
major contributors for food and feedstuff spoilage. They produce mycotoxins, viz.,
aflatoxins, fumonisins, ochratoxins, deoxynivalenol, and zearalenone. Among these
mycotoxins, aflatoxins in particular aflatoxin B1 (AFB1) produced mainly by differ-
ent species of Aspergillus are a severe concern as it pose carcinogenic, teratogenic,
mutagenic, and immunosuppressive potential. Based on the toxicity, it has also been
recognized as class I human carcinogen (IARC 1993). The consumption of these
contaminated products may have a direct effect on the consumer’s health in the form
of chronic and acute toxicity. It is estimated that annually around 200 deaths of adults
and 40% of children’s death up to 5 years are due to illness caused by consumption
of contaminated foods (WHO 2017). In order to reduce these harmful contaminants
from food, several physical methods like heating, UV or ionizing radiation, mem-
brane filtrations (Farkas 2007), and use of synthetic chemical preservatives, viz.,
potassium bromate, butylated hydroxyanisole (BHA), and butylated hydroxytolu-
ene (BHT) (Inetianbor et al. 2015), are widely used; however their irrational use
may cause pest resistance and adverse effect on humans as well as on the environ-
ment, which has enforced the scientists to look toward natural food preservatives in
order to meet sustainable food security (Damalas and Eleftherohorinos 2011)

S. Das · A. K. Chaudhari · A. K. Dwivedy · N. Upadhyay · V. K. Singh

· A. Singh · N. K. Dubey (*)
Department of Botany, Center of Advanced Study, Institute of Science,
Banaras Hindu University, Varanasi, India

© Springer Nature Switzerland AG 2020 17

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_2
18 S. Das et al.

Since antiquity, plant products in different forms like powder or extracts have
been used as preferred alternatives for the protection of food commodities from
storage contaminants; however plant products in the form of essential oils are of
great concerns as they are volatile, biodegradable, with no residual toxicity, safe to
mammalian system, and eco-friendly (Isman 2000; Burt 2004). Many literatures
also claim the importance of essential oils as the source of natural preservatives in
view of their strong antimicrobial and antioxidant potential (Tripathi et al. 2009;
Sánchez-González et al. 2011). Although, essential oils have merit over chemical
preservatives, they often fail to exert their full preservative potential, due to oxida-
tion and instability in presence of heat, light and other abiotic factors (Prakash
et al. 2018).
In view of these obstacles, introduction of nanotechnology has revolutionized the
food industry for the progress of nano based formulation of essential oils and other
bioactive components, to achieve major goal of sustainable food preservation and
security. Nanoparticles enclosing active principles are claimed to enhance the effi-
cacy of bioactive components, as well as the stability, texture, taste and flavor of
food products.
Based on the above background, the present chapter provides an overview of
currently employed nanotechnologies and their application in food sectors to
develop an approach for the preservation of food during storage in order to achieve
sustainable food security.

2.2  Nanomaterials Used for Food Packaging

Recent development in EO formulations based on nanoencapsulation technology

has gained much attention in food sectors. These formulations can take display
several advantages over conventional methods of food preservation. They confer the
controlled release of essential oils and protect them from thermal and photodegra-
dation which assures their improved stability, organoleptic impacts, flavor, and
function, consequently extending the final product shelf life (Liang et  al. 2012;
Madene et al. 2006; Lakkis 2016). There are several methods which have been used
for the preparation of nanoparticles using various coating materials. Some of the
important methods including different types of polymer used for encapsulation of
essential oils or plant bioactive components are discussed and listed in Table 2.1.

2.2.1  Lipid-Based Encapsulation of Essential Oils

Lipids are an important group of natural molecules supporting vital life processes.
Lipids give desired qualities like texture, aroma, color, and flavor and mouth-filling
properties to food products (Bourne 2002). Currently, due to their nontoxicity and
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 19

Table 2.1  List of key nanoparticle types enclosing active materials and their biological properties
S Nanoparticle EO/bioactive
no. type compounds Inference References
1. Nanoemulsion Eugenia brejoensis Antimicrobial Mendes et al. (2018)
Pimpinella anisum Insecticidal Hashem et al. (2018)
Lemongrass Antimicrobial Guerra-Rosas et al. (2017)
Thyme oil Antimicrobial Ryu et al. (2018)
Lemon myrtle Antimicrobial Buranasuksombat et al. (2011)
Cinnamomum Antimicrobial Tian et al. (2016)
zeylanicum
2. Solid lipid NPs Eugenia caryophyllata Antimicrobial Fazly Bazzaz et al. (2018)
Melaleuca alternifolia Insecticidal/ Clerici et al. 2018
repellent
Frankincense and Anticancer Shi et al. (2012)
myrrh
Miconazole (drug) Antifungal Aljaeid and Hosny (2016)
3. Liposome-­ Geranium maculatum Insecticidal González et al. (2017)
mediated NPs Nigella sativa Anticancer Shanmugam et al. (2017)
Torreya grandis Antibacterial Wu et al. (2018)
4. Micelles Tea tree Antimicrobial Ganguly et al. (2018)
Carvacrol and eugenol Antibacterial Gaysinsky et al. (2005)
5. Chitosan-based Gaultheria procumbens Antifungal Kujur et al. (2017)
NPs Zataria multiflora Antifungal Mohammadi et al. (2015)
Garlic Antifungal Yang et al. (2009)
6. Strach-based Menthone, citral, and Antimicrobial Qiu et al. (2017)
NPs lavender oil
Oregano oil Antimicrobial Pelissari et al. (2009)
Cinnamon oil Antimicrobial Souza et al. (2013)
7. Gum-based Carvacrol and thymol Antibacterial Guarda et al. (2011)
NPs Lemongrass and Antifungal Maqbool et al. (2011)
cinnamon oil

high acceptability in food products, lipid-based encapsulation of EOs is gaining

high attention among scientists worldwide for their use in the food system (Aditya
and Ko 2015). Generally lipid-based encapsulation includes emulsions (nano- and
micro-emulsions), solid lipid-based nanoparticles (SLBNs), liposome-mediated
nanoparticles, micelles, etc.

2.2.1.1  Emulsions

The emulsions can be grouped into three major categories, viz., macro-, micro- and
nanoemulsions, which are of major focus for food industries employing bioactives
exhibiting low water solubility including essential oils (Xue 2015). Generally, sur-
factants are used for the preparation of emulsions; however, proteins and lipids have
20 S. Das et al.

also been used. Preparation and characterization of essential oil loaded nanoemul-
sion incorporates different modern technologies such as homogenization, sonication,
X-ray diffraction and scanning and transmission electron microscopy (Gupta et al.
2016; Solans et al. 2005).

2.2.1.2  Solid Lipid Nanoparticle (SLNs)

These are novel colloidal carriers developed as an alternative material to the poly-
mers, where the solid lipids were involved. Solid-phase lipid nanoparticles are one
of the most popular approaches in the field of food sciences for improvement of
essential oils biocompatibility (Mukherjee et al. 2009; Saupe and Rades 2006). So
far, several methods have been used for the preparation of SLNs, among which
high-pressure homogenization, ultrasonication, solvent evaporations, spray drying,
and emulsion-based preparations are the most common (Ekambaram et al. 2012).

2.2.1.3  Liposome as Nanocarriers of Bioactive Molecules

Liposome is one of the important systems formed by one or more phospholipids

bilayer with an internal aqueous compartment. Due to their amphipathic nature,
phospholipids are able to self-organize in the aqueous phase. On account of these
properties, liposome-mediated encapsulation is useful for both the hydrophobic and
hydrophilic components (El Asbahani et al. 2015). They are efficient carrier mole-
cules for incorporating EOs and components, by improving their physicochemical
properties, bioavailability, and solubility (Coimbra et al. 2011). Thin film evapora-
tion, extrusions, sonication, freeze thaw, and saturation of gas-phase solution were
the most commonly used methods in the preparation of liposome-mediated encap-
sulation (Sherry et al. 2013).

2.2.1.4  Micelles

Micelles are the supramolecular complexes consisting of polar and nonpolar

materials containing different interwoven gelling agents (Rodríguez et al. 2016).
Incorporation of essential oils with anticancerous activities into micelles matrix
may be an important strategy to combat the rising incidence of cancers and other
untreated diseases. Micelle sizes vary in the dimension from 2 to 20 nanometers
based on experimental procedures. Commonly used techniques for micelle
­preparation are suspension, solvent removal through appropriate methods, dis-
persion, and dialysis (Hoar and Schulman 1943; Jones and Leroux 1999). An
outline of preparation of different lipid-based nanoparticle has been presented in
Fig. 2.1.
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 21

Fig. 2.1 An illustrated diagram showing methodology for the preparation of lipid-based
nanoparticles

2.2.2  Polymer-Based Encapsulation of Essential Oils

Polymers including chitosan, starch, cellulose, plant gums, dextrin, and alginates
are some of the main wall materials used to entrap essential oils into micro- or nano-­
sized matrix to prevent them from physical degradation and to enhance their antimi-
crobial efficiencies.
Starch is a natural and biodegradable polymer used as energy source by many
plants. It is also an important polymer in nature. Starch and its modified forms
maltodextrins, cyclodextrins, and dextrin whites are being used in the formation of
essential oil loaded nanoparticle owing to their abundance, emulsifier property, high
stability, and biocompatibility. To date, several starch-based nanoparticles have
been developed to enhance the efficacy of bioactive components as evidenced by
recent literatures (Shao et al. 2018; Hasani et al. 2018).
Chitosan is an important biopolymer mostly used for active encapsulation of
essential oils and their components to enhance activity toward a wide range of
pathogens and storage pests (Hosseini et al. 2013). In general, chitosan is isolated
22 S. Das et al.

Fig. 2.2  Important polymer based nanoencapsluation methods for bioactive materials

from outer skeletal part of crustacean members, which  contains different amines
along with primary and secondary alcoholic groups for active binding with essential
oil (Vishwakarma et al. 2016).
Gums are natural plant products serving as excellent wall materials for the
encapsulation of important plant-derived bioactive components. The semiperme-
able character of gums helps in stabilization during the encapsulation process
(Sarkar et al. 2012; Hamid Akash et al. 2015). In addition, some other polymers like
cellulose, wax, gluten, alginate, xanthan, whey, etc. have also been utilized for
essential oil encapsulation. A systemic representation on polymer-based nanoen-
capsulation process for bioactive materials is presented in Fig. 2.2.

2.3  A
 ctive Packaging of EO Nanoparticles as Food
Protectant

Active packaging of EOs and their bioactive components is one of the important
approaches used by food industries to protect food items from microbial and toxic
metabolites contamination thereby maintaining their nutritional status (Coles et al.
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 23

2003). Utilization of essential oils through packaging provides protection against

three major classes of external factors, viz., chemical, physical, and biological.
Therefore, current researchers are focussing on modern delivery systems for encap-
sulation and release of essential oil vapors in a controlled manner. Since, food
industries are facing numerous challenges in developing healthy, safe, and environ-
mentally acceptable foods (Neethirajan and Jayas 2011), nanotechnology may be
exploited successfully as one of the important tools to improve production and pres-
ervation of food, for  extending shelf life (Roco 2002). Nanoencapsulation deals
with the reduction in size of the coating materials up to 1 μm having the bioactive
components enclosed in a tight matrix. The involvement of essential oil based nano-
technology for efficient food packaging supports the preservative potential in terms
of controlled release, greater surface area to volume ratio and optimized interaction
with food components. Another important point of food packaging is the selection
of suitable active packaging polymers, which do not interact with the organoleptic
properties of food  viz. flavor, color, taste and texture. The most commonly used
matrix materials for edible thin film packaging of food products are chitosan, gela-
tin, carrageenan, polylactic acid, and alginate. These edible films are commonly
developed by carbohydrates, proteins, or lipids acting as a barrier of oxygen, carbon
dioxide, and other soluble gases providing off-flavors and odors. Among different
polymeric matrices, montmorillonite (MMT) has been used by some workers due to
associated benefits of potential release of antimicrobial compounds and controlled
permeability of the gas and water vapor inside the packaging matrix (Fabra
et al. 2009).
Polymeric particles are generally of two types, i.e., nanocapsules and nano-
spheres. Incorporation of essential oils into the polymeric matrix provides signifi-
cant antimicrobial and antioxidant properties for control of microbial contamination
in the food products. Essential oils get conjugated with these polymeric materials
and constitute a biocompatible nanoparticle. The antimicrobial property of devel-
oped packaging  film greatly rely  over the  ratio of essential oil and polymeric
matrix utilized. Encapsulation of essential oil enhances effective concentration of
bioactive components in the food system especially in water-rich phases or solid-­
liquid interphases where microbial contamination occurs. For instance, nanoencap-
sulated terpenes and D-limonene showed significant efficacy against Lactobacillus
delbrueckii and Escherichia coli (Donsì et al. 2011). Gaysinsky et al. (2005) per-
formed nanoencapsulation of two important essential oil components eugenol and
carvacrol with different nano-based surfactant for enhancing antimicrobial efficacy
against pathogenic microbes. Citronellal, one of the major components of the
Eucalyptus citriodora essential oil encapsulated in chitosan matrix, has shown
­better antifungal, antioxidant, and insect repellant activity with significant distribu-
tion and polydispersity (Ribeiro et al. 2014). Encapsulation of Zataria multiflora
essential oil within chitosan nanoparticle significantly inhibited the growth and
sporulation of Botrytis cinerea in the storage condition at 4 °C (Mohammadi et al.
2015). Essential oil loaded nanoemulsion delivery system is widely acceptable for
practical application  being stable, transparent and colloidal in nature. The use of
oregano essential oil nanoemulsion with active preservative potential against
24 S. Das et al.

Listeria monocytogenes, Salmonella typhimurium, and Escherichia coli on fresh

lettuce has recently been reported by Bhargava et  al. (2015). Recent findings of
mandarin essential oil enclosed within modified chitosan-based coating for beans
have been investigated for large-scale future application (Severino et  al. 2014;
Donsì et al. 2015). The schematic representation of preparation and role of nanopar-
ticle-based delivery system in food industries is represented in Fig. 2.3.
There are different delivery systems used to achieve maximum oil concentration
and efficient antimicrobial activity in food system. The most common delivery sys-
tems are emulsions, suspensions, and liposomes which are colloidal particles asso-
ciated with essential oils as internal core materials, acting as good delivery system
with potential sustained release properties and significant activity against fungi and
other microbes (Gomes et al. 2011). Essential oil loading within different biopoly-
meric matrices following a variety of fabrication techniques, viz., interfacial polym-
erization, solvent evaporation, and emulsification, has been demonstrated to
maintain good quality and stability of nanoparticles in storage practices
(Akrachalanont 2008).

Fig. 2.3  Brief outline of synthesis and application of essential oil-based nanoparticles in food
sector
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 25

2.4  Mode of Action of Nanoparticles

Recently, there has been an increasing interest for the use of plant essential oils as
fungicide, bactericide, insecticides, and rodenticides to control fungal, bacterial,
and insect- and rodent-mediated deterioration of food items. However, volatile
nature of essential oils and physico-chemical degradation by abiotic factors limits
their long term application. Therefore, use of nano based delivery system may pro-
vide the efficient way to control the pests by involving different mode of action on
cells leading to cell lysis and subsequent death. The smaller size of nanoparticles
allows them to traverse within the cells culminating into loss of cellular activity.
Furthermore, the lipophilic chemical components of essential oils can also easily
cross the plasma membrane of fungi and insects and cause different enzymatic
alterations and biochemical dysfunction inside their body (Lee et  al. 2004).
Inhibition of fungal membrane ergosterol by different essential oils has been
actively reported by Tian et al. (2012). The active ingredients of essential oils can
be used as potent repellant, fumigant, antifeedant, and insecticidal agent. In gen-
eral, the terpenoids and phenolic components of essential oils target nervous sys-
tem of insect by interfering with functions of enzymes such as acetyl choline
esterase (AChE) or neurotransmitters such as octopamine and γ-aminobutyric acid
(GABA). In insects, the toxic effects on octopamine neurotransmitter, GABA gated
chloride channel and cytochrome P450 monooxygenase may ultimately cause hyper-
sensitivity, convulsions and paralysis of organs (Enan 2001). Besides their lipo-
philic nature, the bioactivity of essential oil also depends on different functional
groups (nature and position), volatility, and molecular weight of compounds.
Acetate-derived methyl groups and double-bonded benzene ring of eugenol, saf-
role, and limonene actively take part in knockdown of different enzymes and fumi-
gant toxicity of Spodoptera litura, Callosobruchus chinensis, Tribolium castaneum,
and other storage insects. Lower  solubility, higher  volatility and oxidation ten-
dency, are the major problem in practical application of essential oil for post har-
vest pest management. These problems may be effectively resolved to a greater
extent by nanoencapsulated essential oil-based pesticides (nanopesticides) or
nanoformulated essential oil. Christofoli et  al. (2015) reported on Zanthoxylum
rhombifolium essential oil loaded nanospheres against Bemisia tabaci. Silver
nanoparticles loaded with bioactive principles of Aristolochia indica showed maxi-
mum larvicidal, repellant, and cytotoxic effect on Helicoverpa armigera (Siva and
Kumar 2015). Lead and silver nanoparticle of Avicennia marina plant extract
exhibited prominent toxicity against Sitophilus oryzae (Sankar and Abideen 2015).
The list of chemical and biological nanoparticles used for broad management of
insect pests is described in Table 2.2.
26 S. Das et al.

Table 2.2  Important chemical and biological nanoparticles against fungi, bacteria, insects, and
rodents
Types of nanoparticles Targeted pests References
Silver nanoparticles Spodoptera litura and Achaea Yasur and Rani (2015)
janata
Zinc nanoparticle Aphis nerii Rouhani et al. (2012)
Silver nanoparticle Pseudomonas aeruginosa Salomoni et al. (2017)
Chitosan nanoparticle Spodoptera litura Chandra et al. (2013)
Silver nanoparticle with Helicoverpa armigera Siva and Kumar (2015)
Aristolochia indica
PEG-based garlic essential oil Tribolium castaneum Yang et al. (2009)
nanoparticle
Chitosan nanoparticle Callosobruchus maculatus Sahab et al. (2015)
Silver nanoparticle Sitophilus oryzae Zahir et al. (2012)
Illicium verum essential oil Aspergillus flavus and other storage Dwivedy et al. (2018)
loaded chitosan nanoparticle fungi and aflatoxin B1
Mentha piperita essential oil Aspergillus flavus Beyki et al. (2014)
loaded in chitosan-cinnamic acid
nanogel
Pectin/papaya puree/ Escherichia coli, Staphylococcus Otoni et al. (2014)
cinnamaldehyde nanoemulsion aureus, Listeria monocytogenes,
and Salmonella enterica
Clove/cinnamon loaded Bacillus subtilis, Salmonella Zhang et al. (2017)
nanoemulsion typhimurium, and Staphylococcus
aureus
Mustard oil microemulsion Escherichia coli Gaysinsky et al. (2008)
Eugenol loaded nanoemulsion Staphylococcus aureus Ghosh et al. (2014)
Encapsulated terpene mixture Lactobacillus delbrueckii, Donsì et al. (2011)
and D-limonene nanoemulsion Saccharomyces cerevisiae,
Escherichia coli
Santolina insularis essential oil Herpes simplex virus type-1 Valenti et al. (2001)
encapsulated with liposome

2.5  F
 actors Controlling the Stability of Nanoparticles
in Food System

The rising disciplines of nanotechnology and their applications in food and agricul-
tural industries are of major focus in the current generation. Varied applications of
nanotechnology are expanding rapidly with a multitude of potential factor for
nanoparticle stability and enhancement of food shelf life by maintaining the flavor
properties and ultimately improved nutritional value of food products during stor-
age (Chellaram et  al. 2014). Nanoencapsulation provides protection to bioactive
food ingredients by eradication of incompatibilities and masking the unpleasant
taste or odor. Besides having effective applications, there are some controlling fac-
tors which affect their physical and chemical stability.
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 27

2.5.1  Free Energy of Different Phases

Nonpolar interaction of lipophilic oil with hydrophilic component increases the

thermodynamic instability of nanoemulsion depending upon the free energy status
(Wooster et al. 2016). Therefore, changes in physical characteristics of nanoemul-
sions ultimately result in phase alteration (Chung and McClements 2018). Thus,
nanoemulsion characterization is a major aspect not only in the early stage but also
during long-term storage. Generally, storage practices occur in varied environmen-
tal conditions that may be quite useful to enhance the stability and activity of the
nanoemulsions. Furthermore, under certain conditions, nanoemulsions may become
unstable due to gravitational separations resulting primarily in the differences in
densities as observed by densitometric studies (Chung and McClements 2018).

2.5.2  Droplet Aggregation and Particle Size

Nano-sized droplets in emulsions are always in constant collision reaction because

of gravitational force, Brownian motion, and other mechanical forces (McClements
2015), favoring the aggregations of nano-droplets. Droplets may get associated with
each other without interfering their original size, and this process is known as floc-
culation. In addition, a number of nano-droplets may come across each other and
form a large droplet by the process known as coalescence.
However, for effective commercial applications, it is necessary to avoid nano-­
droplet aggregation as much as possible. For this, attractive forces, viz., hydropho-
bic and van der Waals forces, may be compensated by the repulsive forces, viz.,
electrostatic and steric actions between the nano-droplets. In addition, the decreased
nanoparticle size is correlated with reduction of nano-droplet aggregation (Degner
et al. 2014). According to McClements (2004), along homogenization, differences
in soluble phases and emulsifier concentration and types are the governing factors
regulating the size of the droplets. The stability of nanoencapsule suspension can
also be achieved by drying the nano-suspension (Nakagawa et al. 2011).

2.5.3  Emulsifier Type

The stability and size of nanoemulsion suspension formed after homogenization are
greatly influenced by the nature of emulsifier used. McClements (2004) studied
protein and lipid droplet interaction which are very much susceptible to changes in
ionic strength and pH as their major stabilization by repulsing forces. In contrast to
this, Qian et al. (2011) have described the coating of lipid droplets into polysaccha-
ride and non-ionic surfactants that are not much susceptible to these parameters
such as steric repulsion.
28 S. Das et al.

2.5.4  Ionic Strength and pH

Ionic strength and pH of aqueous phase are two other key factors which have lead-
ing impact over stability as well as properties of nanoemulsion by influencing their
electrostatic interactions. Ionic concentration and its type present in the aqueous
phase can influence the strength of electrostatic interactions by influencing the
effect of ion binding, ion bridging, and electrostatic screening. Besides ionic con-
centration, pH of nano-suspension also has considerable impact over strength of
electrostatic interactions depending on charge potential on nanoparticle surface
(McClements 2004).
Nanoparticles consisting of protein-coated fat droplets have strong affinity
toward flocculation when ionic strength of nano-suspension exceeds beyond a cer-
tain level because of electrostatic screening and ion binding effects (De La Fuente
et al. 1998). Moreover, addition of salt to the nanoemulsion prior to or after homog-
enization may influence the stability and aggregation of nanoparticles (Kim et al.
2005). Similar effects are also observed when pH value of nanoemulsion is near to
their isoelectric point (Demetriades and McClements 1998). As mentioned above,
ionic strength and pH value of nano-suspension influence the aggregation and sta-
bility of nano-droplets. Besides this, some other properties like texture of emulsion
and their optical properties may also get affected.

2.5.5  Thermal Processing

Thermal processing is another factor that governs nanoemulsion stability by influ-

encing the droplet aggregation over and above visual and textural properties of
nano-suspension. Croguennec et  al. (2004) have reported that adsorbed globular
proteins may experience an irreversible change in their structure and chemical reac-
tivity on heating beyond their thermal denaturation. Moreover, Donato et al. (2007)
have reported the formation of protein aggregates after heat treatments.

2.6  N
 anoparticles as Active Biosensor for Detection of Food
Contaminants (Chemicals and Food-Borne Pathogens)

A sensor is a measurement system consisting of specific probe to detect particular

species or element at trace levels. Biosensor have been used for detection of differ-
ent biological organisms such as viruses, bacteria, proteins, nucleic acids and patho-
gens (Pérez-López and Merkoçi 2011). Biosensors contain a bioreceptor and
transducer which interact with specific analyte molecule, generating an electrical
signal. Bioreceptor consists of living systems viz. cells, tissue, enzymes, proteins,
nucleic acids and antibodies which are utilized for the biochemical adhesion prop-
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 29

erty. Nowadays, nanobiosensing technology is being utilized in food safety analysis

to detect various sensitive contaminants in food materials. A nanobiosensor is also
called as a second-generation biosensor due to the involvement of ultrasensitive
nanoparticles and their effective transducers (Sagadevan and Periasamy 2014). The
major advantages of using nanomaterials in biosensing are the combined effect on
biological receptor molecules and higher surface to volume ratio (Kumar et  al.
2012). Among different synthesized nanoparticles, metal nanoparticles, carbon
nanoparticles, semiconductor quantum nanoparticles, and magnetic nanoparticles
have been used for detection of food allergens. Metal nanoparticles, basically col-
loidal gold, have been successfully used in DNA biosensing based on their amount
of immobilized biomolecules in an active sensor (Cai et al. 2002). There are differ-
ent types of nanotubes, viz., one-dimensional nanostructures (1-D), nanotubes with
single or multichannel carbon tape, and carbon nanowires, based on the conducting
polymer and biochemical reaction routes. The organic nanosensors have been
actively applied for detection of organophosphate pesticide contamination in fruits
and other stored products as well as their solubility and residual toxicity in different
food products. Interestingly these nanobiosensors have marked advancement for
detection of mycotoxins and different mycotoxigenic fungi in different food prod-
ucts (Li et al. 2012). Aflatoxin contamination can be measured on pre-harvested and
post-harvested food products at a very low concentration, i.e., 0.3 pg/mL by differ-
ent nanocomposites (Gan et al. 2013). Yotova et al. (2013) have developed a nano-
sensor with modified tyrosinase enzyme for detection of toxigenic fungi. Gold
nanorods (GNRs) have active sensing capacity for AFB1 detection up to 0.04 ppb in
food samples (Xu et al. 2013). Modified gold nanoparticles with electrochemilumi-
nescent aptamers have been used for detection of ochratoxin A. AF-oxidase enzyme
linked with modified carbon nanotubes and poly-o-phenylenediamine integrated
with gold electrode has the ability to detect sterigmatocystin concentration up to
3 ng/mL (Chen et al. 2009). Similarly, immuno-chromatographic biosensors with
attached monoclonal antibodies have been used for rapid detection of zearalenone
in corn samples (Shim et al. 2009). Maragos (2012) has developed colloidal gold
nanoparticles with interferometry principle for detection of deoxynivalenol in wheat.

2.7  Application of Nanoparticles in Different Food Sectors

In today’s world, the applications of nanoscience and nanotechnology in food mate-

rials have contributed a major status for nutrition and health of consumers. Most of
the nanoparticles are colloidal in nature, and stability is achieved by van der Waals
forces and steric stabilization provided by core materials and adsorbing matrix
polymers. In the food industry, nanotechnology have both “top-down” and “bottom-
­up” approaches with smart delivery of nutrients and proteins, rapid identification of
contaminants, and encapsulation of essential oil with adsorbing matrices (Verma
et  al. 2009). Globally, the overall sales of nanotechnology products have been
observed to increase from US$ 150 million to US$ 860 million in between 2002 and
30 S. Das et al.

2004. Application of essential oil in food matrices as biopreservatives and natural

antioxidant is one of the most important aspects in the current generation. This rap-
idly developing encapsulation technology have an ultimate focus on food process-
ing, packaging, transportation, shelf life enhancement, and bioavailability of
nutrient compounds. The microencapsulated essential oils having antimicrobial
agents are used in efficient smart packaging, an effective approach in food indus-
tries (de Barros Fernandes et al. 2014). Use of nanoparticles for the improvement of
food processing involves different biological aspects such as effective preservative
potential, targeted and controlled release of bioactive components, high absorption
rate related to greater surface area, high availability, and improved organoleptic
properties. Active antimicrobial effect, improved barrier properties and biosensing
properties have been applied in nanopackaging of food materials. The active use of
nanosensors for pathogenic microbes and toxin detection in stored foods is an
important aspect of nanotechnology during transportation. Nanoparticles are effi-
cient due to selective binding and easy removal of pathogens from food surface
(Duncan 2011). Industrial application of encapsulated essential oil in food systems
is a very limited approach until now. Wu et al. (2012) have reported efficient antimi-
crobial property of zein nanoparticle loaded with thymol and carvacrol without
affecting organoleptic properties of food commodities. Nano-formulation of
Artemisia arborescens essential oil with solid lipid nanoparticles allowed controlled
release of vapor and served as an efficient ecological pesticide (Lai et al. 2006). A
number of essential oils and their bioactive components have been incorporated into
edible film exhibiting better efficacy against food-borne pests and pathogens. Khalili
et al. (2015) confirmed potential efficacy of thyme essential oil encapsulated within
chitosan-benzoic acid nanogel against growth and aflatoxin secretion by Aspergillus
flavus in stored foods. Hence efficient food packaging, formulation, and delivery
can be assisted by several compatible nanomaterials. A comprehensive diagram rep-
resenting the application of nanoparticles in different food sector is shown in
Fig. 2.4.

2.8  S
 afety Issues Associated with Application
of Nanotechnology in Food Packaging/Food Preservation

Before discussing the possible consequences of nanomaterial ingestion via food, it

is very important to recall that our food naturally comprises of several nanorange
components. Several forms of biopolymers such as proteins, carbohydrates, and fats
are  present in the  nanorange in  variety of food items (Magnuson et  al. 2011;
Cockburn et  al. 2012). Even the digestive processes (mechanical/chemical)
­performed in the gastrointestinal tract leads to the conversion of complex food
structures into simple forms of mono−/disaccharides, fatty acids, or amino acids/
peptides, which can be included under nano−/micro-material range (Martirosyan
and Schneider 2014). Such nanomaterials formed in the gastrointestinal tract are
subjected to absorption or translocation into the blood/lymph through the gut epi-
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 31

Fig. 2.4  Application of nanoparticles in different food sectors

thelia (Powell et al. 2010). Thus, it should be made clear that the gut lumen and
epithelia are well exposed to various nanomaterials ingested orally via food.
The major concern of nanomaterial usage in food packaging is “leaching out” of
active ingredients from the packaging materials into the food items. The incorpora-
tion of nanomaterials in the food as stabilizers, anticaking agents, in order to
improve the shelf life, odour, taste and aroma, will also increase the chances of oral
entrance (Laloux et al. 2017). In this context, there are several issues, most impor-
tantly the very small size of nanomaterials favoring the greater absorption through
the intestinal/gut epithelia (Martirosyan and Schneider 2014). If there is a possibil-
ity of internalization and retention in cells or tissues, the nanomaterials could enter
into the food chain. After entry, the nanomaterials may get coated with lipids/pro-
teins as such forming a “corona” which facilitates the absorption, thus making the
nanomaterial biofunctional (Bellmann et al. 2015). This corona stage is not stable
and is subjected to alterations under changing macromolecules and environmental
conditions it encounters. This property complicates the expected behavior of nano-
materials as well as the absorption/metabolic profile of food components inside the
gastrointestinal tract. Such unknown effects associated with the nanomaterial
behavior inside the gut have been termed as the “Trojan horse effect” (Park et al.
32 S. Das et al.

Nanomaterial
Ingestion ‘Nanomaterial
Lipid/Protein Corona’

Fate in gastrointestinal tract

1
Excretion through
faeces 2 Lumen
Gastrointestinal tract

Selective barrier
Absorption and translocation Mucous
epithelia

Blood/Lymph

Possible consequences

Cytotoxicity Genotoxicity

Oxidative imbalance
1= First possibility
2= Second possibility
Inflammation
Fig. 2.5  The fate and possible effects of nanomaterial ingestion

2010; Souza et al. 2018). The fate and the potential consequences of nanomaterial
ingestion via food have been represented in Fig. 2.5.
The gastrointestinal tract has a mucous layering which functions as mechanical
barrier to foreign particles entering the tract. The nanomaterial may get excreted via
feces if not allowed to pass through the epithelia. However, if it gets absorbed/trans-
located into the blood/lymph, it has the passage to stream through different com-
partments of the body (Bellmann et al. 2015). The consequences of nanomaterial
acquisition in different body parts have been demonstrated in vitro (Owens III and
Peppas 2006; Corbalan-Penas 2010; Athinarayanan et al. 2014). Factors governing
the fate of nanomaterials inside the body include dose, particle size, shape, charge,
solubility, reactivity, and surface coating. The lipid bilayer of the cell membrane has
been speculated as the primary target of nanorange materials. Pores formed in the
membrane due to nanomaterials lead to cytotoxicity. The nanomaterials have been
shown to induce ROS (reactive oxygen species) and RNS (reactive nitrogen species;
nitrosative stress) production (Athinarayanan et al. 2014). The oxidative imbalance
2  Nanoencapsulation Technology: Boon to Food Packaging Industries 33

inside the cell has also been shown to activate the pro-inflammatory cytokines and
inflammasome-mediated inflammation (Dankovic et  al. 2007; Moos et  al. 2011).
Genotoxicity induced by nanomaterial interaction could result in direct interaction
with genomic DNA or indirectly through ROS generation (Singh et al. 2017).
In conclusion, it is essential to perform safety assessment of nanomaterials
before their application in food packaging or processing. Cockburn et  al. (2012)
have provided a five-step systematic approach in this connection. Therefore, d­ efinite
description as well as the comprehensive characterization of the nanomaterials is
vital, followed by risk evaluation through utilization of “decision tree,” whether the
properties favor the need of detailed investigations on toxicological testing or not.

2.9  Future Prospective

In the recent past, there is an increasing interest toward the use and incorporation of
nanometric structures in food industries for active packaging, processing, or preser-
vation of quality. Therefore, the scientific community has focused greatly on the
development of nanoscale materials that could fulfill changing world food demands.
Nanobiotechnology in food packaging has immense potential to preserve food qual-
ity and nutritional profile by serving as antimicrobials and barriers against UV rays,
gas, and moisture. To date, various methods have been proposed to encapsulate the
bioactive compounds in an array of nano-vehicles to facilitate the stability as well
as efficacy. Although research toward nanopackaging has gained momentum, still a
lot of questions remained unanswered regarding their fate in the biological systems,
environmental impacts, consumer acceptance, effects over sensory profile, and the
cost to benefit ratio. Moreover, consumers face hesitation in accepting the incorpo-
ration of nanotechnology in the food system. Nanosensors incorporated in plastic
packaging could be very much effective against detection of food contamination
and spoilage (Thiruvengadam et al. 2018). Rigorous research over safety evaluation
together with efforts for increasing the consumer’s acceptance should be in priority
to further explore the application of nanotechnology in food industries.

Acknowledgments  SD and AKC are thankful to the Council of Scientific and Industrial Research
(CSIR), New Delhi, for providing research fellowship. Authors are thankful to the Head, CAS in
Botany and DST-FIST, Banaras Hindu University, for laboratory facilities.

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Chapter 3
Ecotoxicity of Metallic Nanoparticles
and Possible Strategies for Risk
Assessment

Ifra Zoomi, Harbans Kaur Kehri, Ovaid Akhtar, Dheeraj Pandey,

Pragya Srivastava, and Raghvendra Pratap Narayan

3.1  Introduction

Nanoparticles are defined as particulate matter, usually with nanoscale dimensions

(1–100 nm), whose properties are diverse from their bulk form (Auffan et al. 2009).
Various distinctive properties of nanoparticles such as electronic (Kim et al. 2007),
optical/photonic (Chan et  al. 2013), magnetic (Mornet et  al. 2006), and catalytic
(Nasrollahzadeh et al. 2015) have significant roles in daily human life. Fundamentally,
nanoparticles are categorized in two groups: (i) carbon-containing nanoparticles
and (ii) metal-containing nanoparticles. Carbon-containing nanoparticles are made
of carbon nanotubes and fullerenes. However, most of the metal-containing nanopar-
ticles are made from metals such as gold (Au), iron (Fe), silver (Ag), copper (Cu),
and metal oxides such as titanium dioxide (TiO2), antimony oxide (Sb2O3), cerium
dioxide (CeO2), copper oxide (CuO), nickel oxide (NiO), iron oxide (FeO), and zinc
oxide (ZnO).
Metallic nanoparticles are important because of their physical, chemical, and
optoelectronic properties. Metallic nanoparticles have been used in various products
with different purposes, such as sensors (Li et al. 2007), as catalysts in various pro-
cesses (Carnes and Klabunde 2003), drug delivery (Hola et al. 2015), sunscreens
(Gulson et al. 2015), solar-driven energy production (Sau et al. 2010), and in pollutant
remediation (Kamat and Meisel 2003; Choopun et al. 2009; Raman and Kanmani

I. Zoomi · H. K. Kehri · D. Pandey · P. Srivastava

Sadasivan Myco-pathology Laboratory, Department of Botany,
University of Allahabad, Allahabad, India
O. Akhtar
Department of Botany, Kamla Nehru Institute of Physical and Social Sciences,
Sultanpur, India
R. P. Narayan (*)
Netaji Subhash Chandra Bose Government Girls P.G. College, Lucknow, India

© Springer Nature Switzerland AG 2020 41

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_3
42 I. Zoomi et al.

2016). Additionally, nanoparticles have been shown to inhibit microorganism

growth by exhibiting antibacterial, antiviral, and antifungal properties (Padmavathy
and Vijayaraghavan 2008; Khatami et al. 2015; Rai et al. 2016). As metallic nanopar-
ticles are widely used, their exposure is likely to increase substantially, and they
interact negatively with microorganisms, green plants, animals, human beings, and
their surrounding environment (Navarro et al. 2008; Wise et al. 2010; Singh et al.
2016, 2019; Shweta et al. 2017, 2018; Arif et al. 2018; Vishwakarma et al. 2018).
Therefore, detailed understanding of their synthesis, interaction, and possible risk
valuation would offer a foundation for harmless use of nanoparticles.

3.2  Synthesis of Metallic Nanoparticles

Synthesis of metallic nanoparticles is a timely area of research because their use is

widespread. Various physical and chemical methods are used for the production of
metallic nanoparticles (Tripathi et al. 2017; Koul et al. 2018). For the synthesis of
metal oxide nanoparticles, stabilized precipitation and flame pyrolysis are com-
monly used methods (Christian et al. 2008). Monodisperse nickel phosphide (Ni2P)
nanorods and nanoparticles are made by a one-step solution-phase route (Li et al.
2015). Moreover, there is growing interest in the controlled synthesis of metallic
nanoparticles (Wiley et  al. 2005; Xia et  al. 2009). However, these methods have
certain drawbacks because of the use of poisonous chemicals and radiation and are
an expensive process. Therefore, academic research is shifting toward biological
synthesis of metallic nanoparticles, as it is rapid, feasible, and more productive rela-
tive to its cost. In this context, microorganisms have an increasingly critical role as
they can provide inorganic materials either intra- or extracellularly for the synthesis
of nanoparticles (Simkiss and Wilbur 1989; Mann 1996). Numerous microorganisms
such as bacteria (Shahverdi et al. 2007; Saifuddin et al. 2009; Pantidos and Horsfall
2014), actinomycetes (Abdeen et al. 2014; Golinska et al. 2014), algae (Singaravelu
et al. 2007; Aruoja et al. 2009; Abboud et al. 2014), and fungi (Mukherjee et al.
2001; Ahmad et al. 2003; Yadav et al. 2015) are used for nanoparticle synthesis.
Also, peptides (Tomczak et al. 2007), starches (Kumar et al. 2014), and almost all
parts of plants have been used for the synthesis of metallic nanoparticles.

3.3  Application of Nanoparticles

Nowadays, metal-based nanoparticles have become one of the main and increasing
aims of nanotechnology, as these particles are usually used in cosmetics, antibacterial
agents, tires, stain-resistant clothing, optic devices, toothpaste, sensors, food addi-
tives, and data storage (Fig. 3.1).
3  Ecotoxicity of Metallic Nanoparticles and Possible Strategies for Risk Assessment 43

Bulk matter

Physical/Chemical/Biological Synthesis
of Nanoparticles

Nanoparticles

Antimicrobial Application of Metallic Remediation of

agent Nanoparticles pollutant

Use in Use in
cosmetics sensor

Photo- Use in
imaging fabrics
Drug delivery and
its monitering

Fig. 3.1  Application of metallic nanoparticles

As antibacterial agents, these particles are widely used in medical applications,

food storage, and water treatment (Bosetti et al. 2002; Cho et al. 2005; Singh et al.
2008; Espitia et al. 2012). In the textile industry, silver nanoparticles are used to
prepare cotton fibers that exhibit antibacterial activity (Durán et  al. 2007). It has
been reported that Ag or Au nanoparticles extracellularly produced from Fusarium
oxysporum can be used to prevent or to reduce the infection of Staphylococcus
aureus (Durán et al. 2007). Moreover, metallic nanoparticles are of great scientific
importance regarding their catalytic activity in various metal-based reactions
(Hvolbæk et al. 2007). Metallic nanoparticles also show superior catalytic activity
in the reduction and removal of dye. For instance, gold nanoparticles are reported to
catalyze the reduction of dye in the presence of stannous chloride (Gupta et  al.
2010). Silver and gold nanoclusters were reported to catalyze the reduction of meth-
ylene blue dye (C16H18ClN3S) by arsine in micellar medium (Kundu et al. 2002).
Köhler et al. (2008) reported that the catalytic activities of nanoparticles enhanced
the bleaching of the organic dyes. However, catalytic activity of metallic nanopar-
ticles also varies from metal to metal. For instance, the Ag nanoparticle was found
to be superior to Au and Pt colloid in catalyzing chemiluminescence from the
luminol–hydrogen peroxide system (Guo et al. 2008). Despite the aforementioned
antibacterial and catalytic activity of metallic nanoparticles, the optical properties of
44 I. Zoomi et al.

a metallic nanoparticle also offer a manageable tool for particle sorting and sensing,
for instance, in optoelectronic devices (Djurišić et al. 2010; Choi et al. 2013) and in
sensing devices (Ankamwar et al. 2005).
In the medical field, metallic nanoparticles are used to develop an aggregation-­
based immunoassay for anti-protein A (Thanh and Rosenzweig 2002), and for treat-
ment of B-chronic lymphocytic leukemia (Mukherjee et al. 2007) and oral cancer
(El-Sayed et al. 2005).
Nanoparticles have also found application in remediation of contaminated envi-
ronments (Li et al. 2006). There are several studies on the application of nanopar-
ticles for remediation of various pollutants such as metals, organic pollutants, and
dyes (Mak and Chen 2004; Hoch et al. 2008; Cheng et al. 2013; Zhao et al. 2016).
However, as the benefit obtained from the intended use of nanoparticles for reme-
diation is balanced by potential risk, it is therefore obligatory to assess the probable
environmental risk.

3.4  Toxicity of Metallic Nanoparticles

The toxicity of nanoparticles is principally the result of their small size, their large
surface area compared to volume, and reactive facets. Metallic nanoparticles show
toxic effects on various organisms (Table 3.1). Ge et al. (2011) reported that TiO2
and ZnO nanoparticles reduced the biomass of a microbial community. Among
microbial communities, nitrogen-fixing bacteria are an important component of the
soil ecosystem as they maintain soil health and fertility. Cherchi et  al. (2011)
reported bactericidal effects of TiO2 nanoparticles in Anabaena variabilis. Toxicity
of nanometal oxides in aquatic ecosystems has also been studied by various research
groups (Blaise et al. 2008; Lee et al. 2009; Pradhan et al. 2012; Miller et al. 2012).
Federici et al. (2007) reported that the gills of Oncorhynchus mykiss showed sensi-
tivity toward TiO2 nanoparticles. Furthermore, TiO2 nanoparticles were reported to
inhibit the growth of Desmodesmus subspicatus at higher concentrations (Hund-­
Rinke and Simon 2006). However, the toxicity of metallic nano-sized particles in an
aquatic ecosystem is debatable (Sharma 2009) as their physicochemical properties
are dissimilar from their ionic and bulk form (Christian et al. 2008). Moreover, sol-
uble ions released from metallic nanoparticles appear be the main cause of ecotox-
icity (Aruoja et al. 2009). Green plants are also affected by metallic nanoparticles as
these particles enter into the plant by various means such as stomata, cuts or wounds,
and through the roots. Zn and ZnO nanoparticles negatively affect the growth of
Raphanus sativus (radish), Brassica napus (rape), and Lolium perenne (ryegrass)
(Lin and Xing 2007). Similarly, Yang and Watts (2005) reported the toxicity of alu-
mina nanoparticles in Brassica oleracea (cabbage), Daucus carota (carrot), Zea
mays (corn), Cucumis sativus (cucumber), and Glycine max (soybean). Metallic
nanoparticles are known to induce effects on human health, as they cause gastro-
duodenal corrosive injury (Liu et al. 2004), a cytotoxic effect on glomerular and
3  Ecotoxicity of Metallic Nanoparticles and Possible Strategies for Risk Assessment 45

Table 3.1  Toxic effect of metallic nanoparticles on organisms

Nanoparticles Organisms Effects References
TiO2 Daphnia magna Bioaccumulation may interfere with food Zhu et al.
nanoparticles intake and ultimately affect growth and (2010)
reproduction
TiO2 Daphnia magna Caused mortality Lovern and
nanoparticles Klaper
(2006)
ZnO and TiO2 Escherichia coli Induced oxidative stress and DNA damage Kumar et al.
nanoparticles leading to reduced viability of E. coli (2011a)
ZnO and TiO2 Salmonella Both ZnO and TiO2 nanoparticles were Kumar et al.
nanoparticles typhimurium significantly internalized in the (2011b)
S. typhimurium cells in a concentration-­
dependent manner and these nanoparticles
exhibited weak mutagenic potential
Ag Bacteria Ag nanoparticles inhibited soil-denitrifying Throbäck
nanoparticles bacteria et al. (2007)
Ag Bacteria Inhibited the nitrifying organisms Choi et al.
nanoparticles (2008)
TiO2 and ZnO Bacteria TiO2 and ZnO nanoparticles reduced both Ge et al.
nanoparticles microbial biomass, bacterial diversity, and (2011)
composition
CuO, NiO, Escherichia coli, Toxic to microorganisms: toxicity order Baek and An
ZnO, and Bacillus subtilis, was CuO > ZnO > NiO > Sb2O3 (2011)
Sb2O3 and Streptococcus nanoparticles
nanoparticles aureus
CeO2 Synechocystis E. coli was sensitive to the ‘direct’ effects Thill et al.
nanoparticles PCC6803 and of nanoparticles, whereas Synechocystis (2006)
Escherichia coli was protected by extracellular polymeric
substances, preventing direct cellular
contacts
Ag Zebrafish Induced oxidative stress and apoptosis Choi et al.
nanoparticles (2010)
Au Phytoplanktonic Mortality was 20% at lowest contamination Renault et al.
nanoparticles alga (Scenedesmus condition; the highest reached 50% in (2008)
subspicatus) and a algae. Au nanoparticles were adsorbed by
benthic bivalve the algal cell wall, leading to progressive
(Corbicula intracellular and wall disturbances. In
fluminea) bivalves these nanoparticles
bioaccumulated and penetrated into the
gills and digestive epithelia to cause
oxidative stress
Ag Mytilus edulis Au nanoparticles accumulated in digestive Tedesco et al.
nanoparticles gland causing oxidative stress (2010)

tubular renal cells (Pujalté et al. 2011), and toxic effects on the pulmonary system
(Moos et al. 2010). Karlsson et al. (2009) assessed the effect of metallic n­ anoparticles
on human cell lines and reported that nanoparticles are perhaps more toxic than
their bulk forms.
46 I. Zoomi et al.

3.4.1  Uptake of Metallic Nanoparticles

The detailed mechanisms of biological uptake of metallic nanoparticles are not well
known. However, it has been hypothesized that uptake of nanoparticles in animal
bodies takes place through the gut (Baun et al. 2008) by various mechanisms such
as diffusion through cell membranes, via endocytosis and adhesion (Geiser et al.
2005; Kim et al. 2007). In other biotic components (plants, algae, fungi) the cell
wall restricted the entry of nanoparticles as it acts as a barrier. However, small-sized
nanoparticles enter the cell via the pores in the cell wall (Zemke-White et al. 2000),
and further interaction of these small-sized nanoparticles with the cell wall might
increase the pore size, resulting in the internalization of large-sized nanoparticles
(Navarro et al. 2008). After passing through the cell wall, endocytosis takes place
(Navarro et al. 2008), and inside the cell nanoparticles bind with various cellular
structures, thereby inhibiting cellular activity or damaging the cell organelles. Plants
interact more frequently with nanoparticles by the presence of stomata, cuts or
wounds, and the large surface area of leaf and roots (Navarro et al. 2008).

3.4.2  Mode of Action of Nanoparticles

Internalized metallic nanoparticles inside the cell interfere with several biological
mechanisms, such as causing disruption of the membrane potential, and destabiliza-
tion and oxidation of protein, and affect the stability of nucleic acid, stimulate the
production of free radical species called reactive oxygen species (ROS), disrupting
energy flow and releasing toxic compounds (Klaine et al. 2008). Gold nanoparticles
have been reported to puncture the cell membrane (Tsao et al. 1999) and alter the
cell shape and enzymatic activity (Liu et al. 2004).
Metallic nanoparticles also generate oxidative stress in biological systems by the
production of ROS. ROS disrupt the influx and efflux of electrons and ions, disrupt
membrane permeability, and reduce glutathione content inside the cell (Limbach
et  al. 2007). ROS increase the permeability of cell membrane by oxidization of
double bonds of fatty acids. It has also been reported that TiO2 nanoparticles have
photocatalyst properties (Khus et al. 2006) and, with exposure to ultraviolet radia-
tion (Zhao et al. 2007) produce ROS thereby causing DNA damage. Photosensitive
silver nanoparticles have been shown to break the double-stranded DNA upon expo-
sure of to UV light (Badireddy et  al. 2007). It has also been reported that CeO2
nanoparticles cause oxidation of membrane-bound complexes of respiratory elec-
tron transport chain (Thill et  al. 2006). Moreover, quantum dots cause oxidative
destruction (Hardman 2006), and heavy metals or metal ions released from quantum
dots are toxic to the living cells (Klaine et al. 2008). Silver ions discharged from the
metallic nanoparticles interact with functional thiol groups (derived from the cyste-
ine residues) of enzymes (Matsumura et  al. 2003) and inhibit the respiratory
enzymes (Kim et al. 2007).
3  Ecotoxicity of Metallic Nanoparticles and Possible Strategies for Risk Assessment 47

3.5  Ecotoxicology Assessment and Possible Strategies

According to the U. S. Environmental Protection Agency (EPA), “risk is a measure

of the probability that cause damage to life, health, property, and/or the environ-
ment.” Before assessing the biotic hazard, it is desirable to assess the physical and
chemical properties of nanoparticles. The various techniques for analysis and char-
acterization of metallic nanoparticles include membrane filtration (Akthakul et al.
2005; Howell et al. 2006), size-exclusion chromatography (Wang et al. 2006), and
photon correlation spectroscopy, used to determine the size and sometimes the
shape of metallic nanoparticles (Chrastina and Schnitzer 2010). Additionally, trans-
mission electron microscopy (TEM) (Jose-Yacaman et  al. 2001; Chrastina and
Schnitzer 2010), the scanning electron microscope (SEM) (Rai et  al. 2009), and
atomic force microscopy (AFM) (Viguie et al. 2007) are used to gather evidence
about the configuration, arrangement, charges, and force of nanoparticles. The com-
plex arrangement of crystal metallic nanoparticles can be resolved by X-ray diffrac-
tion (XRD) and energy-dispersive X-ray (EDX) techniques (Rai et  al. 2009).
However, it is difficult to analyze the properties of nanoparticles because their con-
centration in the environment is below the detection limit and test samples also
carry unwanted nanoparticles (Lead and Wilkinson 2006). After the analysis and
characterization of metallic nanoparticles, standard toxicity tests on organisms are
used to assess the impacts of nanoparticles. For aquatic threat evaluation, an algal
growth inhibition assay is commonly used, and Pseudokirchneriella subcapitata is
an ideal organism for envisaging lethal threats to primary producers (Aruoja et al.
2009). Toxicological effects of metallic nanoparticles on diverse algal species, such
as Chlamydomonas reinhardtii (Navarro et  al. 2008; Chen et  al. 2012; Melegari
et al. 2013), Desmodesmus subspicatus (Hartmann et al. 2010), Dunaliella tertio-
lecta, and Chlorella vulgaris (Oukarroum et al. 2012), have also been studied. Also,
Vibrio fischeri, a naturally luminescent bacterium, is widely used for ecotoxicologi-
cal studies, and the bacterial luminescence inhibition assay is economical and easy
to perform (Mortimer et al. 2008). There are various aspects for understanding the
risk assessment of nanoparticles, such as dose of nanoparticles, exposure time, and
endpoint measurement. Furthermore, short- and long-term laboratory experiments
and development of a coordinated approach are still needed for assessing the
toxicity.

3.6  Conclusions

Because of the wide application of metallic nanoparticles, their unintentional release

and exposure pose a serious hazard to organisms and their environments. Only a few
areas have been covered for the assessment and testing of the hazardous effects of
metallic nanoparticles. Therefore, there is a requirement for data on the long-term
effects of metallic nanoparticles, in  vivo interactions of metallic nanoparticles,
48 I. Zoomi et al.

applied methods, databases of well-established toxicity tests, and the establishment

of testing guidelines to enhance the transparency and comparability of obtained data.

Acknowledgments The authors thank the Head of the Botany Department, University of

Allahabad, Allahabad, for providing the necessary facilities, and are also grateful to UGC and CSIR
for providing financial support to Ifra Zoomi, Pragya Srivastava, Dheeraj Pandey, and Ovaid Akhtar.

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Chapter 4
Tripartite Interaction Among
Nanoparticles, Symbiotic Microbes,
and Plants: Current Scenario and Future
Perspectives

Ovaid Akhtar, Ifra Zoomi, Dheeraj Pandey, Harbans Kaur Kehri,

and Raghvendra Pratap Narayan

Abbreviations

AM Arbuscular mycorrhiza
CNT Carbon nanotubes
DOC Dissolved organic carbon
GRSPs Glomalin-related soil proteins
MWCNTs Multi-walled carbon nanotubes
NP Nanoparticles
ROS Reactive oxygen species

4.1  Introduction

Nanoparticles (NPs) are defined as the particles with a size of 1–100 nm in diameter
(Auffan et al. 2009). Because of their high surface-to-volume ratio, they are very
reactive. They can pass even through the cell membrane. These fascinating charac-
teristics make them unique and hence, overwhelming researches have been carried
out to explore their possible roles in biotechnology and agriculture production
(Singh et al. 2016; Mishra et al. 2017; Shweta et al. 2017, 2018; Arif et al. 2018;

O. Akhtar
Department of Botany, Kamla Nehru Institute of Physical and Social Sciences,
Sultanpur, India
I. Zoomi · D. Pandey · H. K. Kehri
Sadasivan Mycopathology Laboratory, Department of Botany, University of Allahabad,
Allahabad, India
R. P. Narayan (*)
Netaji Subhash Chandra Bose Government Girls P.G. College, Lucknow, India

© Springer Nature Switzerland AG 2020 55

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_4
56 O. Akhtar et al.

Vishwakarma et al. 2018; Kehri et al. 2019; Rastogi et al. 2019a, b; Singh et al.
2019). NPs have promising application in the field of nanofertilizer, nanopesticide,
nanoherbicide, nanosensor and as a delivery system for the sustained release of
agrochemicals (Mishra et al. 2017; Koul et al. 2018; Singh et al. 2018; Tripathi et al.
2018; Vishwakarma et al. 2018). It was of thought that NPs could be used for boosting
the agricultural economic growth in the near future (Sabourin and Ayande 2015).
But, unregulated use of NPs has threw the ecosystems at the brink of risk caused by
toxicity of these NPs (Hong et al. 2014). Although NPs have gained the rapid attention
of plant scientists during the recent few years, their fates in relation to sustainable
agriculture are still unexplored.
Despite of achievements in the field of NPs in agronomy, their role is still in a
topsy-turvy stage (Yang et al. 2017). Different types of plants behave NPs differ-
ently. Also, same plant behaves different NPs differently. The response of NPs on
plants as well as microbes depends upon the nature and concentration of NPs, nature
of coating material, nature of growth media, mode of application, part of the plants,
and even stage of plant development (Yang et al. 2017). As most of the NPs are
made up of heavy metals, their elevated concentration in the biological systems
could be detrimental to both aboveground and belowground flora as well.
Yang et al. (2017) have concluded the interaction of NPs with plants and microbes
in their review. They have discussed pros and cons of NPs in details. But unfortu-
nately, no conclusion could be established about the effect of NPs on symbioses in
plants. In this chapter, extensive literature mining has been carried out to collect all
the reports on interactions where effects of NPs have been studied on plants in rela-
tion to the symbiotic bacteria and/or fungi. Although there are very limited reports
on tripartite interaction, it has been tried to find out the nature of interaction. Also,
the possible mechanism behind these interactions is elucidated with the help of
artwork. Eventually, this chapter puts forward the future perspectives and direction
of research to study the behavior of NPs with reference to plant-microbe symbioses
in greater depth.

4.2  Nanoparticles Versus Plant Growth

First stage of NP and plant interaction is the uptake of NPs inside the plant cell.
Usually, plants can accumulate NPs of 40–50 nm dimension (Sabo-Attwood et al.
2012; Taylor et al. 2014). Besides the size, morphology, chemical nature, and coat-
ing properties play crucial roles in the absorption of NPs in plants (Raliya et al. 2016).
After absorption of NPs through roots, they follow either apoplastic pathway
(extracellular spaces and xylem vessels) or symplastic pathway (across the living
cell and through plasmodesmata). On foliar application, most of NPs are absorbed
through the stomata (Pérez-de-Luque 2017). After absorption NPs are transported
to the sink and internalized into the cell by pore formation, carrier proteins, and
plasmodesmata or through the ion channels (Pérez-de-Luque 2017).
4  Tripartite Interaction Among Nanoparticles, Symbiotic Microbes, and Plants… 57

Fe3O4, TiO2, and carbon NPs were reported to inhibit the seed germination rate,
root elongation, and germination index in cucumber plant (Mushtaq 2011). Cu NPs
were found inhibitory on emerging root length, and Ag NPs decreased the plant
biomass and transpiration (Stampoulis et  al. 2009). ZnO NPs caused cytotoxic
(lipid peroxidation) and genotoxic effects (decreasing mitotic index, increasing
micronuclei and chromosomal aberration index) in Allium cepa (Kumari et  al.
2011). CuO NPs have DNA-damaging effect in Raphanus sativus, Lolium perenne,
and Lolium rigidum (Atha et al. 2012).
On the contrary to above findings, carbon nanotubes (CNTs) were reported to
increase the seed germination and growth in tomato (Khodakovskaya et al. 2009).
TiO2 NPs improved the energy utilization and conversion efficiency in D1/D2/Cyt
b559 complex in spinach (Su et al. 2009). Stampoulis et al. (2009) reported no nega-
tive effects of multi-walled carbon nanotubes (MWCNTs) and Ag, Cu, ZnO, and Si
NPs on seed germination in Cucurbita pepo. Lee et al. (2010) reported no negative
or positive effect of Al2O3 NPs on Arabidopsis thaliana. TiO2 NPs were absorbed by
the Triticum aestivum, Brassica napus, and Arabidopsis thaliana but did not affect
their germination and root elongation (Larue et al. 2011).
Despite enormous researches carried out on NP-plant interaction, no clear con-
clusion has been made till date. NPs are reported to play positive, negative, as well
as neutral roles on plant growth. Various fates of NPs in plants and their interaction
have been reviewed in details by Pérez-de-Luque (2017). Accordingly, NPs alter the
physiology, biochemistry, and genetics of plants. The interaction depends upon
various factors, e.g., nature and concentration of NPs, nature of coating material,
nature of growth media, mode of application, part of the plants, and even stage of
plant development (Yang et al. 2017).

4.3  Nanoparticles Versus Soil Microorganisms

Plants are immobile organisms. They are dependent upon root system for water and
nutrient absorption. In the vicinity of root systems, millions of microbes including
plant growth-promoting bacteria (PGPR) dwell. They affect the root systems
through their activity and themselves get affected by the exudates of roots (Philippot
et al. 2013; Zoomi et al. 2017). More often, after continuous absorption, nutrient
and water adjacent to the root systems get depleted. Because of the limited growth
of roots, they cannot extract their need from soil from farther distance. In such con-
ditions it is arbuscular mycorrhizal (AM) fungi and other microbes play key roles in
the survival of plants (Zoomi et al. 2017; Kehri et al. 2018). NPs in the soil also
interact with these microbes, and this interaction can control the growth and sur-
vival of aboveground plants. Therefore, the consequences of NPs on belowground
biodiversity are of prime importance to understand.
The research study carried out on the effect of NPs on soil microbes is still in the
beginning phase. NPs are reported as a good stimulator of soil microbes, but their
58 O. Akhtar et al.

harmful effect cannot be neglected (Rajput et  al. 2018). Some research studies,
however, report NPs as soil microbe neutral. The harmful aspect of NPs on soil
microorganisms has been reviewed by Rajput et al. (2018) in details. The interaction
of NPs with soil microbes depends upon particle configuration and coating (McKee
and Filser 2016). McKee and Filser (2016) summarized the morphological nature of
bacteria with reference to the NPs. In most of the reports, they have found gram-­
negative bacteria as less sensitive than gram-positive bacteria. However, any general
conclusion could not be drawn. Further, toxicity may be related to specific nanoscale
properties of the NPs.
McKee and Filser (2016) concluded that Ag- and Cu-based NPs exhibit antimi-
crobial activities. Suresh et al. (2013) described the toxic effects of Ag, Al2O3, TiO2,
CeO2, CuO, CdSe, CdTe, FePt, and ZnO NPs. 1.0 g/l citrate-coated Ag NPs (c-Ag
NPs) inhibited the growth of E. coli by 90 ± 5% (Doody et al. 2014). Simonin et al.
(2016) reported very strong negative impact of TiO2 NPs on nitrification enzyme
activities and the abundances of ammonia-oxidizing microorganism just after
90 days of exposure to even the lowest, realistic concentration. High concentration
of TiO2 (Du et al. 2011; Ge et al. 2011; Simonin et al. 2015) and ZnO (Du et al.
2011; Ge et al. 2011) reported to inhibit microbial respiration and enzyme activity
in the soil. CuO and Fe2O3 NPs were reported as potentially harmful to soil environ-
ment (Frenk et al. 2013). Besides the negative effects, NPs were also reported to
pose positive effects on soil microorganisms. 1.0 g/l citrate-coated Ag NPs (c-Ag
NPs) enhanced the growth of Bacillus subtilis by 127 ± 23% (Doody et al. 2014).
Also, Si, Fe, Au, Pd, Ag2S, and Pt NPs exhibit no or little effect on soil microbes
(Suresh et al. 2013).

4.4  Nanoparticles Versus Symbioses

4.4.1  ZnO Nanoparticle Versus Symbioses

AM fungi reduced the Zn accumulation in plants (Wang et al. 2016; Li et al. 2015).
Under low phosphorus condition, AM fungi reduced translocation, uptake, and
accumulation of Zn (Jing et al. 2016; Wang et al. 2014, 2018) in plant. AM fungi-­
mediated reduction in the soil pH is responsible for decreased Zn bioavailability
(Jing et al. 2016). Further, under low phosphorus conditions, AM fungi reduce the
translocation and accumulation of Zn released from Zn NP (Jing et al. 2016). AM
fungi secrete a group of glycoproteins called glomalin-related soil proteins (GRSPs)
in the soil. GRSPs bind ZnO NP in the soil (Ghasemi Siani et al. 2017), making
them immobilized. The efficiency of AM fungi is further increased under organic
phosphorus (Wang et al. 2018) and low phosphorus conditions (Jing et al. 2016).
Under low phosphorus condition, the efficiency of AM fungi is at maximum. High
level of phosphorus in the soil inhibits the AM colonization, as plants get adequate
phosphorus and the mutualism starts shifting toward parasitism. Under ZnSO4
4  Tripartite Interaction Among Nanoparticles, Symbiotic Microbes, and Plants… 59

treatment the efficiency of AM fungi becomes more responsive toward the ZnO NP
(Li et al. 2015). It is because AM fungi perceive heavy metal toxicity more quickly.
Other mechanism of amelioration of ZnO NP toxicity in plants is the AM fungi-­
mediated increase in the accumulation of P, N, K, Fe, and Cu (Wang et al. 2014,
2016, 2018; Jing et  al. 2016). Decrease in ZnO NP toxicity was confirmed by
reduced ROS production in AM fungi-colonized plants (Wang et al. 2016).
ZnO NPs enhance the growth performance in plants inhabited by non-AM
symbiotic microbes (Medina-Velo et al. 2017; Singhal et al. 2017; Bandyopadhyay
et al. 2015). ZnO nanorods stimulate the number of fungal pellets, spore size, early
sporulation, and thick hyphae in Piriformospora indica. This caused increased crop
productivity (Singhal et al. 2017). ZnO NPs increased the growth performance in
leguminous plants by accumulation of essential elements – sulfur and magnesium –
assisted by higher nodule formation in the roots.
Contrary to above findings, ZnO NPs were found bactericidal to Sinorhizobium
meliloti (Bandyopadhyay et  al. 2012). However, it is less toxic than ZnCl2 for
Medicago sativa L.  – Sinorhizobium meliloti association (Bandyopadhyay et  al.
2015). Ultra-high-resolution scanning transmission electron microscopy (STEM)
revealed that ZnO NPs were accumulated on the bacterial cell wall and internalized
into the periplasmic space. ZnO NPs also altered the polysaccharide structures of
extracellular polymeric substances on bacterial cell wall (Bandyopadhyay et  al.
2012). ZnO NPs also reduced the root shoot biomass (Bandyopadhyay et al. 2015).

4.4.2  Ag Nanoparticle Versus Symbioses

Ag NPs over 0.01  mg/kg enhanced the growth and ecological behavior and also
decreased the antioxidants’ activity in AM fungi-associated plants by decreasing the
Ag content in plants (Feng et al. 2013). They through X-ray microcomputed tomog-
raphy found that AM fungi decreased the Ag content in plants.
Ag NPs in low concentration (50 ppm) improved growth parameters in legumi-
nous plant (Pallavi et al. 2016). They have found that it increased the total bacteria,
nitrogen fixer, and phosphate solubilizer count. Also, Ag NPs increase root nodula-
tion in the roots of legumes. However, higher concentration (75 ppm) of Ag NPs
was found toxic to nitrogen fixers and other bacteria (Pallavi et al. 2016).

4.4.3  CeO2 Nanoparticle Versus Symbioses

CeO2 NPs were found as bacteriostatic to the symbiotic N2-fixer Sinorhizobium

meliloti. It was accumulated on the surface of bacterial cell. CeO2 NPs altered the
protein and polysaccharide structures of extracellular polymeric substances on
bacterial cell wall (Bandyopadhyay et al. 2012).
60 O. Akhtar et al.

4.4.4  Fe3O4 Nanoparticle Versus Symbioses

Fe3O4 NPs in higher concentration reduced the biomass production in mycorrhizal

clover (Feng et al. 2013). It also decreases the bacterial abundance and dissolved
organic content (DOC) in maize plant rhizosphere (Cao et al. 2016) and shifted the
community composition. At high concentration Fe3O4 NPs reduced the root
mycorrhizal colonization, soil GRSP content, and alkaline phosphatase activity.
This also decreased the availability of P nutrition in plants (Cao et al. 2017).
AM fungi reduced the negative effect of Fe3O4 NPs on the plant-microbe interac-
tion (Cao et al. 2016). They have found that AM fungi enhanced the growth of plant
and organic matter release from root (Cao et al. 2016).

4.5  Conclusions

On the account of controversial results obtained on the interaction of NPs with

plants, soil microbes, and symbionts, it is hard to draw any straightforward mecha-
nism of interaction. However, several common behaviors could be attributed to this
interaction. NPs in higher concentration cause adverse effects on plants as well as
their microbial symbionts including AM fungi. Higher concentration of NPs reduces
AM colonization, soil GRSP content, and alkaline phosphatase activity (Fig. 4.1a).
This decreases the availability of P nutrition in plants (Fig.  4.1a). NPs in higher
concentration are bacteriostatic and sometimes toxic to nitrogen fixers and other
symbiotic bacteria.
In symbiotically associated plants, the effect of NPs toxicity is significantly
lower as compared to the plants without symbionts (Fig. 4.1b). AM fungal and bac-
terial symbionts reduce the NP toxicity to the plants by the mechanism yet to be
much understood. AM fungi have more than one mechanism through which they
dilute the NP toxicity in host plants (Fig. 4.1b). These include (1) immobilization
and, hence, reduced accumulation of heavy metallic NP by secretion of GRSPs, (2)
reduction in NP accumulation by altering the soil pH and production of more DOC,
(3) accumulation of more nutrient resulting in more biomass accumulation, and (4)
reduction in reactive oxygen species in plants (Fig. 4.1b).
Besides the negative roles, regulated dose of NPs has positive roles in plants,
especially those inhabited by endophytic microbes and/or nitrogen fixers. The inter-
action among non-AM symbionts, NPs, and plants is also poorly understood.
However, based on researches carried out, several conclusions could be drawn.
Accordingly, NPs stimulate the plant growth by (1) increased accumulation of
essential elements – sulfur and magnesium – assisted by higher nodule formation in
the roots; (2) stimulation in the number of fungal pellets, spore size, early sporula-
tion, and thick hyphae in endophytes; and (3) increasing the total bacteria, nitrogen
fixer, and phosphate solubilizer count.
4  Tripartite Interaction Among Nanoparticles, Symbiotic Microbes, and Plants… 61

Fig. 4.1  Mechanism of tripartite interaction among NPs, AM fungi, and plants. (a) High concen-
tration of NPs in soil. (b) Low concentration of NPs in soil

4.6  Future Perspectives

Use of engineered NPs in soil which is increasing day by day may pose detrimental
effects on belowground biodiversity. Our understating on the interaction of NPs
with belowground biodiversity is at its preliminary phase. For sustainable use of
NPs in agriculture production, there is a need of extensive research to explore the
effects of various NPs and their optimum dose, coating material, carrier, mode,
time, and frequency of application on different symbiotic microbes with reference
to the host plant. Extensive research is also needed to trace and study the movement
and localization of NPs in symbiotic microbes. Also, consequences of NPs internal-
ization on gene expression and cellular functions should be studied.
62 O. Akhtar et al.

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https://doi.org/10.1007/978-981-10-6847-8_3
Chapter 5
Effect of Nanoparticles on Plant Growth
and Physiology and on Soil Microbes

Muhammad Nafees, Shafaqat Ali, Muhammad Rizwan, Asma Aziz,

Muhammad Adrees, Syed Makhdoom Hussain, Qasim Ali,
and Muhammad Junaid

5.1  Introduction

The use of nanotechnology for potential benefits in agriculture is enormous and

has been increasing day by day (Shapira and Youtie 2015; Resham et  al. 2015;
Nath 2015). Novel applications of nanotechnology have been developed in bio-
technology and agriculture (Siddiqui et al. 2015; Singh et al. 2016, 2019; Shweta
et al. 2017, 2018; Arif et al. 2018; Vishwakarma et al. 2018) to manage food pro-
ductivity (Kumari et al. 2014). Nanoparticles (NPs) are very tiny particles, defined
as the 10−9 part of 1 m (1 m−9) (Huang et al. 2015). NP efficiency relies on their
surface area, size, composition, shape, and above all the effective concentration
at which they work efficiently (Khodakovskaya et  al. 2012; Ranjan et  al. 2014;

M. Nafees
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment,
Nanjing University, Nanjing, China
S. Ali (*)
Department of Environmental Sciences and Engineering, Government College University,
Faisalabad, Pakistan
Department of Biological Sciences and Technology, China Medical University (CMU),
Taichung, Taiwan
e-mail: [email protected]
M. Rizwan · M. Adrees
Department of Environmental Sciences and Engineering, Government College University,
Faisalabad, Pakistan
A. Aziz · S. M. Hussain
Department of Zoology, Government College University, Faisalabad, Pakistan
Q. Ali
Department of Botany, Government College University, Faisalabad, Pakistan
M. Junaid
Key Laboratory for Heavy Metal Pollution Control and Reutilization, School of Environment
and Energy, Peking University Shenzhen Graduate School, Shenzhen, China

© Springer Nature Switzerland AG 2020 65

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_5
66 M. Nafees et al.

Dasgupta et  al. 2016; Jain et  al. 2016; Maddineni et  al. 2015). Nanotechnology
provides a very large variety of techniques and devices to formulate NPs, detect
biotic and abiotic stress in plants, and provide genetic manipulation that allows
more precise plant breeding (Perez-de-Luque and Hermosin 2013; Fraceto et  al.
2016). Fertilizers are very important in the growth, development, and metabolism
of plants (Giraldo et al. 2014), but at most concentrations applied fertilizers are not
available to plants because of leaching, runoff, and degradation. Thus, it is very
important to control or minimize chemical fertilizer loss. With their unique proper-
ties, NPs encapsulate nutrients, which, released as required, control the discharge of
chemical fertilizers for plant growth (Derosa et al. 2010; Nair et al. 2010; Shweta
et al. 2018). Several studies have shown that particular low doses of NPs enhance
plant physiology (Zheng et al. 2005; Klaine et al. 2008). NPs can enter plant cells
through the stomata of leaves and roots to transport nutrients, DNA, and chemicals
(Galbraith 2007; Torney et  al. 2007). Nanomaterials can break down the plasma
membrane, inducing pore formation to enter into the plant cells (Wong et al. 2016)
and reach the cytosol (Serag et al. 2011). These NPs enhance chlorophyll activity,
water uptake, and specific microbial communities in the soil (Fig. 5.1).
With unique physicochemical properties, NPs can enhance the biochemical pro-
cesses of plants (Giraldo et al. 2014). The application of carbon nanotubes (CNTs)
to activate the growth and physiology of different plants has been well documented;

Fig. 5.1  Nanoparticle spray or irrigation and the effects on plant growth and the soil microbial
community
5  Effect of Nanoparticles on Plant Growth and Physiology and on Soil Microbes 67

for example, the root growth of ryegrass, onion, and cucumber was increased by
CNTs (Lin and Xing 2007; Canas et al. 2008; Shweta et al. 2017). NPs have some
toxic effects on plants and other living organisms, but also increase the growth,
physiology, and photosynthesis of plants. This review discusses the impact of
nanoparticles on plants and microbial communities.

5.2  Effect of Nanoparticles on Plants

The impact of nanoparticles on plants depends upon the plant species and the NP
variety (Table  5.1) (Nair 2016; Servin and White 2016; Singh et  al. 2016;
Vishwakarma et al. 2018; Tripathi et al. 2017; Rastogi et al. 2019). Minerals such as
nitrogen and phosphorus act as growth factors, regulating plant growth and also
increasing crop productivity. Phosphorus fertilizer increases the availability of
phosphorus in the soil and increases the uptake of phosphorus from the root sur-
faces. In phosphorus-solubilizing enzymes in which Zn is a cofactor, phosphatase
and phytase enzyme activity was increased by 84–108%. ZnO NPs also enhanced
root length, root volume, and the chlorophyll and protein content of the leaves in
mung bean plants. ZnO NPs also maintained soil health by influencing the soil
microbial community (Raliya et al. 2016).
Germination of cucumber seed was enhanced by exposure to various concentra-
tions of ZnO NPs (de la Rosa et al. 2013). ZnO NPs not only were absorbed by
Vigna radiata and Cicer arietinum roots but also improved the length and biomass
of the roots and shoots of these species (Mahajan et al. 2011). This NP also enhanced
somatic embryogenesis by shoot regeneration, induced the synthesis of proline, and
increased tolerance against stress by increasing the activity of different enzymes
(Helaly et  al. 2014). Gold (Au) NPs enhanced the seed germination of Brassica
juncea, Boswellia ovalifoliolata, and Gloriosa superba (Arora et al. 2012; Gopinath
et al. 2014). The Au NPs increased the number of leaves, leaf area, and length of the
plant and its chlorophyll and carbohydrate content, which increased growth, devel-
opment, and crop yield (Arora et al. 2012; Gopinath et al. 2014). The Au NPs dem-
onstrated importance in seed germination, in antioxidants, and altered the expression
of micro-RNAs that regulate morphological, physiological, and metabolic processes
in plants (Kumar et al. 2013).
The effects of CeO2 were collectively found on seed germination, vegetative
parts, the cotyledon, floral parts, and ripening of fruits. The rate of seed germination
(97%) was high in a 10 mg/l concentration of CeO2. No negative effect on germina-
tion and no significant effect on production of chlorophyll was seen with any con-
centration of CeO2 NPs on tomato plants, although there was a significant difference
in the growth of the vegetative parts of the tomato plant; faster growth was found at
10 mg/l CeO2 NPs. The number of floral buds was slightly higher in the control and
the 10 mg/l concentration of CeO2 NPs, and 67% of buds were converted into the
flower. Fruit size, production, and ripening were enhanced by increasing concentra-
tions of CeO2 NPs; large, heavy fruits were found at 10 mg/l (Wang et al. 2012a).
68 M. Nafees et al.

Table 5.1  Effect of nanoparticles on plant growth/physiology/tolerance against stress

Nanoparticles Plant Impact on plant parts/process References
Al2O3 Lemna minor Increased root length, Juhel et al. (2011)
photosynthetic activity,
biomass accumulation
TiO2 Triticum aestivum Increased root length Larue et al. (2012)
CeO2, ZnO Zea mays Reduced yield Zhao et al. (2012)
CuO Brassica napus Increased plant growth Rahmani et al. (2016)
FeCl3 Lepidium sativum Seed germination, seedling Libralato et al. (2016)
Sinapis alba length, biomass
Sorghum
saccharatum
Ag NO3 Lentil seed Seed germination/elongation Hojjat and Hojjat (2016)
of root and shoot
Fe2O3 Soybean Increased root length, Alidoust and Isoda (2013)
regulated the enzyme
Cu, Zn Wheat seedling Increased RWC and Taran et al. (2017)
stabilized photosynthetic
pigments
Ca3(PO4)2 Rice Increased growth, micro-­ Upadhyaya et al. (2017)
fertilizer and promoter of
growth
Fe3O4, TiO2 Soya bean Enhanced plant growth, crop Burke David et al. (2015)
yield, effect on leaf carbon
and phosphorus
CeO2 Soya bean Stimulated plant growth, Cao et al. (2017)
rubisco carboxylase activity,
relative water content
ZnO Chickpea Effect on root, accumulation Burmana et al. (2013)
of biomass in seedlings,
lowered ROS, promoted
antioxidant activity
Ag Wheat Increased shoot fresh and dry Mohamed et al. (2017)
weight, enhanced salt
tolerance ability of crop
SiO2 Zea mays L., Seed germination, root and Sharifi-Rad et al. (2016)
Phaseolus vulgaris shoot length, fresh weight
L., Hyssopus (except Hyssopus officinalis
officinalis L., L.) and dry weight,
Nigella sativa L., photosynthetic pigments,
Amaranthus total protein and total amino
retroflexus L., acids (except Hyssopus
Taraxacum officinalis L.) significantly
officinale increased at 400 mg l−1; these
F. H. Wigg parameters were decreased in
weeds, and total
carbohydrates decreased in
all plants except
A. retroflexus
(continued)
5  Effect of Nanoparticles on Plant Growth and Physiology and on Soil Microbes 69

Table 5.1 (continued)
Nanoparticles Plant Impact on plant parts/process References
Ag Wheat (Triticum Wheat was unaffected by Ag Pallavi et al. (2016)
astivium var. NPs, but overall growth of
UP2338), cowpea cowpea and Brassica plants
(Vigna sinensis var. was influenced
Pusa Komal),
brassica (Brassica
juncea var. Pusa jai
Kisan), oat
TiO2 Arabidopsis Enhanced germination, root Szymanska et al. (2016),
thaliana (L.) elongation and seedling Andersen et al. (2016),
Heynh, growth Mahmoodzadeh et al.
corn, cabbage, (2013), Servin et al. (2012),
lettuce, Feizi et al. (2013, 2012),
oat, Haghighi and Teixeira da
Brassica napus L. Silva (2014), Dehkourdi and
Cucumber, Mosavi (2013), Gogos et al.
fennel, (2016), Rezaei et al. (2015),
onion, tomato Zheng et al. (2005),
Parsley Mahmoodzadeh and Aghili
(Petroselinum (2014).
crispum Mill.),
red clover,
soybean,
spinach,
wheat
TiO2 Chickpea (Cicer Enhanced tolerance against Mohammadi et al. (2013,
arietinum L.), cold in chickpea, heat in 2014), Qi et al. (2013),
tomato, wheat, tomato, drought in wheat and Jaberzadeh et al. (2013),
Flax (Linum flax Aghdam et al. (2016)
usitatissium L.)
TiO2 Tomato, oilseed Increased chlorophyll Raliya et al. (2015a), Li
rape, Arabidopsis, contents of tomato and oil et al. (2015), Ze et al.
spinach, basil seed rape, promoted activity (2011), Lei et al. (2008),
(Ocimum of rubisco and net Kiapour et al. (2015)
basilicum L.) photosynthesis in
Arabidopsis, spinach, tomato,
and basil (Ocimum basilicum
L.)
TiO2 Barley, corn, mung Enhanced crop yield and Moaveni and Kheiri (2011),
bean, snail clover, biomass Morteza et al. (2013),
tomato, wheat Raliya et al. (2015b),
Rafique et al. (2015)

Clement et al. (2013) determined the effect of TiO2 NPs on algae, rotifers, and
plants. High concentrations of TiO2 NPs have antimicrobial activity and also
­promoted the growth of roots. The collective effect of SiO2 NPs on germination of
seeds, elongation of roots and shoots, and water content of Zea mays L. was deter-
mined. SiO2 NP uptake by plants from a hydroponic environment and increased
70 M. Nafees et al.

growth of seed and elongation of roots was high as compared to control. Seed
­germination was increased at 400  mg/l but decreased at 2000 and 4000  mg/l
­concentrations of SiO2 NPs. SiO2 NPs increased root length but decreased shoot
length of plants at concentrations from 0 to 4000 mg/l. SiO2 NPs showed a negative
correlation between NP concentration and relative water content (RWC) in plants.
The RWC was decreased as the concentration of SiO2 increased from 0 to 4000 mg/l.
It was observed that SiO2 NPs had a significant effect on photosynthetic pigments
(chlorophyll a, b, and carotenoids), which increased at 400–4000 mg/l NP concen-
tration in Z. mays. High photosynthetic content was found at 400 mg/l SiO2 NPs
(Rad et al. 2014).

5.2.1  Effects of NPs on Photosynthesis

Photosynthesis is the key mechanism that transforms light energy into chemical
energy. Rubisco is an enzyme used in carbon fixation during light reactions. SiO2
NP increased the photosynthesis rate by increasing the activity of carbonic anhy-
drase and the formation of photosynthetic pigments (Xie et al. 2012; Siddiqui and
Al-Whaibi 2014). Carbon anhydrase acts as a supplier for CO2 to the rubisco
enzyme, which enhances photosynthesis (Siddiqui et al. 2012). TiO2 has photocata-
lytic properties that not only increase the efficiency of light absorbance but also
increase the conversion of light energy into chemical energy. TiO2 also improved
fixation of CO2, prevented the plant from aging, and ultimately enhanced the photo-
synthesis process (Hong et al. 2005; Yang et al. 2006).
TiO2 NPs increased CO2 fixation by increasing the activity of rubisco and ulti-
mately improving plant growth. TiO2 NPs enhanced the net rate of photosynthesis,
water conduction, and plant transpiration (Ma et al. 2008; Qi et al. 2013). ZnO NPs
showed a positive effect on the growth of cotton (Gossypium hirsutum L.). The
growth (130.6%) and biomass (131%) of cotton were significantly enhanced by
ZnO NPs.
ZnO NPs increased the level of chlorophyll a, b, and carotenoids (141.6%,
134.7%, 138.6%, respectively) and increased soluble protein (179.4%) but reduced
malondialdehyde (MDA) level in plant leaves. Various enzymatic activities of cata-
lase, superoxide dismutase (264.2%), and peroxidase (182.8%) were also increased
and improved the growth of cotton plants (Venkatachalam et al. 2016).

5.3  Effect of Nanoparticles on the Soil Microbial Community

Soil microbes have a significant role in soil health, plant growth, productivity, and
biological and chemical reactions within soil and plants (Table  5.2) (Falkowski
et al. 2008; Schimel and Schaeffer 2012; Philippot et al. 2013; Vacheron et al. 2013;
Singh et al. 2019). NPs enter into the soil through several ways including human
5  Effect of Nanoparticles on Plant Growth and Physiology and on Soil Microbes 71

Table 5.2  Effect of nanoparticles on the soil microbial community

Nanoparticles Impact on soil microbial community/processes References
Fe3O4, TiO2 Changed the soil microbial community, influenced the Burke David et al.
colonies of nitrifying bacteria associated with roots (2015)
CuO Influenced the composition and activity of the bacterial Schlich and
community, decreased the oxidative potential of the soil Hund-Rinke (2015)
ZnO Ammonification, dehydrogenase, and hydrolase activity Shen et al. (2015)
TiO2 Influenced carbon mineralization, pH of soil, organic Simonin et al. (2015)
matter; identified soil type and moisture
CeO2, Fe3O4, No effect on microbial biomass C and N VittoriAntisari et al.
SnO (2013)
Ag Different impact on ion release shape and function of Zhai et al. (2016)
the natural soil microbes
TiO2, ZnO Altered soil microbes, enhanced the degradation of Ge et al. (2012)
organic pollutants
Ag Influenced soil microbial diversity and functional Pallavi et al. (2016)
bacterial diversity
Ag Increased biomass of Aspergillus niger and Penicillium Pietrzak and
chrysogenum Gutarowska (2015)
Enhanced soil extract and inhibited antifungal activity
of Ag
Ag Affected functional diversity of soil microbial Zhai et al. (2016)
community and associated ecosystem processes
CuO, Fe3O4 Increased toxicity toward microbial community Frenk et al. (2013)
SiO2, Pd, Au, Increased number of microbial colonies in soil, Shah and Belozerova
Cu enhanced metabolic rate of soil community 2009

activity, sewage, and industrial waste. NPs of silica, palladium, gold, and copper
have beneficial effects on soil microbes and seed germination of lettuce (Shah
and Belozerova 2009). Biological and physicochemical properties determined
their health and increased soil productivity. Biosolids have been used as organic
fertilizers for decades; silver and titanium NPs were detected above the threshold
level and adversely affected soil microbiota (Kim et al. 2010; Rottman et al. 2012;
Wang et al. 2012a, b). Zinc oxide and copper NPs did not show harmful effects on
soil microbes although silver and titanium NPs showed an adverse effect on the
microbial biomass richness (Cardoso et al. 2013; Shah et al. 2014).
Asadishad et  al. (2017) investigated the efficacy of gold nanoparticles coated
with citrate (50 nm) and polyvinylpyrrolidone (PVP) (5, 50, and 100 nm) on soil
enzymatic activity and soil microbes. They noted that a low concentration of Au
NPs (0.1 mg/kg) reduced the size of PVP. Au NPs stimulate soil enzymatic activity;
the Au NP size and soil enzymatic activity showed no correlation at a high dose
(100 mg/kg). Citrate-coated Au NPs significantly increased soil enzymatic activity
as compared to PVP-coated Au NPs at 50 nm size of both particles. Biomass of the
important soil bacteria Actinobacteria and Proteobacteria was increased by the addi-
tion of citrate-coated Au NPs.
72 M. Nafees et al.

5.4  Impact of Carbon Nanotubes on Plants

Carbon nanotubes are allotropic forms of carbon nanoparticles, open or closed

nano-structure cylindrical tubes that are single-walled carbon nanotubes (SWCNTs)
or multi-walled carbon nanotube (MWCNTs). These layers are composed of rolled
sheets of graphene. These nanotubes vary from 100  nm to some centimeters in
length; the outer diameter of SWCNTs varies from 0.8 to 2 nm and that of MWCNTs
from 5 to 20 nm (De Volder et al. 2013). CNTs were shown to act as growth regula-
tors for plants (Khot et al. 2012). It was also noted that different sizes and composi-
tion of CNTs affect different plant growth parameters (Table 5.3). The stress-related
gene of the tomato seed was regulated by MWCNTs that enhance seed germination
and growth (Khodakovskaya et al. 2009).
CNTs are involved in major cellular processes of plants such as up- or downregu-
lation of gene expression. MWCNTs induced the expression of a gene that codes for
water channels and increased the water intake ability of root cells. CNTs are very
small in diameter, so they can easily pass through the pores of the cell wall and also
can increase the cell-wall pores. CNTs induced pores in the cell wall that enhanced
water uptake, which regulates the activity of starch hydrolase enzymes and increases
seed germination (Santos et al. 2013; Vithanage et al. 2017). These CNTs also act
as a slow-release fertilizer that promotes plant growth (Wu 2013).
MWCNTs are also frequently used in hydroponic culture; CNTs (2000  mg/l)
increase the root length of ryegrass (Lin and Xing 2007). Canas et al. (2008) showed
that CNTs enhanced the physiology of six crops: cucumber, carrot, onion, tomato,
cabbage, and lettuce. Plants were treated with uncoated (0, 104, 315, or 1750 mg/l)
or coated (0, 160, 900, or 5000 mg/l) CNTs for 48 h. The uncoated CNTs signifi-
cantly boosted root length of onion and cucumber more than the coated CNTs, with
an inverse proportion between time and root elongation in these hydroponic crops.
More effective results were seen on the first day as compared to the second day. It
was hypothesized that CNTs may have an obligatory effect on the root length of
plants by obstructing the relationship between roots and microbes, altering vital
biological and chemical reactions. CNTs not only were absorbed by the plant but
accumulated in the epidermal tissue of wheat roots (Wild and Jones 2009). Citrate-­
coated CNTs enhanced the growth and physiology of plants by increasing water
uptake capability and also the uptake of nutrients and minerals, which directly
affected the photosynthesis of the plants. CNTs increased plant length and also
increased the number of leaves, which enhanced plant photosynthetic activity
(Tripathi et al. 2011).
MWCNTs regulated the gene expression of the aquaporin gene (NtPIPI), and of
two water channel genes (CycB and NtLRX), which increased cell permeability for
water absorption and also helped in formation of the cell wall and regulation of
mitosis (Khodakovskaya et al. 2012). MWCNTs also had a significant effect on root
5  Effect of Nanoparticles on Plant Growth and Physiology and on Soil Microbes 73

Table 5.3  Effect of carbon nanoparticles and nanotubes on plant growth processes
Impact on plant parts,
Plant name CNPs/CNT growth/process References
Lycopersicon CNTs Seed germination and Anjum et al. (2014)
esculentum growth
Medicago sativa, CNTs Root elongation Miralles et al. (2012)
Triticum aestivum
Allium cepa, Cucumis SWCNTs Root elongation Canas et al. 2008
sativus
Hordeum vulgare L., MWCNTs Growth (leaf, root and Lahiani et al. (2013)
Glycine max, Zea mays shoot)/germination
Wheat MWCNTs Root growth and yield Wang et al. (2012a)
Lycopersicon MWCNTs Increased uptake of water Tiwari et al. (2013)
esculentum and nutrients
Zea mays MWCNTs Increased nutrient transport Tiwari et al. (2014)
and yield
Mustard plant (Brassica MWCNTs Increased seed Mondal et al. (2011)
juncea) germination, root
elongation
Tomato MWCNTs Increased plant growth Khodakovskaya et al.
(flower and fruit) and yield (2013), Alimohammadi
et al. (2011)
Wheat, maize, peanut, CNTs Increase in root and shoot Rao and Srivastava
garlic length (2014)
Red spinach, lettuce, CNTs Increased growth, root and Begum et al. (2014)
rice, cucumber, chili, shoot length
lady finger (okra),
soybean
Corn CNTs Increased growth, root and De La Torre-Roche
shoot length, biomass et al. (2013)
Hyoscyamus niger SWCNTs Enhanced plant Hatami et al. 2017
performance, antioxidant
activity, and biosynthesis
of protein
Zucchini SWCNTs, No significant change in Stampoulis et al. (2009)
MWCNTs seed germination
Solanum lycopersicum CNPs Seed coat permeability Ratnikova et al. 2015
Buckypaper CNTs Increased permeability Shen et al. (2017)
(SWCNTs, (pore size)
MWCNTs)
Broccoli CNTs Positive effect on growth, Martinez-Ballesta et al.
enhanced CO2 assimilation (2016)
Arabidopsis thaliana MWCNTs Effect on efficiency of Voleti (2015)
photosynthesis and
physiological mechanism
74 M. Nafees et al.

length of wheat seedlings, and on germination and growth of soya bean, corn, and
barley (Wang et al. 2012a, b; Lahiani et al. 2013). The root length of wheat seed-
lings increased 32% with MWCNTs at 40–160 μg/l for 3 to 7 days (Wang et al.
2012a, b). CNTs impacted early plant growth by germination of seed, ­expression of
genes, cell culturing, and physiological processes such as photosynthesis and anti-
oxidant activities (Canas et al. 2008).
SWCNTs enhanced photosynthetic activity threefold as compared to normal
photosynthesis, and increased the rate of electron transport because SWCNTs com-
bine with the chloroplast and enable the leaf to enhance the rate of electron transport
by a photo-absorption mechanism (Giraldo et al. 2014). The germination ability of
seed might be enhanced by increasing concentrations of MWCNTs. The highest
seed germination rate was noted at 60 μg/ml CNTs; increasing CNT concentrations
increased plant growth and also enhanced the yield of cotton per plant. The highest
yield of cotton was found at 100 μg/ml CNTs (Sawant 2016): there was a linear
­correlation between seed germination and CNT concentration. It was observed that
the length of plants (62 ± 5.58cm), boll’ number/ plant (5.8 ± 0.64) and size of boll
(3.41 ± 0.27cm) and yield of cotton (3.4 ± 0.37/hectare) was found highest at 120
μg/ml, 80 μg/ml, 60 μg/ml, 100 μg/ml of CNTs respectively (Sawant 2016).
Various studies have shown that SWCNTs and MWCNTs positively affect ger-
mination and growth of tomato, rice, common gram, and tobacco by increasing their
water uptake ability, which improves germination processes (Khodakovskaya et al.
2009; Nair 2016). The toxic levels of Ag, ZnO, and Al2O3 induced oxidative stress
and produced reactive oxygen and nitrogen species, which reduced plant growth
(Zhao et al. 2012; Thwala et al. 2013; Hossain et al. 2015; Xia et al. 2015). Oxidative
species reduced rubisco activity and decreased the photo-protective activity of pho-
tosystem II (Jiang et al. 2017). The defensive system of plant consists of nonenzy-
matic antioxidants, which include thiols, glutathione, phenolics, ascorbate and
enzymatic CAT, SOD, APX, GR, GPX, and GST (Singh et  al. 2015). Oxidative
stresses were caused by NPs that decreased photosynthetic rate, ultimately inhibit-
ing plant growth (Da Costa and Sharma 2016; Li et al. 2016).
Chegini et al. (2017) observed that physiological parameters were affected by
MWCNTs, drought conditions, and their interactions in Salvia mirzayanii. The leaf
water content and chlorophyll index showed significant alterations under drought
conditions. The various levels of MWCNTs affected electrolyte leakage index and
caused a significant difference in phenolic compounds under the interactions of the
experimental treatments. Phenolic content was significantly influenced at MWCNT
50 and 200 mg/l, to 25% of field capacity (FC), respectively. The concentration of
MWCNTs (50 mg/l) in moderate drought condition changed the physiological traits
and antioxidant activity of S. mirzayanii.
Barbinta-Patrascu et  al. (2017) reported an effect of carbon nanotubes coated
with chlorophyll a and laden biomimetic membrane. The multilamellar lipid vesi-
cles increased antioxidant (85%) activity and antibacterial activity against
Staphylococcus aureus, and the highest antioxidant ability was found in hybrid
CNTs that originated through the multilamellar lipid vesicles (TP3). They were
5  Effect of Nanoparticles on Plant Growth and Physiology and on Soil Microbes 75

widely dispersed and increased the reaction sites for removal of ROS by increasing
their surface area. The TP3 sample showed the highest antibacterial activity result-
ing from good dispersion because a large surface area was provided to destroy bac-
terial contamination. The SWCNTs react directly with bacterial cells and physically
break down their cell membrane by puncture, causing the death of the bacterial cells
(S. aureus) (Bai et al. 2011; Smith and Rodrigues 2015).

5.4.1  Effect of CNTs on Photosynthesis Mechanism

Sunlight is the most available source of energy, which is conserved in many ways in
an ecosystem. One of the most efficient methods for the conservation of sunlight is
photosynthesis. For this purpose, the higher green plants, algae, and bacteria con-
tain special pigments that use water and CO2 to form organic molecules. These
photosynthetic organisms contain the photo-elements chlorophyll a, b, d, and f, and
a series of electron carrier redox reactions (Blankenship et al. 2011). The thylakoid
membrane of plastids acts as a photo-current producer in the presence of potassium
ferrocyanide. The cell surface (1 cm2) produced maximum electric power, 24 mW,
at 625 nm of red light. The thylakoid membrane immobilized with MWCNTs acts
as an anode with MWCNTs as a cathode, which produced the maximum current
density, 38 mA/cm2. The maximum electric power produced at this current density
is 5.3 mW/cm2 (Calkins et al. 2013). The effect of CNTs on chlorophyll f and d was
more than that on chlorophyll a and b: it enhanced the absorption ability of far-red
and infrared light (700–750 nm) and also enhanced the ability of photo-convertors
(Voloshin et al. 2015). The CNTs were synthetic NPs that penetrate into the biologi-
cal matrix and have multifunctional properties such as water uptake and conduction
for electricity in biological systems. MWCNTs were most electro-conductive in
BY-2 tobacco cells as compared to balsam fir wood at high temperature (Di Giacomo
et al. 2013; Leslie et al. 2014).
It was investigated whether CNTs had a positive effect on photosystem I of cya-
nobacteria by enhancing the ability of conversion of light into current. The
MWCNTs were non-encroaching because a carboxylate pyrene derivative formed
the fixed covalent structure of photosystem I (PS I). The PS I was ascribed as the
transporter of photo-current to the electrode (MWCNTs) (Ciornii et  al. 2017).
MWCNTs have a combined effect on thylakoid, the multi-protein complexes PS I
and II, and photo-electrochemical properties. SWCNTs enhanced immobilization
of the reaction center of the bacterium Rhodobacter (Rb.) sphaeroides (sp.) and also
enhanced the photo-electrochemical activity (Ham et al. 2010; Calkins et al. 2013).
MWCNTs significantly enhanced direct transfer of electron in the thylakoid of spin-
ach and of the cyanobacterium Nostoc sp. (Sekar et al. 2014). CNTs enhanced the
expression of Arabidopsis aquaporin in tobacco plant and enhanced photosynthetic
activity by production of the photo-electric current. It was observed that CNTs acti-
vate gene and protein expression of aquaporin in tobacco cells (Khodakovskaya
et al. 2012).
76 M. Nafees et al.

5.5  Effect of CNTs on Soil Microbial Community

The soil contains different microorganisms that form the biota of the soil as the
main source of nutrients which are significant in plant growth (Table  5.4).
Microorganisms have a key role in recycling of nutrients by decomposition of
organic matter (Simonet and Valcarcel 2009; Dinesh et al. 2012). Some microorgan-
isms associate with plant roots; the soil microbial community normally consists of
gram-positive bacteria, gram-negative bacteria, and fungi (Luongo and Zhang 2010;
Santos et al. 2013). The major challenge in the agriculture sector is the conservation
of biodiversity and protection of the biomass of these soil microbes. CNTs can
change a microbial community by increasing or decreasing the toxins present in
organic compounds (Dinesh et  al. 2012). Limited literature is available on the
impact of CNTs on soil microbial communities. It has been also reported that CNTs
had no significant effect on soil microbes. So, there is a need to thoroughly explore
CNT impacts on soil microbes.
Mukherjee et al. (2016) reported that low and high concentrations of CNTs have
no adverse effect on soil microbiota. High (10–10,000 mg/kg) and low (10–1,000 mg/
ml) concentrations of CNTs were used to investigate effects on soil microbial com-
munity and enzymatic activity, but it was found that CNTs had no visible effect on
soil microbes and enzymatic activity, although these high and low CNT concentra-
tions reduced selected species of bacteria. These specific concentrations increased
the amount of polycyclic aromatic hydrocarbon (PAH)-degrading bacteria.
Similarly, when red clover was treated with MWCNTs, the activity of symbiotic
microorganisms as nitrogen fixers was slightly increased at 3000 mg/kg MWCNTs
(Moll et al. 2016).

Table 5.4  Effect of carbon nanoparticles (CNP) and carbon nanotubes (CT) on the soil microbial
community
CNPs/
CNT Impact on soil microbial community/processes References
MWCNTs Enhanced activity of anaerobic ammonium oxidation Wang et al. (2013)
bacteria, high carbohydrate and protein
SWCNTs Strong antimicrobial activity Kang et al. (2007)
SWCNTs Effect on both gram-positive and gram-negative bacteria Jin et al. (2014)
MWCNTs Effect on soil enzyme activity, soil microbial biomass Chung et al. (2015)
MWCNTs Conditionally affect soil microbial community Kerfahi et al. (2015)
CNTs Effects on composition of soil microbes Khodakovskaya et al.
(2013)
CNTs Affect growth of gram-negative bacteria Cordeiro et al. (2014)
SWCNTs Effects on antimicrobial activity of surface bacteria Jackson et al. (2013)
CNTs Toxic effect on microbes Petersen et al. (2014)
5  Effect of Nanoparticles on Plant Growth and Physiology and on Soil Microbes 77

5.6  Future Possibilities

Nanoparticles have great potential to promote plant growth and development by

increasing nutrient uptake, improving water uptake efficiency, and enhancing pho-
tosynthetic activity. However, there is a need to improve NP use in agriculture by
developing target-specific NPs to enhance plant growth, physiological parameters,
and the soil microbial community. There is an urgent need to utilize NPs having
great potential to enhance photosynthesis mechanism because minimal attention is
being given to this area of research. Biosynthesized NPs should be used: by control-
ling their size and concentration we can determine the mechanism of toxicity in
plants. Modulating these factors, we can reduce transportation, toxicity, and bio-
availability to the ecosystem. There is further need to explore the function of NPs
beneath plant roots.

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Chapter 6
Recent Trends and Advancement Toward
Phyto-mediated Fabrication of Noble
Metallic Nanomaterials: Focus on Silver,
Gold, Platinum, and Palladium

Satarudra Prakash Singh, Mohammad Israil Ansari, Brijesh Pandey,

Janmejai Kumar Srivastava, Thakur Prasad Yadav, Humaira Rani,
Ashna Parveen, Jyoti Mala, and Akhilesh Kumar Singh

6.1  Introduction

Materials having sizes smaller than 100 nm are not unusual on our planet because
such materials are naturally produced as a result of photochemical volcanic activity
as well as combustion including food cooking and automobile exhausts. However,
Professor Norio Taniguchi initially introduced the multidisciplinary science in the
year 1974 that covers research as well as technology from chemistry and physics
together with biology usually called nanotechnology (Haleemkhan et  al. 2015).
Nanotechnology has emerged as one of the important areas of contemporary sci-
ence that deals with methodology, fabrication, as well as tailoring of materials’ size
within 1–100 nm range. In such range, the entire properties of individual atoms or
molecules along with their corresponding bulk counterparts undergo drastic trans-
formation that gives rise to a wide range of interesting novel and astonishing physi-
cochemical properties based on their morphology, size, as well as size distribution

S. P. Singh · B. Pandey · A. K. Singh (*)

Department of Biotech and Genome, School of Life Sciences, Mahatma Gandhi Central
University, Motihari, India
e-mail: [email protected]
M. I. Ansari
Department of Botany, University of Lucknow, Lucknow, India
J. K. Srivastava · H. Rani · A. Parveen
Amity Institute of Biotechnology, Amity University Uttar Pradesh, Lucknow Campus,
Lucknow, India
T. P. Yadav
Department of Physics, Institute of Science, Banaras Hindu University, Varanasi, India
J. Mala
D. P. C. S. S. (Miller) Senior Secondary School, Bihar, Patna, India

© Springer Nature Switzerland AG 2020 87

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_6
88 S. P. Singh et al.

(Baker et al. 2013; Ahmed et al. 2016). This is attributable to fact that when the
materials’ size reaches to nanoscale, the % atoms existing at the surface of material
turn out to be substantial, where the greater surface area of nanomaterials (NMs)
results, the role played by small bulk of material (Akhtar et  al. 2013). The NMs
depict exceptional features owing to their high surface energy, large fraction of sur-
face atoms, diminished imperfections, as well as spatial confinement (Bai et  al.
2009). Apart from this, NMs are advantageous compared to corresponding bulk
counterparts because of their surface-enhanced Raman scattering, surface plasmon
resonance, surface-enhanced Rayleigh scattering, and surface plasmon light scatter-
ing properties. Owing to such possessions, NMs could be exploited as building
blocks toward many optoelectronic, electronic, chemical sensing, and biological
applications (Wong and Schwaneberg 2003; Ramanavicius et al. 2005; Singh et al.
2018a, b; Pandey et al. 2018).
A noteworthy field of research in nanotechnology is the fabrication of NMs hav-
ing distinct shapes as well as sizes and chemical structures including regulated
disparities. Since the past two decades, the formation of noble metallic NMs (sil-
ver, gold, platinum, and palladium) has been gaining substantial interest owing to
a wide range of potential uses like shampoos, detergents, cosmetic products, tooth-
paste, etc. (Kim and Song 2010). Table 6.1 summarizes the potential uses of silver,
gold, platinum, and palladium as noble metallic NMs. Such valuable metallic NMs
are produced as a result of either top to bottom or bottom to up techniques.
Figure 6.1 summarizes the top to bottom and bottom to up approaches for the fab-
rication of metallic NMs. In top to bottom strategy, production of metal NMs is
carried out as a reduction of appropriate bulk compounds into nano-size by employ-
ing different physical/chemical approaches (Mittal et  al. 2013). In this method,

Table 6.1  Promising applications of gold, platinum, silver, and palladium NMs
Noble
metallic
NMs Promising applications References
Gold Medicine, disease diagnostic, drug Bhumkar et al. (2007); Bhattacharya and
delivery systems, and antibacterial Murkherjee (2008); Torres-Chavolla et al.
activity (2010); Puvanakrishnan et al. (2012);
Bindhu and Umadevi (2014); Liu et al.
(2017)
Platinum Catalysts as well as in various Hrapovic et al. (2004); Narayanan and
biomedical uses in amalgamation with El-Sayed (2004); Bhattacharya and
other NMs in alloy, core shell and Murkherjee (2008); Cheong et al. (2010);
bimetallic nanostructure, and Lin et al. (2011); Sharma (2017); Rokade
antibacterial activity et al. (2017)
Silver Sensor technology, antimicrobial Gomez-Romero (2001); Qiu et al. (2004);
activity, biological leveling, and AshaRani et al. (2009); Li et al. (2011);
various other biomedical uses Pollini et al. (2011); Patil et al. (2012);
Bindhu and Umadevi (2014); Ashokkumar
et al. (2015)
Palladium Catalysis, electrocatalysis, sensing, as Gopidas et al. (2003); Chen et al. (2007);
well as plasmonic wave guiding and Chen et al. (2010); Coccia et al. (2012);
antibacterial activity West et al. (2010); Rokade et al. (2017)
6  Recent Trends and Advancement Toward Phyto-mediated Fabrication of Noble… 89

Fabrication
of
NMs
or
metallic NMs
or
noble metallic NMs

Top Bottom
to to
down strategy up strategy

Physical processes Chemical/electrochemical Green chemistry routes

Mechanical/ball milling, diffusion processes Bacteria,
flame, chemical etching, Precipitation, vapor deposition, actinomy cetes,
thermal/laser ablation, sputtering, atomic/molecular condensation, yeasts, fungi,
microwave, ultrafilms, plasma sol-gel process, spray pyrolysis, algae, plants
arching, molecular beam epistaxis, laser pyrolysis as well as
lithography aerosol pyrolysis

High consumption of energy,

application
of toxic chemicals, organic
solvents,
and stabilizing
agents

Fig. 6.1  Various strategies employed for the fabrication of metallic NMs including noble
metallic NMs

outwardly precise apparatuses are employed so as to cut and mill for shaping the
substances to anticipated order. Many physical fabrication approaches such as
lithography, pyrolysis, thermolysis, etc., are included in this group (Li et al. 1999;
Tsai et al. 2004; Shubin et al. 2012). The main limitation associated with top to
down method is the inadequacy of the surface assembly of metal NMs that exhibit
a substantial impact upon their physical as well as surface chemistry characteristics
(Treguer et  al. 1998). Additional drawback involves requirement of mammoth
energy for maintaining the high magnitude of pressure and temperature during
such fabrication process (Li et al. 1999; Treguer et al. 1998). However, the bottom
90 S. P. Singh et al.

to top technique involves the fabrication of metallic NMs primarily because of

gathering of the atoms/molecules or the bunches (Thakkar et al. 2010). Such pri-
marily produced metallic NMs then consequently undergo clustering, which lead
to ultimate material by means of chemical/green chemistry approaches. This tech-
nique facilitates to achieve cost-­effective metal NMs having lower surface imper-
fection with more homogeneous chemical composition. This method is normally
exploited toward wet fabrication processes such as chemical, electrochemical,
sonochemical, and polyol reduction. Remarkably, these wet fabrication processes
are shown to be economical toward bulk production of NMs. Nevertheless, these
approaches are also found to depict limitations like wide exploitation of toxic com-
pounds, nonpolar organic solvents, and many stabilizing as well as nonnatural cap-
ping agents, thereby preventing their uses in the clinical as well as biomedical
field. In addition, the chemically synthesized NMs by this approach led to severe
environmental problems including biological systems (Xiong et  al. 2005;
Nemamcha et al. 2006; Pritchard et al. 2010; Gangula et al. 2011; Yang et al. 2013;
Mizukoshi et al. 2010; Devi et al. 2016). Considering these, there is a need to intro-
duce green chemistry strategy as simple, comparatively reproducible, and eco-
friendly alternative over fabrication of NMs. The green chemistry encompasses the
exploitation of a set of ideologies that decrease or get rid of the use/formation of
detrimental substances in the design, production, as well as application of chemical
products. Greener fabrication of NMs exhibits improvement as compared to physi-
cal/chemical approaches for being eco-friendly, simple, eye-catching, inexpensive,
as well as comparatively reproducible. It has the ability to often produce more
stable NMs. In this route, the biomolecules like proteins, terpenes, metabolites,
etc., of biological systems play a role as reducing, capping, as well as stabilizing
agents toward the fabrication of NMs with discrete shape and size. A critical review
of the literature reveals that several biological systems like microorganisms and
plants including human cells can translate metallic ions into metal or metal oxide
NMs (Patete et  al. 2011; Makarov et  al. 2014; Mohammadinejad et  al. 2016).
Among biological systems, microbes like bacterial, cyanobacterial, fungal, and
viral species/strains including actinomycetes are recognized as potential platform
for the fabrication of metallic NMs either intra- or extracellularly (Narayanan and
Sakthivel 2010). The microbe-based NM production rate is sluggish and results in
merely restricted number of sizes as well as shapes over plant-­based substances. In
this context, binary function of phytochemicals as reducing and stabilizing agents
(inexpensive), easy accessibility, the economical cultivation, simple process with
requirement of normal pressure as well as temperature (economical), lack of com-
plex as well as multistage processes such as isolation of microbes, culturing, main-
tenance, etc., biocompatibility of plant extracts (appropriate toward medicinal
application), lesser or no contamination (environmental friendly along with safe
toward human therapeutic application), and faster fabrication of NMs together
with the ability to easily scale up bulk production of NMs make plant systems as
eye-catching route for the NM fabrication together with metal/metal oxide over
other biological systems (Shankar et al. 2004a; Iravani 2011; Dhillon et al. 2012;
Dauthal and Mukhopadhyay 2016; Mohammadinejad et  al. 2016). Overall, the
6  Recent Trends and Advancement Toward Phyto-mediated Fabrication of Noble… 91

potential of plant system as bio-factory for the production of NMs is not only an
underexplored but also a profitable strategy (Harris and Bali 2008; Thakkar et al.
2010; Iravani 2011). Furthermore, plant system is found to be rich in a wide variety
of phytochemicals/biomolecules. Nevertheless, their potential is yet to be com-
pletely exploited under full control for fabricating NMs. Interestingly, it is feasible
for the fabrication of metallic NMs at commercial level with the help of plant tissue
culture methodologies coupled with optimizing the downstream processing (Jha
et al. 2009). This chapter provides an insight toward the recent trends and advances
of phyto-mediated synthesis of noble metallic NMs (silver, gold, platinum, and
palladium).

6.2  A
 n Overview on Phyto-mediated Fabrication of Metallic
NMs/Noble Metallic NMs

Bio-fabrication of metallic NMs by employing living plants (intracellular), plant

extracts (extracellular), as well as phytochemicals has received substantial interest
as suitable alternative over conventional physical as well as chemical approaches
(Iravani 2011). Figure 6.2 depicts the different strategies for the plant-based fabrica-
tion of metallic NMs including noble metallic NMs. The significance and advantage
of plant system-based fabrication of NMs enhances severalfold when the extracts of
cost-effective agricultural wastes are exploited toward the production of metallic
NMs. Nowadays, the investigators are exploiting the individual phytoconstituents
like polyphenols, proteins organic acids, etc. toward the production of metallic NMs
so as to achieve more control on size as well as morphology of NMs (Basha et al.
2010; Tamuly et al. 2014).
A critical review of literature revealed little reports on the intracellular produc-
tion of metallic NMs, which are not only tedious but also involve high-priced pro-
cessing stages for the recovery of the NMs from the biomass. As a result, merely
Medicago sativa, Brassica juncea, Sesbania drummondii, Chilopsis linearis,
Triticum aestivum, Avena sativa, as well as Festuca rubra are reported to date
toward the fabrication of different metallic NMs via intracellular strategy (Gardea-­
Torresdey et al. 2002, 2003, 2005; Armendariz et al. 2004a, b; Sharma et al. 2007;
Harris and Bali 2008; Marchiol et al. 2014). The foremost limitation of intracellular
approach involves the dissimilarities in reducing as well as stabilizing the ability of
phytochemicals/biomolecules present in various portions of plant system, which
leads to the production of extremely polydisperse metallic NMs of varied morphol-
ogies. Also, the tedious recovery of metallic NMs from plant biomass along with
little commercial feasibility of plant biomass-mediated fabrication of metallic NMs
has diminished the potential of this route.
In contrast, the extracellular fabrication of metallic NMs turns out to be an attrac-
tive strategy owing to effortless downstream processing as well as scaling up. The
extracellular approach of metallic NM fabrication employing plant extracts is more
common than intracellular approach because of its potential in various commercial
92 S. P. Singh et al.

Approaches for
fabrication of metallic
NMs or noble metallic
NMs using plant system

Intracellular fabrication Extracellular fabrication Phytochemical-based

fabrication

Living plant or plant Individual

Plant extract
biomass phytocomponent
+
+ +
metallic or noble metal
metallic or noble metallic metallic or noble metallic
salt solution
salt solution salt solution

Bioreduction process of metallic or

noble metallicion
Bioreduction process of Bioreduction process of
metallic or noble metallic or noble
metallicion metallic ion
Purification of metal or noble metal NMs from colloidal
solutions through solvent washing followed by
ultracentrifugation

Cellular disintegration
towards the recovery Purification of metal or noble metal NMs from individual
of metal or noble phytocomponent through approaches like ion exchange
metal NMs chromatography/electric charge-based electrophoresis/diafiltration, etc.

Fig. 6.2  Various plant system-based strategies toward the production of metallic NMs/noble
metallic NMs

uses. Usually, the exploitation of plant extract is found to assist the formation of
NMs with highly energetic favorable spherical shape as well as more reactive fcc
structure. Interestingly, the spherical shape and desired growth together with (111)
plane facilitate the reactivity of NMs toward many industrial uses. This fact advo-
cates that plant extract-based reduction is a regulated equilibrium process, which
controls the formation of NMs up to particular shape as well as structure, thereby
revealing the significance of this route. Nevertheless, it is extremely challenging to
reproduce metallic NMs having monodispersity with definite surface morphology
because of definitely varying phytochemical components along with structure of
6  Recent Trends and Advancement Toward Phyto-mediated Fabrication of Noble… 93

plants from diverse origins (Ahmed et  al. 2014). Besides, there is often more
possibility for the presence of contaminations with plant biomasses/agricultural
wastes. Thus, it is extremely problematic for the synthesis of metallic NMs having
desired size as well as morphology. However, such desired metallic NMs could be
fabricated merely as a result of exploitation of particular phytochemical/biomole-
cule derived from specific portion of plant biomass/living plants. This must be fol-
lowed when the focus is to fabricate metallic NMs with high monodispersity as well
as desired surface morphology. Several investigators have found the biosynthesis of
metallic NMs using plant extracts with their promising uses in various fields
(Niraimathi et al. 2013; Seralathan et al. 2014).
The fabrication of metallic NMs using plant extract is linked with the issue of
varied phytochemical composition (Ahmed et al. 2014). As a result, it is extremely
challenging to forecast the precise mechanism of metallic NM production employ-
ing plant extracts. Nevertheless, there are few investigations which forecasted the
function of polyphenols as well as flavonoids toward the formation and stabilization
of metallic NMs (Basha et al. 2010; Tamuly et al. 2014). Considering this, it is essen-
tial to recognize the exact phytoconstituents accountable toward production of
NM. Therefore, investigators are concentrating on the isolation of specific antioxi-
dant phytoconstituents for formation of metallic NMs. To date, merely limited stud-
ies have been carried out concerning phytoconstituents that are straightforwardly
exploited toward the production of metallic NMs (Kasthuri et al. 2009a, b; Basha
et al. 2010; Safaepour et al. 2009; Singh et al. 2010; Govindaraju et al. 2011; Leonard
et al. 2011; Ahmed et al. 2014; Durai et al. 2014; Iram et al. 2014; Tamuly et al. 2014).

6.3  R
 ecent Fabrication Trends of Silver, Gold, Platinum,
and Palladium NMs Using Plant System

A perusal of literature exhibited that plant system can be effectively employed

toward the fast as well as extracellular fabrication of noble metallic NMs (Shankar
et al. 2004a, b; Kasthuri et al. 2009a; Kim and Song 2010). For instance, Shankar
et  al. (2003) conducted investigations on the fabrication of gold and silver NMs
using geranium leaves, where it was concluded that such noble metallic NMs can be
produced through the exploitation of plant extracts with rates analogous to chemical
approaches. Shankar et al. (2004b) also successfully carried out the phyto-­fabrication
of triangular gold nanoprisms as a result of reaction between lemongrass leaf extract
and aqueous AuCl4− ions. Furthermore, the leaf extracts of many plant systems like
Aloe vera, geranium, lemongrass, neem, and tamarind were not only exploited for
the reduction of gold ions into gold NMs but also silver ions to silver NMs (Chandran
et al. 2006; Shankar et al. 2003; Ankamwar et al. 2005a, b). In the same way, fabri-
cation of platinum as well as palladium NMs was also carried out by exploiting the
extracts of various portions of different plant species (Nadagouda and Varma 2008;
Lin et al. 2011; Coccia et al. 2012; Soundarrajan et al. 2012). Table 6.2 provides the
recent fabrication trends of gold, platinum, silver, and palladium NMs using differ-
ent plant systems.
94 S. P. Singh et al.

Table 6.2  Phyto-mediated synthesis of silver, gold, platinum, and palladium NMs
Nature of
noble
metallic
Plant system NMs Size (nm) Morphology/ Shape References
Tamarindus indica Gold 20–40 Triangular Ankamwar et al.
(2005a)
Aloe vera Gold and Not Spherical and triangular Chandran et al. (2006)
silver reported
Cinnamomum Gold and 55–80 Triangular, spherical Huang et al. (2007)
camphora silver (gold) and quasi-
spherical (silver)
Azadirachta indica Gold 5.5–7.5 Crystalline Ramezani et al. (2008)
Eucalyptus Gold 5.5–7.5 Crystalline Ramezani et al. (2008)
camaldulensis
Pelargonium Gold 5.5–7.5 Crystalline Ramezani et al. (2008)
roseum
Cinnamomum Palladium 15–20 Crystalline Sathishkumar et al.
zeylanicum (2009a)
Curcuma longa Palladium 10–15 Spherical Sathishkumar et al.
(2009b)
Gardenia Palladium 3–5 Not reported Jia et al. (2009)
jasminoides
Chenopodium Gold and 10–30 Quasi-spherical Dwivedi and Gopal
album silver (2010)
Musa paradisiaca Palladium 50 Crystalline irregular Bankar et al. (2010)
Ocimum sanctum Silver 5–10 Spherical Ahmad et al. (2010)
Mangifera indica Gold 17–20 Spherical Philip (2010)
Diospyros kaki Platinum 2–12 Crystalline Song et al. (2010)
Nyctanthes Gold 19.8 Spherical, triangular, Das et al. (2011)
arbor-tristis and hexagonal
Memecylon edule Silver 20–50 Triangular, circular and Elavazhagan and
hexagonal Arunachalam (2011)
Cuminum Gold 1–10 Spherical Krishnamurthy et al.
cyminum (2011)
Murraya koenigii Gold 20 Spherical and triangular Philip et al. (2011)
Vitex negundo Silver 5 and Spherical and fcc Zargar et al. (2011)
10–30
Beta vulgaris Gold Not Spherical, rod-shaped, Castro et al. (2011)
reported and nanowires
Cymbopogon Silver 32 Not reported Masurkar et al. (2011)
citratus
Sphearanthus Gold 39 Spherical Nellore et al. (2012)
amaranthoids
Pinus resinosa Platinum 6–8 Irregular Coccia et al. (2012)
Pinus resinosa Palladium 16–20 Spherical Coccia et al. (2012)
(continued)
6  Recent Trends and Advancement Toward Phyto-mediated Fabrication of Noble… 95

Table 6.2 (continued)
Nature of
noble
metallic
Plant system NMs Size (nm) Morphology/ Shape References
Trigonella Gold 15–25 Spherical Aromal and Philip
foneumgraecum (2012)
Glycine max Palladium 15 Spherical Petla et al. (2012)
Thevetia peruviana Silver 10–30 Spherical Rupiasih et al. (2013)
Rosa hybrid Gold 10 Spherical, triangular, Singh et al. (2013)
and hexagonal
Alternanthera Silver 50–100 Spherical Kumar et al. (2014)
dentata
Angelica, Gold 4–8 Spherical, ovals, and Pasca et al. (2014)
Hypericum, and polyhedral
Hamamelis
Acorus calamus Silver 31.83 Spherical Nakkala et al. (2014)
Podophyllum Gold 5–35 Spherical and triangle Jeyaraj et al. (2014)
hexandrum L.
Gardenia Palladium 3–5 Not reported Khan et al. (2014)
jasminoides
Pistacia atlantica Silver 10–50 Spherical Sadeghi et al. (2015)
Punica granatum Platinum 16–23 Spherical Dauthal and
Mukhopadhyay (2015)
Ficus carica Silver 13 Not reported Ulug et al. (2015)
Stachys Gold 34–80 Spherical and triangle Khademi-Azandehi
lavandulifolia and Moghaddam
(2015)
Diospyros Silver 14–28 Spherical Rao et al. (2016)
paniculata
Ocimum sanctum Gold 1–50, Circular disks with Lee et al. (2016)
10–300, rough edges, spherical
50–300, and large, anisotropic
and >200 platelets with defined
edges
Parkia roxburghii Gold and 5–25 Spherical and Paul et al. (2016)
silver quasi-spherical
Prunus × Platinum 10–50 Spherical and oval Velmurugan et al.
yedoensis (2016)
Piper longum Gold 20–200 Spherical Nakkala et al. (2016)
Dioscorea alata Silver 10–20 Polycrystalline and face Pugazhendhi et al.
centered cubic (2016)
crystalline
Pimpinella Palladium 12.25 Spherical Narasaiah et al. (2017)
tirupatiensis
Rhus chinensis Gold 20–40 Oval and spherical Patil et al. (2017)
Gloriosa superba Platinum 0.8–3 Spherical Rokade et al. (2018)
(continued)
96 S. P. Singh et al.

Table 6.2 (continued)
Nature of
noble
metallic
Plant system NMs Size (nm) Morphology/ Shape References
Gloriosa superba Palladium 5–8 Spherical Rokade et al. (2018)
Saudi’s Dates Platinum 1.3–2.6 Spherical Al-Radadi (2019)
Cannabis sativa Gold 12–18 Quasi-spherical, Singh et al. (2018)
spherical with few
triangular, rods, and
hexagonal
Cannabis sativa Silver 20–40 Spherical Singh et al. (2018)
Caesalpinia ferrea Silver 30–50 Spheroidal Soares et al. (2018)
(Tul.)
Phoenix Silver 43 Not reported Qidwai et al. (2018)
sylvestris L.

6.4  G
 eneral Mechanism of Silver, Gold, Platinum,
and Palladium NM Fabrication in Plant System

The general mechanism of fabrication of metallic NMs like silver, gold, platinum,
and palladium using plant system/plant extract as detailed in Iravani (2011) consists
of three steps: (a) activation step, (b) growth step, and (c) termination step. In the
activation step, reduction of metallic ions as well as nucleation of the reduced metal-
lic atoms takes place. In the subsequent step (growth stage), the small adjacent NMs
spontaneously combine into larger size particles with enhancement in thermody-
namic stability of NMs. Remarkably, the termination step is accountable for defin-
ing the ultimate shape of the NMs. Figure 6.3 summarized the general mechanism
of fabrication of metallic NMs including silver, gold, platinum, and palladium. As
the time period of the growth step enhances, NMs undergo aggregation that results
into the formation of nanotubes, nanoprisms, and nanohexahedrons including vari-
ous other arbitrarily shaped NMs.

6.5  K
 ey Factors/Parameters for Optimal Fabrication
of Silver, Gold, Platinum, and Palladium

The following important factors/conditions must be considered for optimal synthe-

sis including fabrication of extremely stable metallic NMs like silver, gold, plati-
num, and palladium using plant system (Iravani 2011):
(a) Selection of the best plant system: Among plant system, investigators have
emphasized the key inherent features of the candidates like enzyme activities
as well as biochemical routes. For instance, plant systems having massive
6  Recent Trends and Advancement Toward Phyto-mediated Fabrication of Noble… 97

Metallic ions such as ions of silver or gold or platinum or palladium binds to the
plant-reducing agents like terpenoids, polyphenols, sugars, alkaloids, phenolic acids,
and proteins

Reduction

Reduced metallic atoms of silver or gold or platinum or palladium

Nucleation

Organic “coat” stabilizing the metallic nanomaterial of silver or gold or platinum or

palladium
(growth as well as union of distinct small particles into larger ones happens by the
process of coarsening that continues till the particles adopt a stable shape and size)

Fig. 6.3  Mechanism of fabrication of metallic NMs (like silver, gold, platinum, and palladium)
using plant system/plant extract

potential for accumulation of heavy metal as well as detoxification are the best
organisms for the fabrication of metallic NMs including silver, gold, platinum,
and palladium.
( b) Optimal reaction conditions: In an attempt to exploit the plant systems toward
the fabrication of metallic NMs such as silver, gold, platinum, and palladium at
industrial scale, the yield and the production rate are the key issues that need to
be focused. Further, there is a need to carry out optimization of the bioreduction
environments of the reaction mixture. The metal salt concentration, the plant
extract quantity, pH, incubation period of reaction mixture, temperature, and
buffer strength need to be regulated and optimized. Optimization of these
important parameters might regulate morphologies as well as other properties
of metallic NMs including silver, gold, platinum, and palladium.

6.6  C
 haracterization of Metallic NMs (Silver, Gold,
Platinum, and Palladium)

Characterization of fabricated silver, gold, platinum, and palladium is essential as it

allows to comprehend as well as to confirm the effectiveness of fabrication approach.
Even though the technique is exploited toward fabrication, the NMs are usually
characterized for different physicochemical properties (size, shape, surface
98 S. P. Singh et al.

Fabricated
silver, gold, platinum,
and
palladium NMs

Characterizationparameter of fabricated metallic NMs

Nature Particle size

Charge determination Chemical analysis of surface
of of
of silver, gold, platinum, of silver, gold, platinum,
silver, gold, platinum, and silver,gold, platinum, and
and palladium NMs and palladium NMs
palladium NMs palladium NMs

Techniques Techniques Techniques Techniques

TEM, DLS, laser FTIR, SEM, TGA, and

UV-Vis. spectroscopy, Zeta potentiometer
diffractometry, static secondary ion mass
XRD, and EDX and XPS
and AFM spectrometry

Fig. 6.4  Overview on characterization of silver, gold, platinum, and palladium NMs using various
techniques

p­roperties, phase constitution, as well as microcrystal structure). Commonly

exploited methodologies toward the characterization of silver, gold, platinum, and
palladium NMs are UV-Vis spectroscopy, atomic force microscopy (AFM), infrared
spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectros-
copy (XPS), transmission electron microscopy (TEM), dynamic light scattering
(DLS), powder X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy
(EDX), Fourier-transform infrared spectroscopy (FTIR), extended X-ray absorption
fine structure (EXAFS), thermogravimetric analysis (TGA), nuclear magnetic reso-
nance (NMR), and nanoparticle tracking analysis (NTA). Figure 6.4 summarizes the
various techniques used for the characterization of silver, gold, platinum, and pal-
ladium NMs.

6.7  Conclusions and Future Perspective

It is concluded that the conventional physical and chemical approaches toward NM

fabrication are associated with at least one or more disadvantages. In view of the
benefits as well as disadvantages of conventional NM fabrication approaches, one
should select an ideal approach that is eco-friendly, economical, and effortlessly
scalable and controllable with monodisperse fabrication with minimum steps along
with least energy prerequisite. In this context, biogenic fabrication of NMs includ-
ing metallic NMs emerged as the utmost cost-effective as well as eco-friendly
approach over conventional physical and chemical approaches. Among different
biogenic fabrication, microorganisms can be exploited for silver, gold, platinum, as
well as palladium NM synthesis, but the rate of production is slow, and merely a
limited number of sizes and shapes are attainable over plant system. The plant
6  Recent Trends and Advancement Toward Phyto-mediated Fabrication of Noble… 99

system is rich with a wide variety of phytochemicals/biomolecules, which act as

reducing, capping, and stabilizing agents during fabrication of silver, gold, plati-
num, as well as palladium NMs. The potential of plant system as bio-factory for
the production of metallic NMs including silver, gold, platinum, as well as palla-
dium is under exploration as beneficial strategy. But their potential is yet to be
completely exploited under full control for fabricating NMs together with noble
metals. Furthermore, it is feasible for the fabrication of metallic NMs at commer-
cial level with the help of in vitro culture techniques along with optimization of
downstream processing. A detailed understanding of biochemical mechanisms
associated with the phyto-­mediated NM fabrication is a prerequisite so as to enable
this strategy to be economically competitive with the traditional approaches.
Nevertheless, it is menacing because of the complexity as well as huge variability
among various plant systems. A critical review of literature revealed various reports
with a proposed mechanism of phyto-mediated NM fabrication, where nearly all
are just reasonable hypotheses lacking substantial investigational backing. As the
hypotheses also differ with different plant species, therefore comprehensive assess-
ment is needed so as to comprehend the real mechanism of NM fabrication of a
specific plant system, which still remains a key problem. Achieving high reproduc-
ibility, maximizing homogeneity, as well as scaling up of NMs production are
important bottlenecks toward metallic NM synthesis employing plant systems.
Further experimentations are also needed in order to appraise the long-term stabil-
ity of phyto-fabricated NMs including silver, gold, platinum, as well as palladium.

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Chapter 7
Development of Environmental Biosensors
for Detection, Monitoring, and Assessment

Shagun Gupta and Vipan Kakkar

7.1  Introduction

Whatever that can be around us comprises our environment. Environment is

­everything that boosts our ability to live on the planet earth including the chemical,
physical, and various other natural forces. It makes up our surroundings along with
all the nonliving and living things like the water covering most of the earth’s sur-
face, the air we breathe, the soil, the animals and plants near us, the insects, and
much more. Living things such as human beings constantly interact with each other
and with their environment and try to adapt themselves as per its conditions in order
to survive, forming an ecosystem  – a functional unit of environment (Health &
Science 2011). Since several years, scientists have been carefully analyzing this
interaction and examining the different ways in which the humans affect their envi-
ronment. Human beings are playing with natural environment to make their own
lives’ comfortable. As we know, every coin has two sides, and a rose has also a
thorn: the same is true with modernization. There is no doubt that modern tech-
niques play a significant role in making humans’ lives easy, but they are also associ-
ated with major drawbacks that affect our environment badly. Scientists have
observed increasing cases of air and water pollution, acid rains, deforestation,
change in climate such as global warming, and many other problems which are
dangerous not only to the earth but also to ourselves (Fact Monster 2017). Figure 7.1
shows the effect of human activities on the environment. There have also been sub-
stantial occurrences of various natural calamities like cloud bursting, earthquakes,
tsunamis, etc. in the past few years. So, proper monitoring of environment is the

S. Gupta · V. Kakkar (*)

School of Electronics & Communication Engineering, Shri Mata Vaishno Devi University,
Katra, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 107

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_7
108 S. Gupta and V. Kakkar

IRONMEN
NV

T
E
ATMOSPHERE

HUMAN
SOIL ACTIVITIES WATER

OVERALL CLIMATE
LIFE CHANGE INCLUDING
AIR GLOBAL WARMING
POLLUTION

NOISE
SANITATION AND POLLUTION
HYGEINE, INADEQUATE
WATER AND WATER
POLLUTION

CONSTRUCTION (HOUSING,
BIOTHREATS (BOTH ROADS LEADING TO
CHEMICAL AND DEFORESTATION)
BIOLOGICAL AGENTS) RADIATION AGRICULTURAL
(IONIZING AND PRACITCES
ULTRAVIOLET) (PESICIDE-USE ETC.)

Fig. 7.1  Impact of human activities on environment

need of the hour so as to protect ourselves and the whole planet in general from such
life-threatening situations and also to prepare ourselves well in advance in order to
fight and survive such situations (Fact Monster 2017; Health & Science 2011).
Environmental monitoring basically refers to the ways by which we can interpret
the overall condition of our planet indicating how healthy it is. Global manage-
ment of environment firstly requires the thorough investigation of various pollutants
that are contaminating the air, water, food, soil, etc., which ultimately pose greater
ecological threats, and then to find and adopt ways to eliminate these pollutants
completely in the environment (Koedrith et al. 2015). Air pollutants originate from
various sources such as power plants, refineries, laboratory and industrial processes,
vehicle emissions, etc. Sulfur and nitrogen dioxide, volatile organic compounds,
carbon monoxide, particulate matter, etc. are some of the major air contaminants.
Water and soil pollutants are generally categorized as either radioactive elements
(such as tritium), or microbiological (such as coliform) or inorganic compounds
(like arsenic), or synthetic organic elements (like pesticides, herbicides, wee-
dicides, etc.). Some volatile organic compounds like benzene also contribute in
increasing water and soil pollution. Nowadays, food safety and biothreats are other
major concerns gaining much attention (Singh 2017). Figure 7.2 specifies the vari-
ous ways needed to be adopted in order to deal with these several environmental
contaminants.
Strict regulations have been imposed by the US Environmental Protection
Agency (US EPA) on the concentrations of various air and water contaminants pres-
ent in the environment. However, traditional detection and monitoring techniques
(like different chromatographic techniques (Justino et al. 2017; Lang et al. 2016;
7  Development of Environmental Biosensors for Detection, Monitoring, and Assessment 109

ENVIRONMENTAL
HEALTH
MANAGEMENT

THE WATER WE DRINK

By treating and inspecting the quality of drinking water and
examining the septic tanks from time to time in order to prevent
the water-borne diseases

THE AIR WE BREATHE

By monitoring and testing the quality of air in our surroundings
including the places we live and work so as to reduce the impact
of various air pollutants on living beings

THE FOOD WE EAT

By investigating, analyzing and educating

Inspecting the quality of food in restaurants, investigating the

effect of pesticides etc. on crops and vegetables and washing
these carefully before cooking, and examining the hygiene of
grocery stores can reduce the foodborne illness

Fig. 7.2  Different ways to reduce the impact of environmental pollutants on health

Hassani et  al. 2017) are complex, time-intensive, and costly and require skilled
labor and proper laboratory facilities with existing limitations in analytical and sam-
pling methods (Ho et  al. 2005; Looney and Falta 2000; Koedrith et  al. 2015).
Moreover, these conventional techniques also lack the efficiency when used for in
situ measurements essential in emergency situations such as in the cases of acute
poisoning, epidemics, or accidental release of biothreats or pesticides (Arduini et al.
2013; Guo et al. 2017; Zhang et al. 2014). Thus, in order to overcome the magnifica-
tion of various environmental issues, there is urgent need of highly sensitive, rapid,
cost-effective, miniaturized, portable, and easy-to-operate techniques and devices
that can detect and monitor various contaminants responsible for the destruction of
ecosystem (Zhang et al. 2014; Guo et al. 2017; Arduini et al. 2013). Advancements
in nanotechnology and biosensing techniques have made it possible to design such
devices that can achieve all the aforesaid objectives. The analytical performance
such as limit of detection, sensitivity, and specificity, especially for in situ applica-
tions, has been improved to a greater extent with the development of smart and rapid
biosensors employing various nanocomposites or nanomaterials to detect distinct
environmental pollutants (Maduraiveeran and Jin 2017; Zhao et al. 2013).
The subsequent sections of this chapter describe the various available biosensing
techniques and explore their potential for the monitoring and detection of environ-
mental pollutants.
110 S. Gupta and V. Kakkar

7.2  Biosensing Techniques

The term “biosensor” is short form of “biological sensor.” A biosensor is an analyti-

cal device that is made up of a biological component with a physicochemical detec-
tor. The biological element (e.g., an enzyme, cell receptors, organelles, a nucleic
acid, an antibody, etc.) interacts with the analyte being tested producing a biological
response, and then the transducer converts this biological response mostly into an
electrical signal (Robertson 2019) which can be more easily measured and quanti-
fied. The detector element or the transducer works in either one of the following
physicochemical ways: optical, piezoelectric, electrochemical, electrostatic, or
electromechanical. Depending on their specific application, biosensors are also
known as optrodes, immunosensors, resonant mirrors, biochips, chemical canaries,
biocomputers, and glucometers (Robertson 2019; Monošík et al. 2012).

7.2.1  Biosensor System

Every biosensor comprises a bio-recognition component, bio-transducer compo-

nent, and electronic system which includes a signal amplifier, processor, and dis-
play. A typical biosensor system with its working principle is shown in Fig. 7.3.

7.2.2  Classification of Biosensors

As shown in Fig. 7.3, biosensors can be designed to detect and identify different

bio-recognition components using different transduction principles. So, they can be
classified based on these two criteria as shown in Fig. 7.4 (Monošík et al. 2012). The
brief description of each biosensor type is given below:

Piezoelectric Amplifiers
Antibody Mass change
Transduction
Analog to digital
Tissue Electroactive covertors
Material Electrodes
Nucleic Acid Filters
Semconductig Electrical
pH change
pH electrode Signal
Bacteria Multiplexers
Light Photodetector
Cell Compressors

Organelle Heat Themistor Lineraizers

Molecular
Analyte recognizers or Transducer Signal conditioning
Bioreceptors circuit

Fig. 7.3  Working principle of biosensors. (Vargas-Bernal et al. 2012)

7  Development of Environmental Biosensors for Detection, Monitoring, and Assessment 111

Genosensors Immnosensors
Whole-Cell Aptasensors
(Nucleic Acid- (Antibody-based)
based (Aptamers-based)
based) Biomimetic
Enzymatic
(Enzyme-based) Biosensors

CLASSSIFICATION OF
BIOSENSORS

BIORECOGNITION ELEMENT

SIGNAL TRANSDUCTION PRINCIPLE

Electrochemical Magnetic
Biosensors Thermometric Biosensors
Optical
Mass-based Biosensors Biosensors
Biosensors
(Piezoelctric, magnetoelastic)

Fig. 7.4  Classification of biosensors

7.2.2.1  On the Basis of Bio-recognition Element

Biosensors can be used to detect either natural biological materials (such as micro-
organisms, antibodies, nucleic acids, enzymes, cell receptors, tissues, organelles,
other natural products, etc.), or biologically derived materials (like aptamers, vari-
ous engineered proteins including DARPins (designed ankyrin repeat proteins),
bones, biomass, recombinant antibodies, etc.), or biomimics (such as synthetic
receptors, combinatorial ligands, biomimetic catalysts, imprinted polymers, etc.)
(Hashemi Goradel et al. 2018; Justino et al. 2017; Lu et al. 2017). Based on these
recognition elements, biosensors are classified as:

Immunosensors

Immunosensors make use of the specific binding feature of an antibody and antigen
(Salvador et al. 2007). In these types of biosensors, antibodies are used as recogni-
tion receptors. Antibodies are organic compounds that have the capability to control
the grafting process and physicochemical superficial properties so as to improve the
detection specificity and sensitivity (Vargas-Bernal et al. 2012). Such biosensors are
highly selective in detecting various analytes owing to the availability of a wide
range of affinities. Further, monoclonal antibody technology (Peterson 2005) if
used with immunosensors can result in better screening of antibodies with defined
biological and chemical properties at affordable costs.
112 S. Gupta and V. Kakkar

Enzymatic Biosensors

These biosensors use enzymes as recognition elements owing to their easy avail-
ability, varied functionality, and high specificity (Hashemi Goradel et  al. 2018).
Enzymatic biosensors are catalytic biosensors based on the principle of the conver-
sion of a non-detectable substrate into an electrochemically or optically detectable
product (Salvador et al. 2007). Inhibitors, substrates, and modulators of catalytic
reaction can be detected using these sensors. This process allows the detection of
substrates, products, inhibitors, and modulators of the catalytic reaction. Such bio-
sensors can operate in either direct mode or indirect mode. Direct mode involves the
monitoring of concentrations of analytes and products formed during enzymatic
reactions, whereas indirect mode monitors the enzyme inhibition by the analyte
(Nigam and Shukla 2015; Rebollar-Pérez et al. 2016). For the detection of various
environmental pollutants, indirect mode is more favorable. For the successful bio-
sensor design, immobilization of enzyme on the solid surface is one of the crucial
steps. Immobilized enzymatic biosensors are more advantageous in comparison
with the free enzyme-based sensors as they are rapid, require minimal amounts of
sample, and are more sensitive as interference by the differential mode is less in
these biosensors (Vargas-Bernal et al. 2012; Nigam and Shukla 2015).

Whole-Cell Based Biosensors

Whole cells (fungi, yeast, bacteria, or eukaryotic cells) can also be used as bio-­
recognition element as they are better sources of enzymatic activities than isolated
enzymes (Salvador et al. 2007; Gutiérrez et al. 2015). Whole-cell-based biosensors,
like yeast biosensors, microbial biosensors, etc. utilize the immobilization tech-
niques in order to immobilize the cells on transducer electrode. Such sensors are
useful especially when detection of noncommercially available or expensive
enzymes is needed (Ahmed et al. 2014; Hashemi Goradel et al. 2018).

Genosensors

In these types of biosensors, bio-recognition component is a class of small biomol-

ecules or biopolymers known as nucleic acids. Nucleic acids include DNA and
RNA which are very large and complex forms of organic molecules and contain the
genetic information and code of an organism. These are composed of nucleotides
and are essential to all known forms of life (Antonio Blanco 2017). The working of
DNA-based biosensors relies on the principle of hybridization of complementary
strands of DNA in a highly specific manner. Selection of probe and immobilization
plays a significant role in the construction of a genosensor (Hashemi Goradel et al.
2018). Genosensors have a wide range of applications in various fields like in medi-
cal diagnostics for the detection of genetic diseases, in forensic medicine, in envi-
ronmental monitoring to control food and water contamination, for the detection of
various pathogens, and so on (Valle 2011; Orozco et al. 2016).
7  Development of Environmental Biosensors for Detection, Monitoring, and Assessment 113

Aptasensors

Aptasensors are also DNA-based sensors in which selected DNA plays the role of a
highly specific receptor of chemical or biological species (Hashemi Goradel et al.
2018). Aptasensors use aptamer, an artificial nucleic acid ligand, as bio-recognition
agent. Aptamers can be generated against proteins, amino acids, drugs, and other
molecules (O’sullivan 2002). The utilization of aptamers in biosensors for the detec-
tion of biomolecules has many advantages when compared with the use of antibod-
ies due to the chemical stability, cost-effectiveness, and smaller size of aptamers
(Lim et al. 2010).
Genosensors and aptasensors are the affinity-based DNA biosensors in which a
DNA probe is used to capture an analyte or target. The other category of DNA bio-
sensors based on the catalytic capability of DNA is termed as catalytic-based DNA
biosensors. DNAzymes and aptazymes fall under this category of DNA-based bio-
sensors (Hashemi Goradel et al. 2018). DNAzymes are not found in nature and are
basically catalytically active DNA molecules that are obtained and isolated via
in vitro selection (Zhou et al. 2017). Aptazymes are ligand-activated self-cleaving
ribozymes containing integrated aptamer domains and generated by combining
DNAzymes, used for chemically modifying nucleic acids, and aptamers, required
for binding a broad range of molecules (Zhou et al. 2017; Tang et al. 2017; Hashemi
Goradel et al. 2018).

Biomimetic Biosensors

In these biosensors, non-biological receptors are used as bio-recognition element as

these receptors have the capability of mimicking the behavior of natural biomole-
cules. Biomimetic biosensors can be used to analyze the sense of taste, an indis-
pensable perception of human sensory organ. Sense of taste refers to the five basic
tastes including bitterness, sourness, sweetness, umami, and saltiness (Lu et  al.
2017). These biosensors also find applications in medical diagnostics, in monitoring
environment and food safety, etc. (Kozitsina et al. 2018; Huffman et al. 2017).

7.2.2.2  On the Basis of the Transduction Principle

The transducer is an imperative part of a biosensor since it is responsible for the

conversion of a biological or biochemical response into an analyzable and measur-
able electrical signal. Selection of a transducer for a particular application is cru-
cial because appropriate transducers have a dramatic role in providing the optimum
detection with high sensitivity and specificity (Salvador et  al. 2007). Different
transduction mechanisms are available for designing a biosensor, and according to
these signal transduction principles, biosensors can be classified in the follow-
ing ways:
114 S. Gupta and V. Kakkar

Electrochemical Biosensors

The electrochemical transducers are one of the most developed biosensors available
in the literature (Rebollar-Pérez et al. 2016). An electrochemical biosensor exploits
the various physicochemical properties of electroactive substances and detects these
properties in order to realize the bio-recognition so as to provide a measurable sig-
nal such as electrical voltage, current, impedance, or superficial charge (Vargas-­
Bernal et  al. 2012). Depending on the measured electrical signal and mode of
electrical measurement, electrochemical biosensors can be subdivided into different
categories such as potentiometric (measurement of voltage), amperometric (mea-
surement of current), chronoamperometric, conductometric, impedimetric (resis-
tive, capacitative), coulometric, and field-effect transistors (Vargas-Bernal et  al.
2012; Salvador et al. 2007; Hashemi Goradel et al. 2018; Semantic Scholar 2013).
In chronoamperometric transduction technique, the working electrode potential is
stepped which produces the current as a function of time by using faradaic pro-
cesses. This technique is useful for analyzing the kinetics of chemical reactions, for
monitoring the adsorption and diffusion processes, and for measuring protein and
protease activity (El Harrad and Amine 2017). Conductometric technique depends
on the current produced by ions in solution, while impedimetric transduction refers
to the measurement of impedance (voltage as a function of the current). The perfor-
mance of both these biosensing methods is highly influenced by a sensing layer
placed between the two electrodes (Salvador et  al. 2007). Field-Effect Transistor
(FET) based Biosensor mechanism is based on the measurement of current which is
varied due to the potentiometric effect at a gate electrode (Guiseppi-Elie and
Lingerfelt 2005). Coulometric biosensing principle is based on the exhaustive elec-
trolysis of analyte by which we can determine the unknown analyte concentration
in a solution. This is done by converting the analyte completely from one oxidation
state to another (Chemicool Dictionary 2017; David Harvey 2019).

Optical Biosensors

Optical biosensors rely on the principle of detecting the alterations in various

optical properties such as adsorption, reflectance, refractive index, scattering of
light, absorbance, luminescence (bioluminescence, chemiluminescence), fluores-
cence, etc. (Mishra et al. 2017). Optical techniques can be used for the quantifica-
tion of an optical spectrum and for interpreting the changes in a mechanical
measure and are required for overall biological or chemical analysis (Fortin 2009).
The detection of analyte is usually done by employing electromagnetic radiations,
like ultraviolet (UV), infrared (IR), or other radiations (Hashemi Goradel
et al. 2018).
7  Development of Environmental Biosensors for Detection, Monitoring, and Assessment 115

Piezoelectric Biosensors

Piezoelectricity is an electrical effect caused by the variations in the material strain

(Fortin 2009). Piezoelectric biosensors are sensitive to changes in density, mass, or
viscosity of samples in the vicinity of its active surface (Hashemi Goradel et  al.
2018). Acoustic wave biosensors employ the piezoelectric transduction mechanism
for the detection of biomolecules. Such sensors are based on an oscillating crystal
resonating at the fundamental frequency. The bio-recognition element needed to
interact selectively with the target analyte is coated as a layer on the crystal element,
and when the binding of analyte on sensing surface takes place, the mass of crystal
changes which eventually changes the resonance frequency (Monošík et al. 2012).
Such biosensors are easy to operate and offer label-free on-line analysis at afford-
able costs. Cantilever biosensors are the other emerging class of mass-sensitive bio-
sensors that can achieve lower limit of detections when compared with conventional
methods (Salvador et al. 2007).

Thermometric Biosensors

Quantification of the release of thermal energy or the evolution and absorption of

heat during a biochemical reaction is the fundamental principle of thermometric
biosensors (Monošík et al. 2012; Hashemi Goradel et al. 2018). In these biosensors,
immobilized enzyme or cell is directly attached to a thermistor, and the resistance
of transducer changes as a result of the temperature variations in reaction medium
(Salvador et al. 2007; Monošík et al. 2012).

Magnetic Biosensors

Magnetic biosensors utilize magnetic particles (such as paramagnetic or super-­

paramagnetic particles or crystals) for detecting biological interactions (Nabaei
et al. 2018). The size of these particles ranges from micro- to nanometers, and their
surfaces are modified and functionalized in order to recognize and identify specific
biomolecules by measuring the variations in magnetic properties (magneto-optical
properties, resistance, etc.) or by analyzing magnetically induced effects such as
coil inductance alterations, Hall effect, giant magnetoresistance (GMR), etc.
(Monošík et al. 2012; Li and Kosel 2013; Rife et al. 2003).

7.3  Environmental Biosensors

Environmental monitoring is the need of the hour as it is required to protect the

whole ecosystem from various toxic pathogens and pollutants that are present and
can be released into different media including water, soil, food, and air. These
116 S. Gupta and V. Kakkar

e­nvironmental contaminants are associated with various diseases and thus are
­harmful to human health. Such pollutants in environment can be categorized into
two groups: organic and inorganic compounds. Organic pollutants include pesti-
cides, bisphenol A, surfactants, polycyclic aromatic hydrocarbons, hormones, linear
alkylbenzene sulfonates, polychlorinated biphenyls, phenols, dioxins, antibiotics,
alkanes, and toxins. Inorganic phosphates, metals, and nitrate are the types of inor-
ganic pollutants. In recent years, various biosensors including genosensors, aptas-
ensors, immunosensors, and enzymatic biosensors employing different transduction
mechanisms (Monošík et al. 2012) as mentioned in the previous section have been
reported for the monitoring and detection of several environmental pollutants
(Rebollar-Pérez et al. 2016). Some of these pollutants are explained in this section,
and the different biosensor detection systems developed to detect these pollutants
are also discussed. Table 7.1 provides a summary of recently developed environ-
mental biosensors based on different principles with their detection limits.

7.3.1  Pesticides

Pesticides are one among the most important environmental pollutants and are sig-
nificantly present in the environment due to exhaustive utilization in agricultural
practices in order to increase the yield and crop productivity (Justino et al. 2017;
Hashemi Goradel et  al. 2018). Pesticides can be classified on the basis of their
chemical structures into organophosphate (parathion), synthetic pyrethroids,
organochlorine (atrazine), carbamate, and inorganic pesticides (Verma and Bhardwaj
2015). These pesticides are dangerous to health as they can cause respiratory and
immunological problems, nervous system disorders, and even cancers due to their
carcinogenic nature (Sassolas et al. 2012). For highly sensitive detection of these
pesticides without the requirement of sample pretreatment, various simple and min-
iaturized in situ biosensors have been developed (Justino et al. 2017; Vogrinc et al.
2015; Kim et al. 2015), and few of them are summarized in Table 7.1.

7.3.2  Pathogens

Pathogens are present in environmental matrices, especially in water compartments

(Koedrith et al. 2015). These pathogens (like Escherichia coli or E. coli) are danger-
ous to health and can cause several diseases. Some biosensors have been recently
proposed for the environmental monitoring of these pathogens and are described in
Table 7.1 (Justino et al. 2017; Liong et al. 2013; Vidic et al. 2017; Hashemi Goradel
et al. 2018).
Table 7.1  Recently developed biosensors for the detection of various environmental pollutants
Pollutant
category Target/analyte Transduction principle Bio-recognition element Limit of detection References
−1 −1
Pesticides Methyl Electrochemical (impedimetric) Enzyme (hydrolase [16], 0.1 ng mL 0.42 pg mL Zhao et al. (2013),
parathion acetylcholinesterase (AChE) Peng et al. (2017)
[49])
Electrochemical Enzyme (AChE) 5 fg mL−1 Deng et al. (2016)
Electrochemical (amperometric) 1.5–1.8 ng mL−1 Nunes et al. (2014)
Optical Sphingomonas sp. cells 0.01 ppm Mishra et al. (2017)
Atrazine Electrochemical (impedimetric) Aptamers 2.2 pg mL−1 Madianos et al.
(2018)
Electrochemical (amperometric) Phage/antibody (monoclonal) 0.2 pg mL−1 González-Techera
complex et al. (2015)
Electrochemical (FET) Antibodies (monoclonal) 0.01 ng mL−1 Belkhamssa et al.
(2016b)
Electrochemical (voltametric) 0.016 ng mL−1 Liu et al. (2014)
Carbofuran Electrochemical (amperometric) Enzyme (AChE) 0.5 pM, 136 pM Yang et al. (2013), Li
et al. (2017)
Electrochemical (voltametric) 3.6 nM Jeyapragasam and
Saraswathi (2014)
(continued)
7  Development of Environmental Biosensors for Detection, Monitoring, and Assessment
117
Table 7.1 (continued)
118

Pollutant
category Target/analyte Transduction principle Bio-recognition element Limit of detection References
Pathogens Escherichia coli Electrochemical (capacitive) Polymerizable form of 70 CFU mL−1 (CFU- Idil et al. (2017)
(E. coli) histidine colony forming unit)
Piezoelectric (QCM (quartz crystal 1.54 × 106 CFU mL−1 Yilmaz et al. (2015)
microbalance))
Optical (SPR (surface plasmon 3.72 × 105 CFU mL−1
resonance))
Optical 8 CFU mL−1 Chen et al. (2017)
(electrochemiluminescence)
Legionella Electrochemical (amperometric) Antibodies (polyclonal) 104 CFU mL−1 Martín et al. (2015)
pneumophila Optical (SPR) 103 CFU mL−1, Meneghello et al.
10 CFU mL−1 (2017), Manera et al.
(2013)
Optical (SPR) Nucleic acids 104 CFU mL−1 Yilmaz et al. (2015)
Bacillus subtilis Electrochemical (amperometric) Antibodies (polyclonal) 102 CFU mL−1 Yoo et al. (2017)
Potentially toxic Mercury ion Optical (fluorescence) DNA 17.6 nM Wu et al. (2016)
elements (Hg2+) Electrochemical (voltametric) Nucleic acids 3 fM Shi et al. (2017)
Optical (evanescent-wave optical 1.2 nM Long et al. (2013)
fiber)
Optical (SERS – surface 0.84 pM Yang et al. (2017)
enhancement Raman spectrum)
Zinc, cadmium Optical Microorganism (recombinant – Kim et al. (2015)
E. coli DH5)
Lead (Pb2+) Optical (fluorescence) Aptamers 61 nM Chen et al. (2018)
Optical (fluorescence) DNAzymes 5 nM, 16.7 nM Niu et al. (2018),
Ravikumar et al.
(2017)
S. Gupta and V. Kakkar
Toxins Saxitoxin Optical (interferometry) Aptamers 0.5 ng mL−1 Gao et al. (2017)
Electrochemical (voltametric) Cardiomyocyte cells 0.35 ng mL−1 Wang et al. (2015)
Domoic acid Electrochemical (FET) Antibodies (monoclonal) 10 ng mL−1 Marques et al. (2017)
Optical (SPR) Antibodies 1.66 ngmL−1, 0.1 ng mL−1 McNamee et al.
(2013), Colas et al.
(2016)
Brevetoxin-2 Electrochemical (voltametric) Cardiomyocyte cells 1.55 ngmL−1 Wang et al. (2015)
Electrochemical (impedimetric) Aptamers 106 pgmL−1 Eissa et al. (2015)
Endocrine-­ Bisphenol A Optical (fluorescence) Aptamers 0.1 ng mL−1, Ragavan et al. (2013),
disrupting 0.23 ng mL−1 He et al. (2017)
chemicals Optical (evanescent-wave optical 0.45 ng mL−1 Yildirim et al. (2014)
fiber)
Nonylphenol Electrochemical (FET) Antibodies (monoclonal) 5 ng mL−1 Belkhamssa et al.
(2016a)
17 β-Estradiol Photo-electrochemical Aptamers 33 fM Fan et al. (2014)
Electrochemical (capacitive) Antibodies 1 pg mL−1 Singh et al. (2017)
Electrochemical (voltametric) Antibodies 2.25 mL− Dai and Liu (2017)
7  Development of Environmental Biosensors for Detection, Monitoring, and Assessment 119
120 S. Gupta and V. Kakkar

7.3.3  Potentially Toxic Elements or Heavy Metals

Owing to industrialization, the amount of heavy metals (like zinc, mercury, copper,
etc.) in the environment has increased. Over the time, these metals accumulate in
the environment due to their nondegradable nature, and almost all these metals have
toxic effects and produce reactive oxygen species (ROS) (Gutiérrez et  al. 2015).
Water pollution caused by heavy metals and their respective ions can result in sev-
eral human health hazards. So, the rapid and highly sensitive on-field analysis of
heavy metals at affordable costs is a primary concern worldwide. Different portable
biosensors developed (Long et al. 2013; Kim et al. 2015; Hashemi Goradel et al.
2018; Justino et al. 2017; Vogrinc et al. 2015) for the detection of few of these met-
als are described in Table 7.1.

7.3.4  Toxins

Eutrophication of aquatic systems results in the algal blooms of cyanobacteria

which produces harmful toxins such as microcystins and brevetoxins, causing the
water pollution (Justino et al. 2017; Vogrinc et al. 2015). So, in order to prevent the
life-threatening situations, the early detection of such toxins is much needed. Cost-­
effective and reliable biosensor systems have been developed (Marques et al. 2017;
McNamee et al. 2013; Wang et al. 2015) in the recent years for the sensitive detec-
tion of various toxins as specified in Table 7.1.

7.3.5  Endocrine-Disrupting Chemicals (EDCs)

EDCs (such as bisphenol A, 4-nonylphenol, etc.) are present in our environment,

food, and consumer and personal care products and can interfere with our metabo-
lism, hormone biosynthesis, etc. (Diamanti-Kandarakis et al. 2009). They have been
suspected to be associated with the increased breast cancer incidences, immune
function variations, altered reproductive functions in females and males, abnormal
growth patterns, and neurodevelopmental delays in children (World Health
Organization 2012). Different biosensors (Justino et  al. 2017; Hashemi Goradel
et al. 2018; Vogrinc et al. 2015; Kim et al. 2015) developed for the detection of these
deadly EDCs are summarized in Table 7.1.
7  Development of Environmental Biosensors for Detection, Monitoring, and Assessment 121

7.3.6  Other Environmental Compounds

Apart from the abovementioned environmental contaminants, pollutants like harm-

ful algal blooms, pharmaceutical wastes, etc. are also present in the environment.
Electrochemical genosensors have been developed for the detection of Algal RNA
(Orozco et al. 2016; McPartlin et al. 2017). Pharmaceutical wastes contaminate the
water due to the improper excretion of beta-blockers, analgesics/anti-­inflammatories,
antihypertensive drugs, antibiotics, psychiatric drugs, and so on. Therefore, highly
sensitive and specific detection of these compounds is essential in order to prevent
life-threating effects on living organisms including humans. For pharmaceutical
detections, many enzyme-based biosensors based on the use of tyrosinases, lac-
cases, and peroxidases have been developed (Rebollar-Pérez et al. 2016).

7.4  Summary

In this chapter, different biosensing techniques and their applications in the detec-
tion of various environmental pollutants have been summarized. Development of
specific, rapid, sensitive, and cost-effective biosensors is crucial for the protection
of the ecosystem from life-threatening situations and for its survival in fluctuating
and harsh environmental conditions. Conclusively, for the overall environmental
management, we need to find and adopt certain ways and techniques that can reduce
the side effects of modernization and industrialization. The combined use of such
corrective measure techniques and biosensors will help in improving the environ-
ment quality and will protect the mankind from deadly situations, eventually mak-
ing the planet earth a healthy place to live in.

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Chapter 8
Nano-Based Materials and Their Synthesis

Shalini Chaudhary, Atin Kumar Pathak, and Shamshad Ahmad

8.1  Introduction

In recent years, a new promising research area – nanotechnology – has a great deal
of interest in various fields. Nanoparticles (NPs) are particulates characterized as
scatterings of strong particles with not less than one measurement of 10–1000 nm
in size. The surface region is the main vital element of NPs to volume proportion,
permitting corporation with different particles. However, it specifically implies the
precise manipulation of molecules and atoms in order to design and control of prop-
erties of the nanomaterial. Recently, in a couple of years, nanotechnology has
attracted an extraordinary interest due to its potential effects on various logical
ranges, for example, pharmaceutical industries, space and hardware businesses, etc.
Innovation of nanoparticles allows little estimated materials and structures in the
scope of couple of nanometers to fewer than 100 nm. Nanoparticles with the same
synthetic organization show extensively changed substance, organic and physical
properties, in view of their high surface-to-volume extent. Recently these particles
have been used in different fields of drug transport, hyperthermia of tumors, antimi-
crobial activities etc. (Fig. 8.1). A key domain of examination in nanotechnology
discusses about the combination of nanometer ranging particles of diverse sizes,
shapes, and monodispersity. Therefore, development of environmental-friendly and
cost-effective synthesis of nanoparticles is a crucial task. There are different

S. Chaudhary (*)
School for Environmental and Sustainable Development, Central University of Gujarat,
Gandhinagar, India
A. K. Pathak
Department of Energy Management, Sri Mata Visnao Devi University, Katra, India
S. Ahmad
Department of Environmental Science, Babasaheb Bhimrao Ambedkar University,
Lucknow, India

© Springer Nature Switzerland AG 2020 127

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_8
128 S. Chaudhary et al.

Fig. 8.1  Application of nanoparticle in various systems

­ icroorganisms possessing the ability to synthesize nanoparticles, having the ability

m
to be modified and exploited to fulfill the purpose. The metallic nanoparticles are
becoming increasingly important due to their potential application in many fields.
Thus using nanotechnology may extend service life, limit the potential for environ-
mental damage, and reduce failure rates. The present chapter focuses on providing
an overview and a discussion of metallic nanoparticle synthesis by various biologi-
cal and non-biological ways. Therefore, a green, nontoxic way of synthesizing
metallic nanoparticles is needed in order to allow them to be used in a wider range
of industries. This could potentially be achieved by using biological methods. This
review will focus on how material science and biology can work together to create
a green way of synthesizing metal nanoparticles for a wide range of uses.

8.2  Green Synthesis of MNPs (Biological/Bioreduction)

Much literature has been reported till date on the biological synthesis of MNPs
using microbes, i.e., bacteria and fungi, and plants, because of their antioxidant/
reducing properties typically responsible for reduction of metallic compounds to
their respective MNPs (Fig. 8.2). Since the early 19th century, plant extracts have
been known to have the ability to reduce MNPs, but the mechanism involved was
not well understood. Recently, in medical science, MNPs synthesized using green
technology have attracted a great deal of interest. Magnetic nanoparticles ­synthesized
using green technologies over chemical-based methods have several advantages,
i.e., more eco-friendly, easily scaled up, cost-effective, and comparatively require
8  Nano-Based Materials and Their Synthesis 129

Fig. 8.2  Parameters for producing biological nanoparticles

less energy, pressure, temperature, and other toxic chemicals. In the synthesis of
MNPs, plant extracts may act as both stabilizing and reducing agents which directly
influence the characteristics of nanoparticles (NPs). Different plant extracts contain
different phytoconstituents like catechins, flavonoids, polyphenols, enzymes, alka-
loids, vitamins, and functional groups, i.e., plant pigments, polysaccharide, tannins,
which are responsible for bioreduction process of metal salts to MNPs. Bioreduction
process typically involves simple mixing of aqueous extract with aqueous metallic
salt solution, and reaction is carried out at room temperature. The biological synthe-
sis of MNPs involves microorganisms and is considered as bottom-up approach. In
this process nanoparticle formation occurs due to oxidation of metal ions occurs in
presence of biomolecules i.e. sugars, enzymes, proteins secreted by microorgan-
isms. However, the complete mechanism for synthesis of metallic nanoparticles is
not well explored due to the fact that a different microorganism interacts differently
with metal ions. Thus the formation of nanoparticles by biochemical processing,
130 S. Chaudhary et al.

environmental factors, and its interaction ultimately determine the formation, size,
and morphology of the nanoparticle.

8.3  G
 reen Synthesis of Metallic Nanoparticles Using Plant
Extracts

The use of different parts of plant or plant extracts for synthesis of silver nanopar-
ticles has drawn attention, due to its economical, rapid, eco-friendly, non-­pathogenic,
and a single step technique for the biosynthesis processes. The stabilization and
reduction of silver metal ions by combination of biomolecules of plant extract, i.e.,
saponins, proteins, polysaccharides, amino acids, phenolics, enzymes, vitamins,
tannins, terpenoids, and alkaloids, are already established to have medicinal values
and are environmentally benign.
Various plant extracts are reported to facilitate synthesis of nanoparticles, as
mentioned in Table  8.1. Various MNP types (of different metals) were achieved
using GS methodology. This is an indication of high reducing potentials of plant
phytochemicals that neutralize uni- or multivalent metallic cations (Mn+) into neu-
tral atoms (Mo) for MNP synthesis. This might be due to the failure of the plant
biomolecules to reduce metal cations with lower reduction potentials. Thus screen-
ing of plant biomolecules having high electron-donating capacity can be one of the
efficient options for making GS a common modality of MNP synthesis. The innu-
merable angiospermic plant species are being used as remedies for diseases and also
as a part of our diet. Therefore, during plant selection, important technical aspects,
such as availability, socioeconomic importance, edibility, ethnobotanical back-
ground apart from the reducing nature of selected plant species. Randomized selec-
tion procedure might result in MNP synthesis, but biocompatibility issue may put it
in a nonprogressive research interest. Angiospermic plant species, such as Centella
asiatica, Azadirachta indica, Camellia sinensis, and Aloe vera, are the frontline
examples of plant species that have been highly explored for their medicinal values
and also have clinical relevancy (Table 8.1).

8.4  Nanoparticle Synthesis Using Microorganisms

Microorganisms are the main nanofactories that hold massive, eco-friendly, and
cost-effective tools, which avoid toxic, harsh chemicals and decrease high energy
demand required during physiochemical synthesis. Microorganisms have the capa-
bility to accumulate and detoxify heavy metal potential due to several enzymatic
action and reaction, which reduces metallic salts to metallic nanoparticles (MNPs)
with a narrow range of size distribution with less polydispersity. The mechanism
and experimental methods of synthesizing nanoparticles in microorganisms. Over
the past decades, microorganisms, such as bacteria, fungi, and yeasts, have been used
8  Nano-Based Materials and Their Synthesis 131

Table 8.1  Plant species used for green synthesis of different metallic nanoparticles (MNPs)
Size of
Plant Type of Mechanism/causative MNPs
Plant species material MNPs agent (nm) References
Azadirachta Kernel Au, Ag Azadirachtin 50–100 Shukla et al. (2012)
indica
Camellia sinensis Leaves Au Catechins 15–42 Nune et al. (2009)
Jatropha curcas Latex Pb Curcacycline A and 10–12 Joglekar et al.
B (2011)
Geranium Leaves Ag Terpenoids (not 16–40 Shankar et al.
specified) (2003a)
Nelumbo nucifera Leaves Ag Not mentioned 25–80 Santhoshkumar
et al. (2011)
Lemongrass Leaves Au Sugar derivative 200–500 Shankar et al.
plant extract molecules (2005)
Avena sativa Stems Au Not specified 5–85 Armendariz et al.
(2004)
Aloe vera Leaves Ag Not specified 70 Medda et al. (2015)
Cinnamomum Leaves Ag Polyol compounds 64.8 Huang et al. (2007)
camphora
Syzygium Flower Cu Eugenol 5–40 Subhankari and
aromaticum buds Nayak (2013)
Euphorbia esula Leaves Cu Flavonoids and 20–110 Nasrollahzadeh
phenolic acids et al. (2014)
Camellia sinensis Leaves Fe2O3 Polyphenols 5–15 Hoag et al. (2009)
Eucalyptus Leaves Fe2O3 Epicatechin and 20–80 Wang et al. (2014)
quercetin glucuronide
Aloe barbadensis Leaves ZnO Phenolic compounds, 25–40 Sangeetha et al.
miller terpenoids (2011)
Nephelium Peels MgO Not mentioned 100 Suresh et al. (2014)
lappaceum L.
Nephelium Peels NiO Nickel-ellagate 50 Yuvakkumar et al.
lappaceum L. complex formation (2014)
Clitoria ternatea Whole MgO Bioactive compounds 50–400 Sushma et al.
plant (2016)
Cintella asiatica Leaves Au Phenolic compounds 9.3 and Das et al. (2010)
11.4
Camellia sinensis Leaves Pt Pure tea polyphenol 30–60 Alshatwi et al.
(2015)
Asparagus Tuber Pd Bioactive compounds 1–6 Raut et al. (2013)
racemosus cortex

to synthesized extra- and intracellular MNPs given in Table 8.2. A biological proce-

dure for MNP synthesis has been informed using bacterial biomass, ­supernatant,
and derived constituents. Among the several methodologies, extracellular synthesis of
MNPs has received much attention because it removes the downstream processing
process which is required for the recovery of MNPs in intracellular methodologies.
Moreover, metal-resistant genes, proteins, enzymes, cofactors, and organic substance
132 S. Chaudhary et al.

Table 8.2  Microbial synthesis of different metallic nanoparticles (MNPs)

Bacteria Nanoparticle Size Morphology References
Bacterial
Aeromonas sp. Ag 6.4 Spherical Rai et al. (2009)
Bacillus megaterium Au 1.9 Spherical Sanpo et al. (2013)
Escherichia coli (DH5?) Au, Ag 10–50 Spherical, triangular Mahanty et al.
(2013)
Klebsiella (aerogenes, CdS, Ag ~52 Spherical Shahverdi et al.
pneumoniae) (2007)
Nocardiopsis sp. MBRC-1 Ag 45 Spherical Manivasagan et al.
(2013)
Shewanella Au, Fe3O4 Konishi et al.
(2006)
Thermoanaerobacter Co, Cr Ni and 5–25 Octahedral Rai et al. (2008)
ethanolicusTOR-39 Fe3O4
Pseudomonas stutzeri Ag, Ag2S 20–50 Nanocrystal Joerger et al.
AG259 (2000)
Lactobacillus sp. Au, Ag, 50 Hexagonal/counter Nair and Pradeep
Au-Ag (2002)
Desulfovibrio Pd 10–15 Yong et al. (2002)
desulfuricans
Corynebacterium sp. Ag 0.3–30 Zhang et al. (2005)
SH09
Lactobacillus sp. Ti Spherical Prasad et al.
(2007)
Shewanella oneidensis Fe3O4 40–50 Rectangular, Perez-Gonzalez
hexagonal et al. (2010)
Yeast cells Fe3O4 Wormhole-like Zhou et al. (2009)
Saccharomyces cerevisiae Sb2O3 2–10 Spherical Jha et al. (2009)
Lactobacillus sp. BaTiO3 20–80 Tetragonal Jha and Prasad
(2010)
Fusarium oxysporum TiO2 6–13 Spherical Bansal et al.
(2005)
Fusarium oxysporum ZrO2 3–11 Spherical Bansal et al.
(2004)
Fungus
Fusarium oxysporum Au 20–40 Spherical, triangular Mukherjee et al.
(2002)
F. oxysporum Zr 3–11 Quasi-spherical Bansal et al.
(2004)
F. oxysporum Au-Ag 8–14 Senapati et al.
(2005)
F. oxysporum Si 5–15 Quasi-spherical Bansal et al.
(2005)
F. oxysporum Pt 10–50 Triangle, hexagons, Riddin et al.
square, rectangles (2006)
(continued)
8  Nano-Based Materials and Their Synthesis 133

Table 8.2 (continued)
Bacteria Nanoparticle Size Morphology References
F. oxysporum BaTiO3 4 Bansal et al.
(2006)
V. luteoalbum Au 10 Spherical Gericke and
Pinches (2006)
Aspergillus flavus Ag 8.9 Vigneshwaran
et al. (2007)
Coriolus versicolor Ag 25–75 Spherical Sanghi and Verma
(2009)
Fusarium oxysporum PbCO3, 120– Spherical Sanyal et al.
CdCO3 200 (2005)
Fusarium oxysporum SrCO3 10–50 Needle like Rautaray et al.
(2004)
Brevibacterium casei PHB 100– – Pandian et al.
125 (2009)
Yeasts Zn3(PO4)2 10–80 Rectangular Yan et al. (2009)
Fusarium oxysporum CdSe 9–15 Spherical Kumar et al.
(2007)
Aspergillus fumigatus ZnO 1.2– Spherical and Raliya and
6.8 hexagonal Tarafdar (2013)
Aspergillus oryzae FeCl3 10– Spherical Raliya (2013)
24.6
Aspergillus tubingensis Ca3P2O8 28.2 Spherical Tarafdar et al.
(2012)
Rhizopus oryzae Au 10 Nanocrystalline Das et al. (2009)
Aureobasidium pullulans Au 29 ± 6 Spherical Zhang et al. (2011)
Colletotrichum sp. Au 20–40 Decahedral and Shankar et al.
icosahedral (2003b)
Helminthosporium solani Au 2–70 Polydispersed Kumar et al.
(2008)
Neurospora crassa Au 32 Spherical Castro-Longoria
et al. (2011)
Penicillium Au 10–50 Spherical Mishra et al.
brevicompactum (2011)
Verticillium luteoalbum Au <10 Spheres and rods Gericke and
Pinches (2006)
Cylindrocladium Au 19.5 Spherical Narayanan and
floridanum Sakthivel (2013)
Coriolis versicolor Au 20– Spherical and Sanghi and Verma
100 ellipsoidal (2010)
Verticillium sp. Ag 25 Spherical Mukherjee et al.
(2001)
Aspergillus fumigatus Ag 5–25 Mostly spherical, Bhainsa and Souza
triangular (2006)
Pleurotus sajorcaju Ag 30.5 Spherical Vigneshwaran and
Kathe (2007)
(continued)
134 S. Chaudhary et al.

Table 8.2 (continued)
Bacteria Nanoparticle Size Morphology References
Aspergillus flavus Ag 8.92 Spherical Vigneshwaran
et al. (2007)
Trichoderma asperellum Ag 13–18 Nanocrystalline Mukherjee et al.
(2008)
Penicillium fellutanum Ag 5–25 Mostly spherical Kathiresan et al.
(2009)
Penicillium strain J3 Ag 10– Mostly spherical Maliszewska et al.
100 (2009)
Cladosporium Ag 10– Mostly spherical Balaji et al. (2009)
cladosporioides 100
Phoma glomerata Ag 60–80 Spherical Birla et al. (2009)
Coriolus versicolor Ag 25–75 Spherical Sanghi and Verma
(2009)
Trichoderma viride Ag 5–40 Spherical, rodlike Fayaz et al. (2009)
Amylomyces rouxii Ag 5–27 Spherical Musarrat et al.
KSU-09 (2010)
Aspergillus flavus NJP08 Ag 17 Spherical Jain et al. (2011)
Aspergillus terreus CZR-1 Ag 2.5 Spherical Raliya and
Tarafdar (2012)
Fusarium oxysporum Au-Ag 8–14 Quasi-spherical Senapati et al.
(2005)
Verticillium sp. Fe3O4 100– Cubo-octahedral, Bharde et al.
400 quasi-spherical (2006)
Aspergillus flavus TiO2 62–74 Spherical Rajakumar et al.
(2012)
Aspergillus flavus TFR7 TiO2 12–15 Extracellular Raliya et al.
(2015)
Fusarium spp. Zn 100– Irregular, spherical Velmurugan et al.
200 (2010)
Aspergillus versicolor Hg 20.5 Alteration Das et al. (2008)
Algae
Shewanella algae Au 9.6 Spherical Sau and Murphy
(2004)
Sargassum muticum Zn 30–57 Spherical Azizi et al. (2014)
Chlorococcum humicola Ag 16 Jena et al. (2013)
Plectonemaboryanum Pt <300 Spherical Lengke et al.
(2006)
Sargassum bovinum Pd 5–10 Momeni and
Nabipour (2015)
Phormidium tenue Cd 5.1 MubarakAli et al.
(2012)
Phormidium valderianum Ag 15 Parial et al. (2012)
Chlorella vulgaris Ag 44 Xie et al. (2007)
Chlorella pyrenoidusa Au 25–30 Oza et al. (2012)
8  Nano-Based Materials and Their Synthesis 135

play significant roles by working as reducing agents. Moreover, these provide

natural topping to synthesize MNPs, thus avoiding the accumulation with and
increasing stability of MNPs. In recent research, bacteria, including Pseudomonas
deceptionensis (Jo et al. 2015), Weissella oryzae (Singh et al. 2015), Bacillus methy-
lotrophicus (Wang et al. 2015), Brevibacterium frigoritolerans (Singh et al. 2016),
and Bhargavaea indica (Singh et al. 2015), have been explored for synthesis of Ag
and Au NPs. Similar potential for producing NPs has been showed by using several
Bacillus and other species, including B. licheniformis, B. amyloliquefaciens,
Rhodobacter sphaeroides, Listeria monocytogenes, B. subtilis, and Streptomyces
anulatus. Various genera of microorganisms have been reported for metal nanopar-
ticle synthesis, including Bacillus, Pseudomonas, Klebsiella, Escherichia,
Enterobacter, Aeromonas, Corynebacterium, Lactobacillus, Pseudomonas,
Weissella, Rhodobacter, Rhodococcus, Brevibacterium, Streptomyces, Trichoderma,
Desulfovibrio, Sargassum, Shewanella, Plectonemaboryanum, Rhodopseudomonas,
Pyrobaculum, etc. These investigations suggest that the main mechanism of the
synthesis of nanoparticles using bacteria depends on enzymes, for instance, the
nitrate reductase enzyme was found to be responsible for silver nanoparticle synthe-
sis in B. licheniformis (Singh et al. 2016).
Rather than using bacteria, mycosynthesis is a straightforward approach for
achieving stable and easy biological nanoparticle synthesis. Most fungi containing
important metabolites with higher bioaccumulation ability and simple downstream
processing are easy to culture for the efficient, low-cost production of nanoparticles.
Moreover, compared with bacteria, fungi have higher tolerances to, and uptake
competences for, metals, particularly in terms of the high wall-binding capability of
metal salts with fungal biomass for the high-yield production of nanoparticles.
Three possible mechanisms have been proposed to explain the mycosynthesis of
metal nanoparticles: nitrate reductase action; electron shuttle quinones; or both.
Fungal enzymes, such as the reductase enzymes from Penicillium species and
Fusarium oxysporum, nitrate reductase, and /-NADPH-dependent reductases, were
found to have a significant role in nanoparticle synthesis, similar to the mechanism
found in bacteria. The synthesis of nanoparticles using actinomycetes has not been
well explored, even though actinomycete-mediated nanoparticles have good mono-
dispersity and stability and significant biocidal activities against various pathogens.
The synthesis of silver, copper, and zinc nanoparticles using Streptomyces sp. has
demonstrated that the reductase enzyme from Streptomyces sp. has a vital role in the
reduction of metal salts. Similar to other microorganisms, yeasts have also been
widely investigated for the extracellular synthesis of the nanoparticles on a large
scale, with straightforward downstream processing. Furthermore, virus-mediated
synthesis of nanoparticles is also possible. Viruses can be used to synthesize nanow-
ires with functional components that are assembled for various applications, such as
battery electrodes, photovoltaic devices, and super capacitors. Nanoparticles are
slow with low productivity, and the recovery of nanoparticles requires downstream
processing. Furthermore, problems related to microorganism-based synthesis for
nanoparticles also include the complex steps, such as microbial sampling, isolation,
culturing, and maintenance.
136 S. Chaudhary et al.

8.5  Conclusion

The green method for nanoparticle synthesis, which is rapidly replacing traditional
chemical syntheses, is of great interest because of eco-friendliness, economic views,
feasibility, and a wide range of applications in several areas such as nano-medicine
and catalysis medicine. Recently, various types of biological units which serve a
dual role as both the reducing and stabilizing agents have been used in the synthesis
of bioactive nanoparticles.

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Chapter 9
Nano-based Composites and Their
Synthesis

Shalok Bharti, Lalit Thakur, Sanjeev Anand, and Varun Dutta

9.1  Introduction

In today’s world the type of material used in a device plays a significant role. The
conventional materials like metals, polymers and ceramics have their limitations.
Therefore the use of composites is introduced in various applications. In composites
two or more materials are combined to increase the property of the material. This
approach is further increased by introducing one of the components in the compos-
ite at nanoscale level (Hussain et al. 2006). Such a composite is called nanocompos-
ite. Nanocomposites are multiphase solid materials in which one of its parts has
dimensions in nanometre series (i.e. 109  m) (Roy et  al. 1986). Because of the
increase in the area of surface and the effect of quantum at such a small scale, it’s
mechanical, electrical, chemical and other properties get improved. Nanocomposites
are different from the conventional composite materials. In conventional composite
materials, reinforcements are added to the base in order to increase its properties,
e.g. SiC when added to the aluminium alloy, its hardness and tensile strength
increase (Gupta et  al. 2018). But nanocomposites are different from the conven-
tional composites due to the fact that it contains exceptionally high aspect ratio. It
is known as the material of the present era because of the property and design
uniqueness which is not found in the traditional form of composites. There are still
many areas in nanocomposites which are to be understood (Schmidt et al. 2002);
on the other hand, it is to be noted that the first research was carried out in 1992

S. Bharti · V. Dutta (*)

School of Mechanical Engineering, SMVD University, Katra, J&K, India
L. Thakur
Department of Mechanical Engineering, NIT Kurukshetra, Haryana, India
S. Anand
School of Energy Management, SMVD University, Katra, J&K, India

© Springer Nature Switzerland AG 2020 141

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_9
142 S. Bharti et al.

(Gleiter 1992). For understanding the structure-property relationship, the area/volume

ratio of reinforcement materials which is present in the synthesis of nanocomposites
is very crucial. There found the opportunity to use the spinning CNTs into the prod-
ucts of composites (Dalton et al. 2003) which opens the way for the use of CNTs in
the nanocomposites. In these days nanocomposites seem to provide the new tech-
nology to the industry along with its eco-friendly nature (Choa et  al. 2003).
Nanocomposites can be differentiated into three categories according to the mate-
rial matrix as (Henrique et al. 2009):
1 . Polymer matrix nanocomposites (PMNC)
2. Ceramic matrix nanocomposites (CMNC)
3. Metal matrix nanocomposites (MMNC)
They are appropriately in Table 9.1 (Henrique et al. 2009).
It must be kept in mind that the properties of the composites based upon the
polymer are yet to be reached. The properties include electrical, chemical and oth-
ers. Various recent reports are present which show recent development in the char-
acterization, properties, preparation and crystallization behaviour of the matrix and
layered nanocomposites (Ray and Bousmina 2005; Pandey et al. 2005). Ceramics
has high thermal and chemical stability along with good wear resistance. But they
are brittle in nature which limits its commercial use in the industry. Due to this rea-
son, ceramic matrix nanocomposites come to existence which help to enhance its
properties. A significant work on ceramic matrix nanocomposites (CMNC), primar-
ily on the Al2O3/SiC system, is done by Niihara. The use of high-strength nanofibre
in ceramic matrices helps the preparation of advanced nanocomposites which
results in high toughness and superior failure properties as compared to the rapid
failure of ceramic materials (She et al. 2000). Similarly metal matrix nanocompos-
ites (MMNC) are the materials which contain the alloy matrix or ductile metal in
which the nanosized reinforcement is entrenched. These materials increase the
properties, e.g. ductility and toughness, and help to compensate the limitation of
each other. Hence metal matrix nanocomposites are appropriate for the manufactur-
ing of materials with more service temperature abilities and more strength in shear/
compression practices. MMNC show potential for their use in areas such as aero-
space and automobile industries (Tjong and Wang 2004). Due to the easy process of
manufacturing polymer materials and due to its properties, they are widely used in
the industry. However, they have the limitations of having low modulus and strength
as compared to metals or ceramics.

Table 9.1  Different types of nanocomposites with examples (Henrique et al. 2009)
Category Examples
Polymer Thermoplastic/layered silicates/thermoset polymer, TiO2/polyester, CNT/polymer,
layered double hydroxides/polymer
Metal Co/Cr, 2O3, Fe/MgO, Ni/Al2O3, Al/CNT, Mg/CNT
Fe-Cr/Al
Ceramic Al2O3/CNT, Al2O3/TiO2, 2O3/SiO2, Al2O3/TiO2, Al2O3/SiC, SiO2/Ni, Al
9  Nano-based Composites and Their Synthesis 143

The addition of reinforcement to polymer resins results in great improvement of

its biodegradability. There are incredible rewards for the use of nanocomposites,
and hence worldwide attention is given to them. In this paper the synthesis and
overview of the three different types of nanocomposites are reviewed. Various
developments and mechanisms related to them are also discussed along with their
potential uses in present and future perspectives.

9.2  Synthesis of Nanocomposites

Although the three types of nanocomposites are of nanosize, the preparation tech-
niques for all of them are similar to that of microcomposites. These techniques are
the same to those of CNT-reinforced composites. The techniques for the synthesis
of the three types of nanocomposites are discussed below.

9.2.1  Ceramic Matrix Nanocomposites (CMNC)

The ceramic matrix nanocomposites are the nanocomposites in which the main ele-
ments consist of ceramic (a chemical compound made from nitrides, silicides,
oxides, etc.) and have metal as the secondary element. There are various techniques
from which the ceramic matrix nanocomposites can be synthesized. The most com-
mon technique is the “powder process” technique.
Several techniques which are useful for the synthesis of various nanocomposites
by powder process (Palmero 2015) are shown in Fig. 9.1 (Ravichandran et al. 2018).
There are many different methods that have been given for the manufacturing of
ceramic matrix nanocomposites (Thostenson et al. 2001; Stearns et al. 1992; Balázsi
et al. 2005). The most common methodologies, as applied for microcomposites, are
spray pyrolysis; polymer precursor route; vapour techniques (PVD and CVD); con-
ventional powder method; and chemical methods. They include the colloidal and
precipitation approaches; sol-gel process; and the template synthesis.
Table 9.2 gives the list of the systems manufactured by certain techniques,
whereas Table 9.3 presents their limitations and advantages.
The flexible control of the chemical and structural properties of the final oxide
materials is affected by various factors that affect the sol-gel process like timing,
precursor, solvent, water/metal ratio, pH, etc. (Ennas et al. 1998).

9.2.1.1  Synthesis of Ceramic CNT Nanocomposites

There are various different methods which are available for the synthesis of CNT-­
reinforced nanocomposites (Thostenson et al. 2001; Ning et al. 2003; Balázsi et al.
2005). Some of them are given in Table 9.4.
144 S. Bharti et al.

Fig. 9.1  Different powder process methods for the manufacturing of ceramic nanocomposites

9.2.2  Metal Matrix Nanocomposites

When the hard ceramics or soft reinforcement contains the hard metallic matrix,
then the resultant nanocomposite is known as the metal matrix nanocomposite
(Shiva Shankar and Basavarajappa 2015). There are various benefits of metal matrix
nanocomposites as compared to monolithic metals such as the low thermal expan-
sion coefficient, improved wear resistance and greater modulus and specific strength
(Henrique et al. 2009; Kori et al. 2014). Some of the common approaches in the
preparation of metal matrix nanocomposites include liquid metal infiltration; vapour
techniques (CVD, PVD); chemical methods; spray pyrolysis; rapid solidification;
and electrodeposition. The chemical method consists of the sol-gel and colloidal
processes (Baker et al. 2004; Schadler et al. 1998).
Table 9.5 shows the list of these methods, whereas Table 9.6 shows their benefits
and drawbacks.
The techniques which are used for the preparation of metal matrix composites
can be divided into mainly five types. These types are mainly based upon the tem-
perature which is used for the preparation of the metal matrix during the process
(Sealy 2004). These types can be named as:
1. Solid-phase processes
2. Deposition techniques
3. Liquid-phase processes
4. In situ processes
5. Two-phase (solid-liquid) processes
9  Nano-based Composites and Their Synthesis 145

Table 9.2  Techniques for the synthesis of ceramic nanocomposites (Henrique et al. 2009)
Method System Procedure Reference
Powder Al2O3/SiC (i) Choose the correct raw material. The Stearns et al.
process raw materials are generally powders (1992)
having small size, high purity and
uniformity
(ii) In aqueous or organic media, mix the
material by attrition milling or wet-milling
method
(iii) After mixing, dry them with the help
of lamps or oven or with the help of freeze
drying
(iv) After that the solid material must be
merged by means of hot pressing or gas
pressure or injection moulding or slip
casting or sintering or pressure filtration
method
Polymer SiN/SiC, Al2O3/SiC Silicon polymeric predecessors are Sternitzke
precursor merged in matrix material. After that the (1997),
process pyrolysis of the mixture should be done in Riedel et al.
the microwave oven which will ultimately (1995)
produce the reinforced particle
Sol-gel TiO2/Fe2O3, ZnO/Co, (i) Perform the polycondensation reaction Mathur et al.
process La2O3/TiO2, Al2O3/ and hydrolysis of the organic/inorganic (2002)
SiC, TiO2/Al2O3, molecule whose parent molecule dissolved
Al2O3/SiO2, SiO2/Ni, in the organic media
Al2O3/SiO2/ZrO2, (ii) Due to the reactions in them, there will
TiO2/Fe2, TiO5, be formation of three-dimensional
NdAlO3/Al2O3 polymers which will consist of metal and
oxygen bonds
(iii) The obtained material is then lead to
the drying stage. This will convert it to a
solid material, and consolidation process
can be obtained by thermal treatment
further

1. Solid-Phase Processes
In it the elemental powders are blended together to form the particular reinforced
metal matrix composite. The main method consists of powder metallurgy. The main
steps in this technique consist of:
• Preparing the powder
• Blending the powder
• Squashing
• Sintering
• Sizing
• Machining
146 S. Bharti et al.

Table 9.3  Benefits and drawbacks of ceramic nanocomposite synthesis techniques (Henrique
et al. 2009)
Technique Benefits Drawbacks Reference
Polymer In this technique there is the probability There is the dispersion of Sternitzke
precursor the ultra-fine particles
for synthesising the particles that are finer (1997),
process in nature and have better reinforcement and accumulation in the Riedel et al.
dispersion product which result into (1995)
the phase-segregated and
inhomogeneous material
Powder It is simple to synthesize High temperature, poor Stearns
process phase dispersion, low et al. (1992)
formation rate, secondary
phases are formed in the
product, accumulation
Sol-gel Production of polymers which consist of In comparison with other Mathur
process metal-oxygen bonds has three mixing methods, it has et al. (2002)
dimensions. Products are highly pure and lower amount of voids
simple; chemical homogeneity is high; in and has more shrinkage
it the processing time is low; matrices
may be single or multiple and versatile in
nature; this technique is exclusively
applicable for those composite materials
that have liquid or viscous fluids in it
which is obtained from the alkoxides

Table 9.4  Techniques for synthesising the ceramic CNT nanocomposites (Henrique et al. 2009)
Method System Procedure Reference
Catalytic Al2O3/ In it the Al2O3 powder is saturated with iron Ning et al. (2003)
decomposition CNT catalysts by using acetylene over it
Solvothermal Fe3O4/ With the help of ultrasonic treatment, carbon Jiang and Gao
process CNT nanotubes are dispersed in the ethylenediamine (2003)
(EDA); iron (III)-urea complex is then added; at
200 °C the Teflon-lined autoclaves are heated
for about 50 hours and then cooled at room
temperature
Hot pressing SiO2/ (i) Firstly the glass powders of CNTs and SiO2 Thostenson et al.
CNT; are dispersed into the ethanol (2001), Ning
SiC/ (ii) Ultrasonic treatment and stirring process are et al. (2003)
CNT then applied
(iv) The obtained product is then taken for
drying process by hot pressing in atmosphere
having pure N2
(i) Nanoparticles of SiC and CNTs are then
mixed with each other
Spray pyrolysis Al2O3/ In the porous walls, anodization of the growth Xia et al. (2004a,
or CVD CNT of carbon nanotubes is performed to produce b), Kamalakaran
the alumina matrix. From substrate to matrix et al. (2003)
surface, carbon nanotubes develop into the
hexagonal straight pores
9  Nano-based Composites and Their Synthesis 147

Table 9.5  Techniques for the processing of metal matrix nanocomposite (Henrique et al. 2009)
Process System Procedure Reference
Liquid Pb/Fe; Nb/ (I) Firstly the matrix metal material and Choa et al. (2003),
infiltration Cu; Al-C60; the reinforcement particles are mixed Yoon et al. (2002),
Pb/Cu; W/ together Khalid et al. (2003)
Cu; Nb/Fe (II) The thermal treatment is carried away
which helps the reinforcement material to
be surrounded by the melted metal matrix.
This is done with the help of liquid
infiltration
(III) In order to get rid of the internal
porosity and support the merging of the
metal matrix and reinforcement, further
heat treatment is carried away below the
melting temperature of the metal matrix
RSP with Al/SiC To improve the properties like wettability Li et al. (2004)
ultrasonic and blending of the reinforcement and the
metal matrix, this method is used
PVD/CVD Cu/Pb, Al/ CVD: In it the material’s vapours are Choy (2003), Holtz
Mo, Cu/W obtained with the help of chemical and Provenzano
reactions. After which the consolidation (1994), Chow et al.
process is carried away (1990)
PVD:
 (I) Vapour phase of various components
is formed by evaporation/sputtering
 (II) In order to support the condensation
of the metal nanoparticles, the vapour
phase is carried out by super saturation
in the inert atmosphere
 (III) In the inert atmosphere, merging of
the nanocomposites is done with the
help of thermal treatment
Spray pyrolysis W/Cu; Fe/ (I) Firstly the inorganic material is Choa et al. (2003)
MgO dissolved into the relevant solvent in order
to have the liquid source
(II) With the help of the ultrasonic
atomizer, a mist is generated in the form
of liquid
(III) The mist is then carried towards the
chamber which is already heated with the
help of carrier gas.
(IV) The generated vapours are then
vaporized. These vapours are then trapped
with the help of filters. It is done in order
to assure the decomposition which will
further help to form the oxides of the
respective materials.
(V) Some of the metal oxides are reduced
so that particular metallic materials are
produced respectively
(continued)
148 S. Bharti et al.

Table 9.5 (continued)
Process System Procedure Reference
Rapid Al/X/Zr (I) In his technique, firstly the metal Bhattacharya and
solidification (where components are melted with each other Chattopadhyay
process (RSP) X = Cu, Ni, (II) The melting is done in such a way that (2004), Branagan
Si); Iron the homogeneity is ensured. It is done by and Tang (2002)
(Fe) alloy; ensuring the melting temperature more
Al/Pb than the miscibility gap critical line
(III) With the processing like melt
spinning, the melts are then taken to rapid
solidification
Chemical Au/Fe/Au, For Fe/Au consisting of nanocomposites: Cushing et al.
processes Ag/Au, Fe/  (I) Firstly iron shell is produced (2004), West et al.
(sol-gel, SiO2  (II) Secondly shell is prepared, and (2003)
colloidal) after that the second gold coating is Carpenter et al.
done which is followed by drying the (2000)
powders
 (III) The final material is then obtained
by pressing the mixture
Colloidal method:
 (I) In order to form the metal particles,
the inorganic salts are removed from
the solution chemically
 (II) Dry materials are then undergoes
consolidation
 (III) To promote the preparation of the
metal component and to encourage the
reduction of the selective oxides from
the solution, the thermal treatment and
drying of the solid are carried away in
atmosphere such as h2, i.e. reducing
atmosphere
Sol-gel process:
 (I) With the help of mesoporous silica
comprising of 0.1 chloroauric acid (aq.)
and 0.6 M sodium borohydride (aq.),
two micelle solutions are prepared
 (II) The mixing of the solution is
carried away until the whole gold is
removed from it
High-energy Cu/Al2O3 Powders are milled with each other till we Ying and Zhang
ball milling get nanocomposites (2000)
9  Nano-based Composites and Their Synthesis 149

Table 9.6  Benefits and drawbacks of the production techniques of metal matrix nanocomposites
(Henrique et al. 2009)
Technique Benefits Drawbacks Reference
Liquid Different types of material Reinforcement can be Khalid et al. (2003),
infiltration with better wear resistance separated Yoon et al. (2002),
and better stiffness can be High temperature can be Choa et al. (2003)
mould in various shapes and used
near net shapes Through the processing
Solidification is rapid stage, the undesired
The contact time between the formation of various
reinforcement and matrix is products can be seen
short
By this method production at
industrial level as well as lab
level can be done
RSP with In this technique the Baker et al. (2004)
ultrasonic distribution without the
accumulation of even fine
particles is good
PVD/CVD Films are uniformly thick Price Choy (2003), Holtz
Reproducibility is better Comparative complexity and Provenzano
This technique has the ability Development of various (1994)
to form pure and highly parameters
dense materials
In it the adhesion is seen at
the rate when deposition is at
high rate
Spray pyrolysis In it the homogeneous, In order to produce the Choa et al. (2003)
ultra-fine and spherical uniformed particles in
powder can be prepared with nanosize at large
quality, multicomponent quantity, high cost is
system and reproductive size involved
RSP (rapid Efficient and simple It encourages separation Bhattacharya and
solidification of particles Chattopadhyay
process) In it nanocomposites can (2004), Branagan
be prepared which are and Tang (2002)
having metal-metal
nature
In it the fine particles are
distributed in the
non-homogeneous way
Chemical It is flexible in nature Permeability is really Cushing et al.
processes Treating temperature is low high (2004), Carpenter
(sol-gel, Severe stoichiometry control Wear resistance is low et al. (2000), West
colloidal) Chemical homogeneity is Porosity control is et al. (2003)
high difficult
It is a simple process Bonding is weak
Products are highly pure
High-energy Distribution is uniform Ying and Zhang
ball milling Mixing is homogeneous (2000)
150 S. Bharti et al.

2. Deposition Technique
Some of the important deposition methods are PVD, CVD, electroplating, spray
deposition and immersion plating. In this technique, the matrix material which is
required to form the composites is coated upon the individual fibres in a tow. After
this it is observed that the structural shape or consolidated composite plate is formed
by the action of successive diffusion.
3. Liquid-Phase Processes
With the help of various property methods, the particular ceramics are merged in
the metal matrix. After that the material is then mixed with each other which is then
followed by casting of the resultant composite. The eligibility for the selection of
the reinforcement material consists of:
(i) Temperature of the melting
(ii) Thermal stability
(iii) Shape and size of the reinforcement particles
(iv) Matrix alloy
(v) Cost
(vi) Tensile strength
(vii) Modulus of elasticity
4. In Situ Processes
With the help of in situ process, the reinforced phase is prepared. From the par-
ticular alloy at starting stage, the production of composite material is performed.
5. Two-Phase Processes
In this technique the matrix and the ceramics are mixed at the location in the
phase diagram where the matrix consists of both the liquid and the solid phases. In
this technique, the major method includes the rheocasting/compocasting and spray
deposition.

9.2.2.1  Synthesis of CNT-Reinforced Metal Matrix Composites

There are various different techniques by which the carbon nanotube-reinforced

metal matrix composites can be prepared (Laurent et al. 1998; Chen et al. 2000;
Yang and Schaller 2004). Some of the techniques are shown in Table 9.7.
9  Nano-based Composites and Their Synthesis 151

Table 9.7  Techniques for the preparation of metal-CNT nanocomposites (Henrique et al. 2009)
Technique System Procedure Reference
Nanoscale Al/CNT With the help of ethylene propylene and natural Noguchi et al.
dispersion rubber, the precursor of MWCNT is prepared (2004)
which is 10–50 mm long and 13 mm in diameter
It is then mixed with aluminium powder
With the help of compression moulding, it is
then rolled into sheets at 353 K temperature
The procurer is then placed over the
28-micrometre grain-sized aluminium plate
It is then heated in N2 atmosphere for 1 hour at
1073 K temperature
It is then finally cooled
Hot pressing Al/CNT With the help of grinding, powders are mixed Xu et al.
for 30 minutes (1999)
Under the pressure of 25 MPa, hot pressing is
done at 793 K
PM/ Mg-Al2O3f-­ (I) With the help of acid and alcohol, the mg Yang and
infiltration CNT powders are then mechanically mixed with Schaller
multiwalled carbon nanotube which is 1% in (2004)
volume
 After that the sinterization process is applied
under 25 MPa pressure at 550 °C
(II) The Al2O3 fibres which are 40–100 mm in
length and 25% in volume are then covered
under pressure with the multiwalled carbon
nanotubes which are then used for the
infiltration of the molten mg
Electroless Sn2Sb/CNT, In the occurrence of CNTs, the SbCl3 and SnCl2 Chen et al.
coating SnSb 0.5/CNT, precursors are reduced by potassium (2003), Chen
Sn/CNT borohydride et al. (2002)
Electroless Co-CNT (I) The electrolysis plating bath is used which Chen et al.
coating consists of cobalt precursor, activated CNT, a (2000)
buffer, reducing agent CoSO4.7H2O and the
complexing agent. It results when the CNTs are
coated with CO
(II) The thermal treatment is done with 200 torr
pressure in 10% H2/N2 at 873 K temperature

9.2.3  Polymer Nanocomposites

Polymers have many applications in many fields. The polymers are known for their
ductility, capability of being easily processed, less weight, etc.
But in comparison with metals or ceramics, polymers show several limitations
such as low stability, less strength, poor mechanical properties, etc.
But these limitations can be overcome with the help of polymer nanocomposites.
With the help of fillers made of nanofibres or nanoparticles, polymer nanocompos-
152 S. Bharti et al.

ites emerge as the material which is more efficient and is widely used in areas such
as solar cells, aerospace, sports material, supercapacitors, etc.
The improvement in the properties of polymer nanocomposites is due to the
nanostructures having larger aspect ratio. But this is not wholly dependent upon
this; it also depends on the type of constituents used and the type of method used for
the preparation. Nanocomposites are also dependent on the processing factors and
method for synthesis.
There are various different types of methods which are employed for the prepara-
tion of the polymer nanocomposites including that of the carbon nanotubes and that
of the layered materials. Important methods include:
I. In situ polymerization
II. Introduction of the prepolymer or polymers from the solution
III. Injection of the melts
IV. Solution blending
V. Template synthesis
VI. Sol-gel process
VII. Particulates and the polymers having direct mixture
Commonly used methods are in situ polymerization, melt processing and solution
blending.

9.2.3.1  In Situ Polymerization

In this method, usually the solvents are avoided, and it produces the uniformly dis-
tributed polymer matrix with fillers in it. The preparation includes the typical tech-
niques of polymerization such as stirring, UV curing, ultrasonic, etc. which are used
to polymerize the mixture-containing fillers and monomer particles. This method is
ideal for the production of nanocomposite constituents having covalent bonds in
them. Those polymers can also be prepared by this method, which cannot be pre-
pared by the methods such as melt blending or solution mixing. This method is also
useful for the preparation of thermally unstable and insoluble polymers.

9.2.3.2  Melt Processing

Every method needs the use of solvents which are generally toxic in nature. But this
method is one of the simplest methods which do not requires the use of such toxic
solvents. It is a cost-effective technique. Melt processing is also known as the
solution-­blending technique. In this method, the fillers are directly scattered in the
9  Nano-based Composites and Their Synthesis 153

melted polymers. Techniques such as moulding, extrusion or injection are used to

blend the melts. Thermoplastic polymers have high viscosity due to which high
temperature is required in this method to melt the polymers. High shear force along
with high temperature is required to scatter the fillers uniformly.

9.2.3.3  Solution Blending

It is one of the most used and simple methods for the synthesis of nanocomposites.
Solution blending technique includes the solvent in which the scattered solution of
fillers and polymers are mixed. The most common type of solvents includes toluene,
water, chloroform, etc. Production of the nanocomposite includes the mixing of the
solution and further removal of the solvent. Simple filtration and precipitation can
result in the preparation of the nanocomposites. This technique includes the limitation
of firstly seeking and then removing the solvent in end stage. The solvent used in
this method is toxic in nature. The preparation of the graphene oxide or graphene is
done by combining it with the polymers such as polyimides, polyacrylamides, poly-
styrene, etc. with the help of blending method of their solution (Potts et al. 2011).
To encourage covalent bonding and effective scattering with the matrix, the gra-
phene is fabricated acidically. In these nanocomposites, one of the important steps
is to exfoliate the fabricated graphene.

9.2.3.4  Other Techniques

There are various other different types of techniques which can be employed for the
preparation of polymer nanocomposites. The synthesis of polymer nanocomposites
which is reinforced by carbon nanotubes can be synthesized by various methods
such as melt mixing, solution mixing, in situ polymerization, direct mixing, etc. In
the same way for the synthesis of the conducting polymer nanocomposites, various
methods such as electrochemical and chemical methods are employed (Sanchez
et al. 1999).
Table 9.8 shows the various techniques for the processing of polymer-based
nanocomposites; Table  9.9 shows the benefits and drawbacks of polymer-based
nanocomposite synthesis approaches, whereas Table 9.10 shows the methods for the
synthesis of polymer-CNT nanocomposites.
154 S. Bharti et al.

Table 9.8  Techniques for the processing of polymer-based nanocomposites (Henrique et al. 2009)
Method Structure Procedure Reference
In situ Montmorillonite (I) Firstly, wrapping of the silicate of Kojima et al.
intercalative through PCL/ layered stage in the liquid monomer (1993),
polymerization Epoxy/N6/PMMA solution is done Messersmith
(II) After that the polymers are and Giannelis
prepared in the introduced sheets (1994), Yao
(III) With the help of radiations or et al. (2001)
heat, the polymerization is carried
away
(IV) In the interlayer, the suitable
catalyst is diffused prior than step of
swelling
Template Hectorite with Within the aqueous solution having Tomasko et al.
synthesis HPMC, PDDA, polymer in it, the in situ preparation (2003), Carrado
PVPR, PANI, PAN of inorganic material is done. This and Xu (1998),
inorganic structure consists of the Watkins and
layered structure. In the preparation McCarthy
of layers, the polymers, which are (1995)
water soluble in nature, act as the
models. This is less used for the
preparation of the layered silicates
but is widely used in the preparation
of the LDH nanocomposites
Sol-gel process 2-hydroxyethyl (I) Inserting the monomers and the Liu et al.
acrylate (HEA)/ organic molecules over the sol-gel (2002), Ver
SiO2 matrices Avadhani et al.
Poly(amide-imide)/ (II) The creation of the chemical (1997),
TiO2 bonds leads to the initiation of the Kickelbick
PMMA/SiO2 organic group (2003)
Polycarbonate/SiO2 (III) In the polymer, the sol-gel
Polyimide/SiO2 matrices are formed by in situ action
Polyimide/silica (IV) Other process of formation of
Polyethylacrylate/ organic/inorganic networks can also
SiO2 be done by simultaneous action
Prepolymer/ Clay with PCL, (I) It is used in the material having Alexandre and
intercalation by PLA, HDPE, PEO, layered reinforcement and into which Dubois (2000),
solution PVA, PVP, PVA, the introduction of polymer is Jimenez et al.
etc. possible (1997)
(II) It is generally applied for the
layered silicates, which allow the
introduction of prepolymer/polymer
from the solution
(III) In it only those solvents are
used, in which the silicate layers get
swells and the solubility of
prepolymer/polymer is good
(continued)
9  Nano-based Composites and Their Synthesis 155

Table 9.8 (continued)
Method Structure Procedure Reference
Melt Montmorillonite by (I) The process of annealing is carried Hasegawa et al.
intercalation using PEO/PVP/PS/ out of the mixture of the layered (1998), Gilman
Clay-PVPH/PP reinforcement and the polymer. The (1999)
softening point for this process under
the shear or at static mode must be
high than that of the polymer
(II) During the annealing process, the
polymer chains from the melt of the
polymer get dispersed into the
passages of the reinforcement layers
Mixing and in TiO2/PMMA/Pd (I) Firstly the monomers or either the Aymonier et al.
situ polyester polymers are mixed with the (2003), Evora
polymerization γ-Fe2O3/Epoxy reinforcements and Shukla
vinylester (II) The inorganic particles are then (2003), Di
CuSO4, AgNO3 and scattered into the precursor made of Lorenzo et al.
NiSO4 the monomers (2002)
Ag/PVA (III) The relevant catalyst is then used
Fe3O4/Epoxy in the mixture for the polymerization
vinylester, CaCO3/ process
PET (IV) The traditional moulding process
PAA/Cu, Ag/PAA is then carried out in order to process
(acrylic acid), PAA/ the material further
Ni (V) The ultrasonic are used for the
scattering of the epoxies
(VI) In order to encourage the
formation of the metal nanoparticles
and instantaneous polymerization, the
exposition of the AG systems to 60
Co γ-ray is carried out

9.2.3.5  Synthesis of Polymer-CNT Nanocomposites

Some of the techniques for the synthesis of polymer-CNT nanocomposites are

shown in Table 9.10. The structure and method for their synthesis are also shown
along with remarks.

9.3  Conclusion

It is concluded that technology is emerging day by day, and hence it requires the
material that should have novel properties and have the improved performance as
compared with the existing materials. Therefore, nanocomposites are the materials
that are the need of the today’s technological world. There are various techniques
and methods available to us for the synthesis of these nanocomposite materials, but
still there is need for the improvement in these techniques. Nanocomposites show
improved performance as compared to microcomposites or monolithics and therefore
156 S. Bharti et al.

Table 9.9 Benefits and drawbacks of polymer-based nanocomposite synthesis approaches

(Henrique et al. 2009)
Method Benefits Drawback Reference
In situ (I) This method depends    (I) The control for the Kojima et al.
intercalative upon the scattering of intragallery (1993),
polymerization fillers inside the polymerization is Messersmith and
precursors of polymers difficult Giannelis (1994),
(II) It is an easy method    (II) It has very limited Okamoto et al.
applications (2001)
Synthesis of (I) Procedure is easy      (I) Its applications are Tomasko et al.
template (II) Production can be done very limited (2003), Watkins
at large scale    (II) It can be polluted and McCarthy
by the side (1995), Carrado
products and Xu (1998)
(III) I t is generally
based upon the
polymers that are
soluble in water
Sol-gel process (I) I t is a simple process      (I) The amount of Reuter (1991),
(II) It has the ability to cavities is low Vorotilov et al.
produce products with    (II) It has more (1999), Ennas
maximum purity shrinkage et al. (1998)
(III) I t is a versatile process
(IV) It requires low
processing temperature
(V) The chemical
homogeneity in this
process is high
Prepolymer/ (I) In it the preparation of This process utilizes the Kamigaito (1991),
intercalation intercalated nanocom­ huge quantity of the Alexandre and
from solution posites having less or no solvents in term of Dubois (2000),
polarity can be obtained industrial level Jimenez et al.
which is established on (1997)
the basis of polymers
(II) Fillers with
homogeneous scattering
can be synthesized
Melt (I) This process is well It has a very restricted Vaia and Giannelis
intercalation suited for the industrial application for the use (1997a, b), Gilman
polymer processes in polyolefin, which (1999), Vaia et al.
(II) It is characterizes most of (1995)
environment-friendly the used polymers
(III) The practice of using
the polymers for other
processes is not suitable
9  Nano-based Composites and Their Synthesis 157

Table 9.10  Methods for the synthesis of polymer-CNT nanocomposites (Henrique et al. 2009)
Technique Structure Method Remarks Reference
Solution Thermoplastic       (I) The behaviour
     (I) Scattering of the Qian et al.
mixing resins (Epoxy/PS) 0.2–1% of the of the polymer (2000),
CNTs having is firstly Koerner
10 mm length and modified et al. (2004)
100 nm of (III) The effect of
diameter synergistic is
   (II) The solvent of the done
polymer is then    (II) The shape
removed memory
(III) Curing nanocomposites
can be formed
In situ Polyether-­      (I) The scattering in       (I) The CNTs are Park et al.
polymerization polyester; Epoxy/ the matrix or used for the (2003),
CNT; Polyaniline/ monomers is done synthesis of the Andrews
CNT; MMA/CNT by using the polymers et al. (2002)
ultrasonic    (II) It has better
technique chemical
   (II) Curing bonding
Direct mixing Thermoset resins       (I) Scattering of Sandler
are used CNTs is done et al. (1999)
   (II) Curing
Melt mixing N6       (I) The CNTs are       (I) The 0.2–2.0% Tang et al.
Polymers mixed with the of the (2003),
melts of multiwalled Andrews
prepolymer by carbon et al.
the mechanical nanotubes are (2002),
action used Liu (2004)
   (II) After that the    (II) The mixer
extrusion process having twin
is carried out screw is used
(III) The compression
or injection
moulding process
can be applied
Others PANI/SWCNT;       (I) The mechano­ 0–10% of CNTs by Xia et al.
PP-CNT; chemical weight is used (2004a, b),
IPP-SWCNT; pulverization Valentini
PVK-SWCNT process of the et al. (2003)
solid state takes
place
   (II) The sonication
and blending
together take
place
(III) The melt blending
is done
(IV) VDP
158 S. Bharti et al.

are the best materials for today’s industry to be incorporated in modern machinery
and devices. There are various applications of these materials in today’s world, but
we should not limit the use of nanocomposite materials to only these applications;
nanocomposite materials can do great in future devices and machinery. Due to the
unique properties and vast field of applications, nanocomposite materials are
becoming the interest of the modern industry and proving itself a great field of
research for the researchers.

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org/10.1016/S0263-4368(02)00003-3
Chapter 10
Appraisal of Chitosan-Based
Nanomaterials in Enzyme Immobilization
and Probiotics Encapsulation

Subham Rakshit, Suman Kumar Halder, and Keshab Chandra Mondal

10.1  Chitosan

Chitin is most plenteous amino-polysaccharide in biosphere, found in the shells of

crustaceans (such as lobsters, crabs, shrimp, shellfish), fungal cell wall, insect cuti-
cles and exoskeleton, radula of mollusks, and the cephalopods beaks (Gooday et al.
1986; Choi et  al. 2004). Henri Braconnot, a French pharmacist and chemist, first
discovered chitin in 1811. It is a linear polymer of N-acetyl-D-glucosamine (GlcNAc)
linked by β-(1 → 4) bond, and chitosan is the deacetylated form of chitin. The main
dissimilarity between chitin and chitosan is that in the latter acyl groups are absent
which are attached by the amide bond in the chain of chitin. The free amines in the
chitosan polymer act as functional group. The reactivity and solubility of the chito-
san polymer are better than chitin and nontoxic in nature. Practically chitosan is
β-(1 → 4)-linked D-glucosamine (GlcN) along with few GlcNAc. The physicochem-
ical and functional properties of chitosan can be modified by changing the degree of
deacetylation (DD), derivatization, and chemical hydrolysis (depolymerization) of
the polymer (Halder and Mondal 2018). Chitosan is water insoluble but soluble in
acidic pH. This is due to the fact that at low pH most amino groups transformed into
protonated form and the positive charge reacts with water to solubilize (Sorlier et al.
2001). In case of commercially produced chitosan, molecular weight varies between
3800 and 20,000 dalton. Viscosity of chitosan varies between 10 and 1000 centi-
poise. High superiority polymers of known molecular weight are essential in biomedi-
cal uses of chitosan. It has wide varieties in degradation mechanism like
oxidation-reduction of free radical polymerization and enzymatic-catalysis.
Chitosan has numerous employments in pharmaceutical, medical, agricultural, cos-
metics, biotechnology, food technology, textile sectors because of its (i) nontoxic,

S. Rakshit · S. K. Halder (*) · K. C. Mondal

Department of Microbiology, Vidyasagar University, West Bengal, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 163

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_10
164 S. Rakshit et al.

(ii) biodegradable, (iii) biocompatibile, (iv) cationic, (v) bioactive, and (vi) bioadhe-
sive natures, and it is also easily commercially available at low cost (Chen et  al.
2006; Klotzbach et al. 2006; Halder and Mondal 2018).

10.2  Why Chitosan Is Useful in Enzyme Immobilization

According to many literature surveys, chitosan is one of the most common biopoly-
mer used for enzyme immobilization. Chitosan has a special property to control
over the discharge of the active mediator and eliminate the hazardous solvents while
constructing the particles in aqueous condition (Sheldon 2007). It is a very useful
property to make immobilized enzymes. It is a polyamine comprising of free amino
groups which are freely available for cross-linking with multivalent ions. The reac-
tive hydroxyl groups exert a better enzyme coupling effectiveness in adsorption and
covalent bonding of enzyme immobilization methods (Cao et  al. 2012). At the
absorption site of enzyme, the residual time increases because of chitosan’s muco-
adhesive character. Owing to its membrane-forming ability, low immunogenicity,
good adhesion property, and hydrophobicity, chitosan is a potential immobilization
matrix which provides excellent stability of the immobilized biocatalyst (de Moura
et  al. 2008). Chitosan is also used in immobilization techniques because of its
unique characteristics like enhanced resistance in degradation of chemical and elim-
ination of metal ion disturbances to enzyme (Yang et al. 2010). It also can act in
numerous shapes and forms. For example, in nuclease immobilization cross-linked
with bifunctional glutaraldehyde with chitosan provides the support through inter-
action of amino group with the aldehyde groups. Chitosan acts through other func-
tional groups like phenols, thiols, and imidazoles.

10.3  Nanoparticles

Nanoparticles are organic or inorganic particles which range varying between 1 and
100  nm. “Nano” word originated from Greek literature known as “Nanos” which
means dwarf or extremely short (Pal et al. 2011). Nanoparticles have various special
properties than other particles, which made a bridge between bulk materials and
molecular structures. When a particle size reduces in nanometers, their properties and
behavior (e.g., melting point, chemical reactivity, fluorescence, electrical conductiv-
ity, magnetic permeability, etc.) change from those at high scales, known as quantum
effects, and they can imprison their electrons. The unique properties of nanoparticles
are higher surface/volume ratio and melting temperature which provides tremendous
driving force for diffusion. Due to size-dependent properties of nanoparticles, surface
plasmon resonance is observed in some metal particles. It is used as enzyme immobi-
lization because of its higher permeability properties through barriers (e.g., biological
membrane, blood-brain barrier) and improved biocompatibility and some drug or
active materials can be encapsulated, entrapped, adsorbed, or attached in micromo-
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 165

lecular particles on the matrix surface (Janssen et  al. 2002; Sheldon 2007).
Nanoparticles acquire the various sites for enzyme molecules to make them a rigid
particle. Due to its high surface to volume ratio, it is encouraging for enzyme immo-
bilization. Nanoparticles on biocatalytic system provide elevated retention activity, as
enzymes attached to the particle surface make them available for substrates. Numerous
inorganic materials such as nanogold and graphene are used as matrices for immobi-
lization of enzymes. Not only that, various biopolymeric supports are widely used for
this purpose such as starch, agarose, cellulose, gelatin, albumin, chitosan, etc.
(Katchalski-Katzir and Kraemer 2000; Lozinsky et al. 2003; Salemi 2010). The main
ambition of the utilization of nanoparticles for releases of enzymes is to preserve the
structures and performance of the attached substance for a long time (Jia et al. 2003).
With the application of nanoparticles, it produces metabolites which effortlessly
degrade in biological environment.

10.3.1  Methods of Preparation of Nanoparticles

Nanoparticles are synthesized by both (i) top-down method and (ii) bottom-
­up method.
Top-down method  In this method the desirable material is formed from the bulk
material after cutting down into nano sizes.
Bottom-up method  In this method desirable material is formed by gathering the
building block particles.

10.3.2  M
 ethods of Preparation of Chitosan Nanoparticles
for Enzyme Immobilization

There are several methods to prepare the chitosan nanoparticles. These are (i)
reverse micelle method, (ii) ionic cross-linking method, (iii) coprecipitation method,
(iv) emulsion cross-linking method, and (v) ionotropic gelation method.

10.3.2.1  Reverse Micelle Method

A narrow range of polymeric nanoparticles are prepared following this method. In the
solvent, the surfactant is liquefied to form reverse micelles. In this process low molec-
ular weight of chitosan has greater control in particle size distribution. Following this
method, bovine serum albumin (BSA)-loaded chitosan nanoparticles are synthesized,
and 143–428 nm particle size was obtained. It also established that high chitosan con-
centration decreases the BSA release. Magnetic nanoparticles of chitosan can also be
prepared by reverse micelle method by employing glutaraldehyde and Span-80,
respectively, as cross-linking agent and emulsifier (Brunel et al. 2008).
166 S. Rakshit et al.

10.3.2.2  Ionic Cross-Linking Method

This is based on the ionic interaction of positively charged chitosan with oppositely
charged (negative) molecules. Tripolyphosphate (TPP) has frequently used for this
owing to its multivalent, nontoxic, and gel-forming properties. The preparation of
chitosan/TPP depends on pH, component ratio, concentrations, and process of mix-
ing. TPP concentration does not affect the surface amino groups of chitosan
nanoparticles. Ironic chitosan nanoparticle can be easily prepared by this process
having a diameter that varies between 50 and 100  nm (Nasti et  al. 2009; Wu
et al. 2009a).

10.3.2.3  Coprecipitation Method

Single step coprecipitation can be adopted for preparation of chitosan-coated magnetic

nanoparticles. Electron microscopy, X-ray diffraction, and magnetic measurements con-
firmed that the nanoparticles diameter stands between 10 and 11 nm. It is very essential
for removal of heavy metal ions from water (Gregorio-Jauregui et al. 2012).

10.3.2.4  Emulsion Cross-Linking Method

Acidic solution of chitosan is treated with n-hexadecane and sunflower oil mixture
for emulsification. This method revealed that wide range of particles size from 20 to
500 μm may be produced (Nagpal et al. 2010).

10.3.2.5  Ionotropic Gelation Method

In this method various sizes of chitosan nanoparticles can be obtained by using dif-
ferent gelation agent. The mean nanoparticle size of 162 nm and 517 nm were
obtained when sodium tripolyphosphate and sodium sulfate were used respectively
as gelation agent (Avadi et al. 2010).

10.4  Enzyme Immobilization

Enzymes are biological catalysts which are accelerating the chemical reaction
within the body to maintain life. Enzymes are large in size and very delicate mole-
cules unlike inorganic catalysts. Conventional soluble enzymes have many disad-
vantages due to the instability and sensitivity in reaction conditions. So, the uses of
solid phase catalysts have become very important. Enzyme immobilization is a
method of imprisonment of the enzyme molecules to a solid support that are insol-
uble in the reaction mixture. There are many benefits for using immobilized enzyme.
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 167

These are (i) it prevents the contamination of the substrate to reaction with enzyme
which indirectly decreases the purification cost; (ii) it provides longer half-­life and
less degradation of enzymes; (iii) it also make possible the efficient retrieval and
reuse of enzymes for the same reaction; (iv) it helps to control reaction rate and
time; (v) product stability is very high; (vi) after binding of enzyme to substrate,
enzyme changes into heterogeneous form to homogeneous form which results in
simple separation, and higher purified product is formed; (vii) the matrix or solid
support protects the enzyme in harsh reaction condition like pH, temperature, etc.;
(viii) and enzyme immobilization gives high catalytic activity.

10.4.1  Methods of Preparation of Immobilized Enzymes

10.4.1.1  Support Binding

It can be physical such as salt linkages, hydrophobic interaction, van der Waals
interaction, ionic, or covalent. Adsorption of enzyme is made by physical bonding.
For this bonding enzyme is dried on the electrode surface. Proteolysis of enzyme is
protected by contact with hydrophobic interfaces through adsorption (Spahn and
Minteer 2008). Hydrogen bonding also gives successful immobilization on the pore
walls silanols by use of silanized molecules sieves (Mitchell and Pérez-Ramírez
2011). The physical bonds are too weak and incapable to keep the enzyme fixed to
the supports in high temperature in industries. Ionic and covalent binding have
higher strength than physical bonding to support the enzyme and better performance
(Sheldon 2007). Covalent binding also helps magnetic nanoclusters to interact with
various active sites of enzymes (Patel et al. 2009). There are some limitations in this
type of immobilization like if somehow enzyme deactivates the carrier then it will
lost its function and become unusable. For this, support should be a synthetic poly-
mer such as resin, silica, etc.

10.4.1.2  Cross-Linking

Cross-linking acts a vital role to conserve both structural and functional properties
by using bifunctional chemicals. The most stable bifunctional cross-linking reagent
is glutaraldehyde because of its covalent bond subunits and solubility in aqueous
solution (Cirillo et al. 2014). Cross-linking is very valuable technique because in
carrier-dependent techniques, the enzyme lost its native property up to 50% (Roy
and Emilia Abraham 2004). Moreover, carrier bound technique is very laborious
and time based. Some carrier-free approaches have been developed for highly con-
centrated enzymes activity, high stability, and low production costs. These
approaches are cross-linked enzyme crystals (CLECs) (Roy et al. 2005) and cross-­
linked enzyme aggregates (CLEAs) (Sheldon et al. 2005, 2011). In nanotechnology,
cross-linking technique is very important because of enhanced porosity and more
168 S. Rakshit et al.

surface area to support nano-diameters. Cross-linked enzyme has been composed of

ionic polymer or organic solvents to make precipitation of aggregates (Sheldon and
van Pelt 2013).

10.4.1.3  Entrapment

Imprisonment of enzyme within the polymeric network (like organic polymer, sol-­
gel, and microcapsule) with the help of covalent and non-covalent bonds is known
as entrapment. In this process mechanical stability is enhanced; leakages of enzyme
from carrier are less and easily can operate in the target (Shen et al. 2011). In this
method enzyme is trapped on the external/internal surface of the prefabricated car-
rier. In different field application such as biofuels, fine chemistry, biomedicine, and
biosensors, the entrapment method has great impact through the nanostructure car-
rier (Wang et al. 2009; Wen et al. 2011). Important particle of entrapment is meso-
porous silica for its large surface area, high adsorption capacity of enzyme, etc.
characteristics (Chen et al. 2011). For instance, the lipase activity increases when
entrapped in sol-gel matrix of calixarene. Entrapment of both lipase and magnetic
nanoparticles in biomimetic silica improved biocatalytic activity.

10.4.2  Supports to the Enzymes

To enhance the efficacy of the immobilized enzyme, various materials can be used
as supports. These materials could be inorganic, organic, or composite. A support
can significantly increase the physiochemical properties as well as kinetic proper-
ties of an enzyme. The support protects the structure of enzymes in harsh industrial
conditions. It also provides high mechanical strength as well as high catalytic activ-
ity. The support should be nontoxic for the immobilized enzyme and for the product
and has to consist of various functional groups for binding with enzyme. The sup-
port should have high loading capacity of enzyme. The structural characteristics
such as porosity, compression, particle behavior, biodegradability, attract to protein
are very essential for a good support (Krajewska 2005). If a support contains small
pore size, it leads to diffusional limitation that can cause subsequent inactivity of
enzyme (Wong et al. 2009). The particles used as supports are classified as (i) clas-
sic materials and (ii) new materials.

10.4.2.1  Classic Materials

Inorganic Materials

Silica is the most frequent inorganic resources employed in enzyme immobiliza-

tion due to its chemical and high thermal resistance. Silica is also used as sol-gel
silica, colloidal silica nanoparticles, and fumed silica. Other inorganic materials
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 169

like aluminum, titanium, and zirconium oxides are widely used (Narwal et  al.
2014; Zou et al. 2014; Foresti et al. 2010; Vallés et al. 2011; Reshmi et al. 2007;
Yang et al. 2008).

Mineral Materials

Enzyme stability enhanced by using mineral materials as a support. Minerals are

used because of its easy availability and several reactive groups present on the sur-
face which helps formation of the covalent bond (Mbouguen et al. 2006).

Carbon-Based Materials

Due to high porous structure and surface area, carbon-based materials such as char-
coals is used as a robust support in enzyme immobilization (Daoud et al. 2010; Rani
et al. 2000).

Organic Materials

Due to some limitations of inorganic materials like restricted biocompatibility,

lower affinity, and inability to create geometrical shapes, organic support is applied.
Organic support is divided into synthetic and renewable materials.

10.4.2.2  New Materials

Synthetic Materials

The main advantage of this is that support material that constructs the polymeric
chain can be decided according to the requirement of enzymes. In a polymeric
structure, many chemical functional groups may be seen like carboxyl, hydroxyl,
amine, carbonyl, and diol groups as well as trialkyl ammine and alkyl groups (Kirk
and Christensen 2002; Ferrario et al. 2011). Polymer supports can be very effective
because of its improved properties like reusability and thermal stability. The layer
of polymer plays an essential role for protecting the active sites of enzyme in the
reaction mixture. Various polymers having different functional groups are used as
matrix for enzyme immobilization. For example, tyrosinase immobilized via –NH
and C=O groups on nylon 66 and via –NH group of polyaniline alpha-amylase is
immobilized (Ashly et al. 2011).
170 S. Rakshit et al.

Biopolymers

Besides synthetic polymer, biopolymers are also used as an alternative matrix mate-
rial for enzyme immobilization. Carbohydrate and proteins are used as biopolymer
support. For immobilization collagen, keratins, cellulose, carrageenan, alginate, as
well as chitin and chitosan are used. For various advantages like availability, abun-
dance, and simple process in synthesis, these materials play an essential role as
support for enzyme immobilization. The biopolymers have various special proper-
ties like biocompatibility, nontoxicity, and high affinity to proteins. Biopolymer
reduces the structural deformation and properties of enzyme and helps to maintain
high catalytic activity. Moreover, biopolymers are less expensive and therefore
decreases the cost of immobilization process (Horchani et al. 2012; Vijayaraghavan
et al. 2009; Homaei et al. 2013; Krajewska 2004).
Alginates act as biopolymeric supports for its capability for gelation by using
calcium and sodium ions and also for production of capsules which is capable of
immobilization of single or multiple enzymes (Hwang and Gu 2013; Coradin et al.
2003). So, alginates are used for entrapment and encapsulation methods. But due to
some limitations such as diffusional limitations and mechanical stability, its appli-
cation is hampered. Immobilization of lipase through entrapment in calcium algi-
nate beads and polyphenol oxidase encapsulated in copper alginate beads shows
fine catalytic activity but poor reusability. Agarose is widely used as support because
of its heteropolysaccharide chain composed of β-D-galactose and 3,6-anhydro-­
alpha-L-galactose linked by glycosidic bonds. It has high gelation capability like
alginates. It is used as capsules, beads, and fibers, leading great attention in indus-
tries. Agarose beads were used for entrapment of alpha-amylase and increase five
times reusability of biocatalyst (Ball and Morell 2003; Delattre et al. 2011). Chitosan
is the most used biopolymer because it can be used in different forms and shapes.

10.4.3  I mmobilization of Enzyme Through Chitosan

Nanoparticles

There are many researchers that tried to establish the suitability of chitosan nanopar-
ticles on enzyme immobilization by using various methods. Few researches had
assessed the optimum conditions for the enzymatic reaction like temperature, pH,
and kinetic parameters as well as enzyme stability, maximum yielding, reusability,
etc. In the following sections successful immobilization of different industrially
valuable enzymes on chitosan based matrix were documented.

10.4.3.1  β-Galactosidase

β-Galactosidase commonly used to prepare low lactose milk from galactose and
lactose through the transglycosylation reaction, and this enzyme has various indus-
trial applications. For this purpose the reusability, production of product, and stabil-
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 171

ity should be higher for real-life application at low cost. For immobilization of
β-galactosidase, various methods like covalent linking, cross-linking, and adsorp-
tion techniques have been industrialized. It was reported that magnetic (Fe3O4)-
chitosan nanoparticles preparation through electrostatic adsorption with Fe2+ and
Fe3+coprecipitation and glutaraldehyde-mediated coupling is a simple and quite
efficient technique (Pan et al. 2009). This study shows that there is improvement in
stability and provides structure rigidity which reduces the conformation changes.
The study also revealed that immobilized β-galactosidase shows higher enzymatic
activity in wide range of pH and temperature than the free enzyme. After 15 times
of utilization, immobilized enzyme retains its 92% initial activity and also increases
the storage capacity. Similarly, immobilization of β-galactosidase of Kluyveromyces
lactis was carried out through covalent binding with chitosan nanoparticles which
enhances the thermal stability and reused up to 50  times without loss of activity
(Klein et  al. 2012). Križnik et  al. (2018) successfully synthesized magnetic
maghemite nanoparticles with chitosan and amino-organosilanes for the immobili-
zation of β-galactosidase of Aspergillus oryzae.

10.4.3.2  Cellulase

Cellulase is essential to produce glucose by enzymatic hydrolysis used for conver-

sion of reducing sugar from cellulose. Zang et al. (2014) and Lin et al. (2017) docu-
mented that Fe3O4 nanoparticles coated with chitosan can be used in the
immobilization of cellulase by covalent binding using glutaraldehyde as cross-
linker. After 10 successive reuses, half of the initial enzyme was upheld in the
immobilized matrix. The production rate of glucose remains higher than 80% with
enhanced thermal stability. Cellulase is immobilized in chitosan-coated magnetic
nanoparticles (10 nm in diameter) through covalent binding where glutaraldehyde
was used as coupling reagent (Sánchez-Ramírez et al. 2017). The immobilized bio-
catalyst retained 37% of initial activity and 80% after 15 cycles of carboxymethyl-
cellulose hydrolysis reaction. It can be easily separated from the reaction mixture.
This also shows enhanced storage and thermal stability. It has various industrial
applications like bioethanol production.

10.4.3.3  Glucose Oxidase

Chitosan nanoparticle is also applied in glucose sensing. Kang et al. (2007) success-
fully immobilized glucose oxidase by cross-linking with chitosan gold/platinum
nanoparticles on carbon nanotubes (CNTs). This component shows great advantages
like broad range of glucose sensing, fast response to glucose (<5 seconds), and low
detection limit (0.21  M) with reasonable stability, reproducibility, and selectivity.
Nanocomposite of glucose oxidase/platinum/functional graphene sheets/chitosan for
sensing of glucose was prepared by Wu et al. (2009b). It shows very good sensitivity
of glucose up to 0.6 μM. The nanocomposite biosensor has long-term stability and
reproducibility and protects the signal from noise molecules. Onay et  al. (2018)
172 S. Rakshit et al.

immobilized glucose oxidase on electrode modified with Fe3O4 chitosan silver

nanoparticles. This helps to find out 5–30 mM glucose concentration. The stability of
electrode increases and shows good shelf life, and repeatability. It also provides fast
amperometric response.

10.4.3.4  Invertase

Invertase is a catalyst found in Saccharomyces cerevisiae which plays an important role

in sucrose hydrolysis and convert the sucrose in invert syrup which contains equal
amount of β-D-fructose and α-D-glucose. It is a very essential enzyme in food industry
to make sweeter product as fructose is sweeter than sucrose and helps to maintain the
softness of product. Valerio et al. (2013) prepared chitosan nanoparticles and immobi-
lized invertase by covalent modification. The immobilized invertase retains its maxi-
mum activity after 59 cycles. However, the storage and thermal stability of both free
and immobilized enzyme remain unaltered. Invertase was immobilized on chitosan
coated γ-Fe2O3 magnetic nanoparticles which increases the conversion rate and mag-
netic separation (Waifalkar et al. 2016). The immobilized invertase was more stable in
a broad range of temperature for 20 cycles with high activity.

10.4.3.5  Glucoamylase

Glucoamylase also known as amyloglucosidase is an essential enzyme for diges-

tion, and it has wide industrial-scale applications, viz., textile, beverage, food,
detersive, pharmaceutical, papermaking, and brewing. Glucoamylase from
Aspergillus niger immobilized into 1,3,5-triazine functionalized chitosan-coated
superparamagnetic nanoparticles through covalent attachment which retained 70%
of its initial activity after ten cycle (Amirbandeh et al. 2017).

10.4.3.6  Glucosidase

Liu et al. (2017) successfully immobilized α-glucosidase in chitosan-enriched mag-

netic composites by embedding method. Immobilized enzyme shows greater range
of tolerance of pH and temperature. Reusability of enzyme was increased, and
62.2% initial activity was retained after ten times of use. The storage stability is also
increased up to ~83%.

10.4.3.7  Xylanase

Xylanase (xylan degrading enzyme) is a very important enzyme in food industry

because it can produce xylooligosaccharide and also produce reducing sugar
from agricultural by-product. The bifunctional enzyme was incorporated onto
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 173

carbon-­coated chitosan nanoparticle by covalent bonding (Liu et al. 2015). It also

retains 82.6% of its activity after seven reactions and exhibited increased thermal
and storage stability.

10.4.3.8  α-Amylase

It is glycosyl hydrolase enzyme which breaks down the α-1,4-glycosidic bond of

starch and produces glucose, maltose, maltotriose, etc. It is widely applied in paper,
baking, textile, and food industries. Alpha-amylase is successfully immobilized onto
chitosan-TiO2 nanocomposite via adsorption method which increases the stability of
the enzyme and encourages its industrial applicability (Bindu and Mohanan 2017).

10.4.3.9  Pectinase

Pectinase is an essential enzyme in fruit juice technology employed to break pectin.

Sojitra et  al. (2017) immobilized pectinase onto magnetic chitosan nanoparticles
using cross-linker dextran polyaldehyde. Thermal stability of immobilized enzyme
was improved two times than free enzyme. The Km and Vmax values are approxi-
mately the same as free enzyme. Immobilized enzyme retains its conformational
flexibility. About 85% and 89% of the residual activity was retained by using the
immobilized biocatalyst for seven successive reuses and after 15 days of storage,
respectively.

10.4.3.10  Laccase

Laccase (dioxygen oxidoreductase) is blue copper oxidase enzyme found in bacte-

ria, insects, plant, and various fungus families. It degraded and detoxifies various
non-aromatic and aromatic compounds by using molecular oxygen. Fang et  al.
(2009) synthesized reversed-phase suspension-based magnetic chitosan nanoparti-
cles and immobilized laccase onto it by means of adsorption. The immobilized lac-
case showed good operational stability and storage capability. Laccase of Trametes
versicolor was immobilized into chitosan-coated magnetite nanoparticles cova-
lently by adsorption (Kalkan et al. 2012). Here, chitosan binds with cyanuric chlo-
ride (CC) or carbodiimide (EDAC) through hydroxyl group. The kinetic parameters
revealed that all combination of nanoparticles with CC and EDAC has lower Km
value than free enzymes, while chitosan nanoparticles with laccase show highest
catalytic efficiency. After 30  cycle uses, immobilized enzyme retains 71% of its
initial activity. Likewise, immobilized laccase in chitosan nanoparticles exhibited
reusability, enhanced half-life, and thermal stability for Congo Red decolorization,
and 98% of decolorization ability was retained in the immobilized matrix after 25
uses (Sadighi and Faramarzi 2013). Alver and Metin (2017) synthesized chitosan
nanoparticles chelated with Cu (II) and immobilized laccase into it by adsorption,
174 S. Rakshit et al.

and the immobilized biocatalyst was applied to remove phenol from aqueous solu-
tion. The immobilized enzyme displayed activity in a wide range of temperature and
pH and retains 50% of its initial activity after eight times of uses. The immobilized
enzyme removes 96% of phenol from aqueous solution. Tarasi et al. (2018) synthe-
sized chitosan-coated Fe@PA-CD (Fe@PACD-Cs) and immobilized laccase by
physical adsorption. The immobilized biocatalyst showed 100% of its activity in
temperature between 15 and 55 °C at pH 4.0. It also increases storage ability up to
70% after 12  days at 25  °C.  Fe@PACD-Cs removes phenol and bisphenol A by
96.4% and 85.5%, respectively. Therefore, this method can be useful in waste
treatment.

10.4.3.11  Lipase

Lipase (triacylglycerol acylhydrolase) is a hydrolase enzyme which generates free

fatty acids, glycerol, monoacylglycerols, diacylglycerols from fats, and oil. It is
found in fungi, bacteria, some plants, and animals. It has many biological roles like
esterification, enantioselective hydrolysis, and enantio-enriched monomer synthesis
and polymerization of macromolecules. But the free lipase has poor stability and
reusability. Moreover, after enzymatic reaction, separation of enzyme is very diffi-
cult. Therefore, to improve activity of lipase, immobilization is the best approach.
The enzyme lipase is immobilized in magnetic Fe3O4 chitosan nanoparticles with
the help of sodium tripolyphosphate (TPP) by covalent binding which shows higher
loading capacity and better stability of catalysts and decreases the loss of enzymes.
In this technique 129  mg/g enzyme adsorption and 20.02  μmol/min/mg enzyme
activity were acheived with improved retention capacity (Wu et al. 2009a). Liu et al.
(2011) synthesized magnetic Fe3O4 chitosan nanoparticles, and lipase is immobi-
lized through adsorption. The immobilized biocatalyst showed greater benefits like
enhanced storage stability and higher activity than free form. Kuo et  al. (2012)
immobilized lipase of Candida rugosa into magnetic Fe3O4 chitosan nanoparticles
covalently using N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (EDC) and
N-hydroxysuccinimide(NHS) as coupling agents. It was found that highest immo-
bilization can be achieved by performing immobilized reaction time 2.14 hours at
pH 6.3. It shows wide range of pH and thermal stability, and higher operational and
storage stability was also increased. Immobilized enzyme retains 83% of its initial
activity after 20  times of uses. Liu et  al. (2012) successfully developed alginate/
chitosan nanospheres immobilized with lipase where ethylene glycol (oxidic poly)
was used for functionalization. The alginate-chitosan nanosphere diameter was
60 nm and showed superparamagnetic properties. Alginate-chitosan contains posi-
tive charges and directly adsorbed lipase. Candida rugosa lipase (CRL) success-
fully immobilized through covalent binding and adsorption onto chitosan-alginate
nanospheres, respectively. Layer-­by-­layer (LbL) assembly process was utilized for
coat made up of chitosan and alginate to immobilized CRL (ICRL). Kinetic
study revealed that Km of alginate-ICRL was higher than chitosan-ICRL but Vmax of
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 175

chitosan-ICRL was higher than alginate-ICRL. The reusability of chitosan-ICRL is

far better than alginate-ICRL. Lipase of Thermomyces lanuginosus was also immo-
bilized in magnetic Fe3O4 chitosan nanoparticles through covalent modification
(Wang et al. 2015). Immobilized lipase can tolerate broad pH and high temperature.
After ten cycles of reaction, immobilized lipase retains its 70% initial activity. On
the contrary, chitosan nanoparticle was synthesized by ionic gelation method and
lipase was immobilized by cross-linking method (Devnani and Bahadur 2017). The
concentration of preparatory reagents (like chitosan, acetic acid, glutaraldehyde,
sodium) were checked and observed that changes in concentration of reagents it can
alter the activity and stability of immobilized enzymes. Ghadi et al. (2015) prepared
chitosan magnetic core-shell nanoparticles (CMNPs) in which lipase of Burkholderia
cepacia was immobilized. Total relative activity and stability was increased in
CMNP immobilized lipase. So, it is considered as suitable carrier for immobiliza-
tion of lipase. An innovative support for the cross-linking of chitosan shell coated
on magnetic nanoparticles with squaric acid (SqA) was developed in which lipase
of C. rugosa was immobilized by EDC and NHS. In immobilized state the activity
of lipase increased up to two times (Ziegler-Borowska et  al. 2017). Immobilized
lipase in magnetic chitosan/chitin nanoparticles was employed to produce biofuels,
and 97.8% yield was achieved only in 5 hours. Moreover, the immobilized biocata-
lyst can be used successively up to eight esterification cycle (Rahman et al. 2018).
In recent years for better activity of immobilized enzyme, the immobilization tech-
nique is improved and upgraded to nanocomposites. Magnetic chitosan nanocom-
posites were also designed for immobilization of porcine pancreas lipase (PPL) by
Suo et al. (2018). The immobilized biocatalyst has better reusability and enhanced
operational stability than free enzyme. Kinetic parameters also showed the improve-
ment of affinity between substrate and immobilized enzyme. In another study,
Xiang et al. (2018) synthesized SBA-CIL-chitosan nanocomposite as a carrier for
immobilization of PPL. It also provides higher immobilization efficiency with toler-
ance at varied pH and temperature, stability, and reusability. The enzymatic activity
increased up to 8.3 times and 82% of initial activity was retained.

10.4.3.12  Protease

Neutral proteinase is an essential catalyst in the industry like food, medicine, tan-
ning, etc. because it produces peptides and free amines through hydrolyses of pro-
tein. So, its stability should increase by immobilization. To improve the activity of
immobilized neutral proteinase, it was immobilized into chitosan nanoparticles by
ionization gelation method (Tang et al. 2006). After immobilization storage stabil-
ity, operational activity and thermal stability were increased, and it increased the
enzyme activity up to 13.17%. In acidic condition its stability was also increased.
Shojaei et  al. (2017) immobilized protease from Penaeus vannamei in chitosan
nanoparticles by ionic and electrostatic interaction which showed board range of pH
and temperature tolerance. Immobilization also improved reusability as well as stor-
176 S. Rakshit et al.

age stability. Trypsin was immobilized in carboxymethyl chitosan-functionalized

magnetic nanoparticles, cross-linked with 1-ethyl-3-(3-dimethylaminopropyl)
carbodiimide (EDC) and glutaraldehyde (GA) (Sun et  al. 2017). Immobilized
enzyme retained 71% and 88.5% residual activity when cross-linked with EDC and
GA, respectively, after six times of uses. After 14 days of storage, 80% and 88% of
initial activity was retained in the immobilized biocatalyst cross-linked with EDC
and GA, respectively. Demirkan et al. (2018) synthesized chitosan-blended cellu-
lose monoacetate nanofibers by electrospinning method and immobilized protease
by physical adsorption technique. The activity of enzyme was measured by utilized
casein as substrate. After seven cycles of reaction, 20% of activity of enzyme still
remain after glutaraldehyde activation. After glutaraldehyde and NaOH activation,
the operational stability of immobilized enzyme was increased and hence can be
utilized repeatability in textile and detergent industries.

10.4.3.13  Alcohol Dehydrogenase

Alcohol dehydrogenase oxidizes alcohols and converts into ketones and aldehydes.
Li et al. (2008) immobilized alcohol dehydrogenase from Saccharomyces cerevisiae
onto magnetic Fe3O4 chitosan nanoparticles. Thermal stability was increased and
durability was also enhanced.

10.4.3.14  Penicillin G Acylase

This enzyme converts penicillin G to 6-aminopenicillanate and aminodeacetoxy-

cephalosporanate. Both are essential for the construction of β-lactam antibiotics.
This enzyme was immobilized onto magnetic (Fe3O4) chitosan nanoparticles via
Schiff base reaction. Through this, higher thermal stability and wide range of pH
tolerance was achieved. After 10 times of uses, immobilized enzyme retains its 75%
of native activity (Ling et al. 2016).

10.4.3.15  Serratiopeptidase

It is a very important enzyme for the treatment of inflammation and pain. It is

widely used in treatment of atherosclerosis, arthritis, carpal tunnel syndrome,
chronic bronchitis, sinusitis, fibrocystic breast disease, postoperative swelling,
etc. (Tiwari 2017). Serratiopeptidase was also immobilized onto chitosan-assisted
magnetic nanoparticles (Kumar et al. 2014). It shows better storage stability than
free form of the enzyme.
Not only that, there are numerous number of enzymes which were immobilized
onto chitosan nanoparticles for improvement of their quality, stability, reusability,
etc. That is summarized in Table 10.1.
Table 10.1  Enzyme immobilized onto chitosan nanoparticles, optimization, and application
Optimum pH
Mode of and
Enzyme Support immobilization temperature Reusability Storage stability Applications Reference
Arsenite oxidase Chitosan Physical Wide range It retains its normal Conversion of As(III) to Pandey
(AOase) from nanoparticles adsorption of pH activity about 57.7% As(V) and Bhatt
(Exiguobacterium sp. (5–10) and and 39.7% at (2018)
As-9) temperature 40 °C–60 °C,
(4–37 °C) can respectively
sustain
β-Fructofuranosidase Chitosan-coated Covalent Optimum pH After 10 times of Conversion of sucrose to Chen et al.
magnetic bonding and FOS reaction, it fructooligosaccharides (2014)
nanoparticles temperature sustains its 55%
were 5.5 °C activity
and 60 °C,
respectively
α-Chymotrypsin Fe3O4−chitosan Covalent Optimum pH After 12 times of The developed Ju et al.
nanoparticles bonding and dipeptide immobilization model (2012)
temperature synthesis, it provides a simple,
were 7.6 °C sustains its 60% effective, and inexpensive
and 21.7 °C, activity process for industry
respectively application
Pullulanase Magnetic Covalent Optimum After 6 times of Free enzyme retains Due to high storage Long et al.
chitosan/Fe3O4 bonding temperature reuses, its activity by 11% stability and easy (2017)
nanoparticles above 60 °C co-immobilized whereas sol-gel recovery, it is applied in
via cross-linking encapsulation and food industry
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization…

retains its 85% co-immobilized

activity retains 52% and
69%, respectively,
at 62 °C after
5 hours
177

(continued)
Table 10.1 (continued)
178

Tannase from Amino-­ Optimum pH After 8 times of Application in tea Li et al.

Aspergillus niger functionalized and utilization, it infusion (2018)
magnetic temperature sustains its 50%
Fe3O4−chitosan were 4.5 °C initial activity
nanoparticles and 30 °C,
respectively
Acetylcholinesterase Chitosan Malathion detection Rodrigues
enzyme (AChE) magnetic iron et al.
nanoparticles (2018)
Horseradish Gold After 34 times of Applied for the detection Luo et al.
peroxidase (HRP) nanoparticle use, the biosensor of H2O2 in biosensor (2005)
enzyme customized shows its normal incorporates in indium tin
chitosan activity oxide (ITO) electrode
membrane
(Au–chitosan)
S. Rakshit et al.
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 179

10.5  Probiotics

From the very ancient times the living microorganisms in fermented products were
used for maintaining of our health. In the last century the Russian scientist Elie
Metchnikoff delivered the concept of consumption of live microorganisms for
health benefits (Gordon 2008). Generally probiotics are nonpathogenic live micro-
organisms which exert health beneficial effects when consumed in sufficient
amounts. There are various health-promoting properties of probiotics, like (a)
improves immune system in which it will supply, (b) maintains the natural gut
microflora, (c) increases the lactose tolerance, (d) decreases cholesterol level, (e)
exerts anti-carcinogenic properties, (f) inhibits pathogen by obstructing them to
adhere the activation sites, (g) provides available supply of nutrient, and (f) removes
toxin and its receptors (Prakash et al. 2011; Sullivan and Nord 2005). The various
functions of probiotics assist in the decrease of the gene expression related with
colonic cancer, prevent acute diarrhea, reduce the abdominal pain, defend the assault
of pouchitis, and decrease the chance of ulcerative colitis and necrotizing enteroco-
litis. Probiotics can prevent or reduce the intestinal diseases such as (a) infectious
diarrhea, (b) antibiotic-associated diarrhea (AAD), (c) irritable bowel syndrome
(IBS), and (d) inflammatory bowel disease (IBD). Lactobacillus and Bifidobacterium
genera were employed as probiotic product (Hoffmann et  al. 2013). Probiotic
microorganisms belong to the genus Lactobacillus, Bifidobacterium, Enterococcus,
Propionibacterium, and certain yeasts like S. boulardii. Probiotics can exert their
effect through various mechanisms. With the gut bacteria, probiotics can interact
through three different portions such as epithelial layer, mucus layer, and GALT or
gut-associated lymphoid tissue (Johansson et  al. 2011). Probiotics act on mucus
layer and intestinal layer and make team with gut microbiota for the interference of
pathogenic microorganisms through increases of the production of SCFA, blocking
the adhesion of pathogens to lumen. Moreover, it has also produced some toxin like
bacteriocin. Probiotics also enhance the barrier functions of Paneth cells, colono-
cytes, goblet cells, and enterocytes to increase the production of mucin, defensin,
and IgA (Quevrain et al. 2016; Hong et al. 2011). It also acts upon M cells, macro-
phages, dendritic cells, and T cells to regulate cytokine production and Treg responses
as well as some receptors situated on epithelium such as toll-like, C-type lectin,
Nod-like and RIG-I-like receptors, etc. Some probiotics bacteria like Lactobacillus
can exert their effects of immunomodulation through enhancing the production of
some peptides (Bouskra et al. 2008; Wang et al. 2014).

10.5.1  Probiotic Encapsulation

To ensure the favorable role, probiotics should survive in the digestion pattern of
host. After colonization and growth of the probiotics in the GI tract, they will
perform the beneficial activities. The major hindrances are acidic pH of stomach,
180 S. Rakshit et al.

the immune system of host, competition with commensal, and pathogenic microor-
ganisms (Mawad et al. 2018). There are many obstacles until or unless the probiot-
ics bacteria reach the target portion. Therefore, the protection in the passage of
digestive system should be given to probiotics through encapsulation (Ramos et al.
2018). Encapsulation of probiotics provides improved survivality of the organism in
the digestive system and provides protection from acidic condition, high oxygen
levels, throughout the gastrointestinal passage. The most essential advantages of
encapsulation are the following: (1) increase the adherence to mucosal tissue of the
intestine, (2) enhance the resistance of bacteria, and (3) keep the cell viable for a
long time (Chandramouli et al. 2004; Ramos et al. 2018).

10.5.2  Methods of Encapsulation

Encapsulation is the incorporation of essential ingredients in food to protect the

function and manage the discharge of ingredients. In microencapsulation solids,
liquids, and gaseous substances are packed in small capsules which release the con-
tents at controlled rates through long time (Champagne and Fustier 2007). The main
characteristics of encapsulation are: (a) should be water soluble, (b) keep their
structure after incorporation, and (c) release probiotics in the target portion. There
are mainly three types of technique for encapsulation, these are (1) spray drying
(Burgain et al. 2011), (2) extrusion (de Vos et al. 2010; Rokka and Rantamäki 2010),
and (3) emulsion (Heidebach et al. 2012).

10.5.3  Techniques of Coated Capsules

For better performance of encapsulated capsules, they need to be coated by edible

polymers. Coating provides various advantages like (a) higher stability in acidic pH
and wide range of temperature, (b) reduces capsules permeability, (c) proper release
of micronutrient, (d) proper delivery to the target. There are mainly two coating
techniques: (i) layer-by-layer (LbL) (Decher 1997) and (ii) coacervation (Eratte
et al. 2015). Among the various materials for coating of microcapsules, alginate,
chitosan, poly-l-lysine (PLL), whey protein, etc. are extensively utilized.

10.5.4  P
 robiotics Encapsulation in Chitosan-Based
Nanomaterials

In the digestive tract and the whole time between processing of food and consump-
tion, the viability of probiotics becomes low and failed to exert their effects.
Encapsulation provides storage (such as increase shell life of foods) and packaging
10  Appraisal of Chitosan-Based Nanomaterials in Enzyme Immobilization… 181

(from oxygen, temperature, humidity). Li et al. (2011) reported that high viable cell
count of 7.38 and 7.91 log cfu/g of Lactobacillus casei was maintained at immobi-
lized state in alginate-chitosan and alginate-chitosan-carboxymethyl chitosan
microcapsules after 2  hours in simulated gastric fluid. Similarly survival rate of
Bifidobacterium breve is reasonably good (6.6 ± 0.5 log cfu/mL) in immobilized
state in alginate-­chitosan after 1 hour in simulated gastric fluid (Cook et al. 2011).
Saccharomyces boulardii yeast cells were encapsulated in chitosan and dextran sul-
fate which protect it from acidic condition in simulated gastric fluid (Thomas et al.
2014; Shori 2017). Gandomi et al. (2016) successfully encapsulated probiotic bac-
teria Lactobacillus rhamnosus GG incorporated in chitosan-alginate with inulin and
examine their survival effect under stimulated gastric fluid and through storage of
apple juice. The storage study was done during storage at 25 and 4 °C for 90 days.
After the 90 days, the free bacterial survival diminished to 13.6%, but encapsulated
L. rhamnosus provides 4.5-fold improved survival rate than free cells. Sensory
scores revealed that encapsulation bringing the improvement of all characteristics of
probiotics. This study advocated that probiotic encapsulation enhanced the bacteria
survival rate both during storage of apple juice and in stimulated GI fluid without
any adverse effect. Two probiotics bacteria Lactobacillus acidophilus and
Lactobacillus rhamnosus were microencapsulated in calcium alginate-chitosan and
Eudragit S 100 nanoparticles (Ansari et al. 2017). In the study free cells (unencap-
sulated), single coated (only with chitosan), and double-coated beads (chitosan and
Eudragit nanoparticles) were applied in gastric juice without pepsin at pH 1.55 and
in intestinal juice with 1% bile sat at pH 7.5. The outcome of the study showed that
free bacterial counts diminished significantly (P < 0.001). The rate of decrease of
free L. acidophilus and L. rhamnosus was significantly faster than single- and dou-
ble-coated formation of encapsulated probiotics. Due to the lack of strength of sin-
gle chitosan-coated beads under pH  1.55, the counts reduced 5-log and 4-log of
L. rhamnosus and L. acidophilus, respectively. But double-coated beads showed
more viability of bacteria than that of single coated. Therefore, this study proved
that encapsulation with chitosan and Eudragit S 100 nanoparticles showed improved
survivability of L. acidophilus and L. rhamnosus probiotics in the acidic environ-
ment of stomach. Kim et al. (2017) successfully encapsulated probiotics bacteria
L. acidophilus through ionic gelation method and examine the encapsulated probi-
otics in stimulated gastric condition and storage. At first L. acidophilus encapsu-
lated in biocompatible and biodegradable capsules constructed by ionic gelation
between chitosan (CS) and phytic acid (PA). To increase the stability of capsules,
calcium carbonate (CaCO3) and starch were utilized. After 2 hours in acidic condi-
tion (pH  1.5, stimulated gastric fluid), the cells of L. acidophilus decreased only
0.64 log CFU/g. Among them, PA-CS-CaCO3 capsules are more stable than other
two capsules in pH 1.5 and 2.0. This study proved that encapsulation provides more
viability and storage capacity of probiotics bacteria. Likewise, Ebrahimnejad et al.
(2017) demonstrated that nanoencapsulation of probiotic Lactobacillus acidophilus
in chitosan endorse good probiotic viability and stability in intestinal juice.
182 S. Rakshit et al.

10.6  Conclusion

As renewable and biodegradable nanoparticles, chitosan continuously draws atten-

tion of both academicians and industrialists. In recent ages, chitosan-based nanoma-
terials have acquired a remarkable advantage over their conventional counterparts.
The amazing and unique physicochemical properties of chitosan advocate its wide-
spread application in immobilization of many important enzymes as well as encap-
sulation of probiotic microorganisms. In the arena of enzyme immobilization,
chitosan-based nanomaterials endorsed enhance stability and activity of the immo-
bilized biocatalyst which attested their long-term use and reuse. Encapsulated
­probiotic microbes in chitosan-based nanomaterial enhance the stability and viabil-
ity of the microbes especially in simulated gastrointestinal environment. In conclu-
sion, chitosan-based nanomaterials can be considered to be a promising outlook for
long-­term repetitive use of industrially viable enzymes as well as introducing of
viable probiotics for enhanced activity and stability.

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Chapter 11
Nano-Based Drug Delivery Tools
for Personalized Nanomedicine

Shama Parveen, Neera Yadav, and Monisha Banerjee

11.1  Introduction

Recent chemotherapeutics are not so effective; therefore, the development of new

alternative strategies is necessary to fight lethal diseases such as cancer, HIV, hepa-
titis, etc. Nanotechnology provides the manipulation of compounds at nanorange
and has the possibility to increase response, compatibility, and reduce the expense
of diagnosis. The generative biomolecules such as DNA or proteins can be analyzed
by red-shifted absorbance of gold nanoparticles or alteration in the conductance of
nanowires and declination of a nano-cantilever. Different types of nanocarriers, for
example, quantum dots and metal oxides have shown adequate benefits over con-
ventional detections, tagging of intracellular, and image of the target site.
Nanotechnology has also provided many routes which enable increased detection of
target cells. Proteins and DNA are used over a point for care of tool. Chips (protein
or gene) can be developed by using nanomaterials which could be attached to con-
venient nanofluidic tools for better diagnosis of diseases. Nanomaterials have design
flexibility and small size and can be modified easily for compatibility to the target
site. Interactions of nanosized materials with the biological system will benefit from
knowing their effects and development of differently sophisticated nanodevices.
Different nanocarriers are being used for delivery of compounds like inorganic
nanocarriers (metal nanoparticles, graphene, mesoporous silica, etc.), lipid-based
nanovesicles (liposome, nanoemulsion, solid lipid nanocarrier, etc.), polymer-based
nanocapsules (dendrimer, ligand decorated nanoparticles, core-shell nanocapsule,
etc.), and molecular complexes (protein nanocomplexes, cyclodextrin nanocom-
plexes, etc.) (Fig. 11.1). The main goal of nanobiotechnology is to use this t­ echnique

S. Parveen · N. Yadav · M. Banerjee (*)

Molecular & Human Genetics Laboratory, Department of Zoology, University of Lucknow,
Lucknow, India

© Springer Nature Switzerland AG 2020 189

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_11
190 S. Parveen et al.

Fig. 11.1  Types of nanocarriers

to study how biological systems work and, in turn, can perk up existing nanotech-
nologies or create more beneficial nanomaterials.

11.2  Applications of Nanotechnology in Biological Sciences

11.2.1  Drug Delivery in Cancer

11.2.1.1  Gelatin Nanoparticle

A targeted drug-reaching system followed by reformed “decrease in size and hydro-

phobic/hydrophilic modification” was processed by the addition of gelatin nanopar-
ticles (GNPs) with a drug Doxorubicin-Lactose (Dox-Lac). The effect of
GNPs-Dox-Lac nanoformulation lasting in the circulatory system has a more effec-
tive accumulation toward the tumor region. Nanocarrier breakdown is stimulated by
MMP2 (matrix metalloproteinase) present in tumor cells, and drugs are released to
make an easy penetration in tumor tissues and cellular uptake. The pH change will
result in dissociation of drug Dox-Lac in tumor cells, and free Dox (Mw 543 Da)
will stimulate toxicity. GNPs-Dox-Lac promotes inhibition of tumor growth rate up
to 90.4% by less in vivo toxicity, indicating that the activity was improved in the
nanoform for hepatocellular carcinoma (HCC) (Liu et al. 2018).

11.2.1.2  PEGylated Liposomes

PEGylated liposome (PEG-LS) formulation mostly is used as a targeted drug deliv-

ery tool. The inflexibility and hydrophilicity of liposomal PEG corona membranes
limited cellular uptake of the drug (Sadzuka et al. 2003). A new assembly for drug
11  Nano-Based Drug Delivery Tools for Personalized Nanomedicine 191

release was developed on lipid-based self-assembled nanoparticles that are compe-

tent for increased cellular uptake, penetration in tissues, and release of drug.
Researchers characterized a better bicellar nanoformulation with the addition of a
PEGylated phospholipid which presented a remarkable change of physicochemical
property in morphology, i.e., the bicelles (disc-shaped) equally distributed into very
small (~12 nm) circular micelles. The converted lipid nanoparticles were defined as
hyper-cell-permeable micelles (HCPMi). The HCPMi confirmed not only extended
stability in serum but also higher cellular and tumoral uptake than the usual
PEGylated liposomal system (PEG-LS) (Saw et al. 2017). HCPMi exhibited fast
cellular intake and release of cargo in the cytoplasm of cancerous cells. Cancerous
cells treated from the drug (docetaxel) loaded with HCPMi compared to the DTX
(docetaxel) loaded with PEG- LS showed about fivefold decrease in viability of
cells, showing best effectiveness in HCPMi intake and discharge of drug. HCPMi
entered deeply into the tumor cells and found more uptake than PEG-LS as shown
by in  vivo tumor imaging analysis. Studies showed that in  vivo treatment with
HCPMi (DTX) increased tumoral uptake and remarkable tumor growth inhibition,
about 70% tumor weight reduction in an experimental model (Saw et al. 2017).

11.2.1.3  Nanovaccines

Nanoformulation is useful in the development of cancer vaccines. Earlier PLGA

(poly lactic-co-glycolic acid) nanoformulations were modified with toll-like recep-
tor 7 agonist, imiquimod. These, immune adjuvant nanoparticles (NP-R) was
coated with membranes of cancer cell (NP-R@M). These formulations were further
modified by mannose moiety (NP-R@M-M). The resulting nanovaccine exhibited
increased cellular uptake through dendritic cells that are antigen-presenting cells,
which could be further stimulated for enhanced antitumor immune response by
delaying tumor development and thereby act as a preventive vaccine (Yang et al.
2018). Combination of vaccine (NP-R@M-M) by cellular checkpoint-regulator
treatment provides us with more effective therapeutic impact to treat established
tumors. It would be helpful to design cancer nanovaccines, and the principle may
apply to a broad range of tumor types (Yang et al. 2018).

11.2.2  Phytochemical-Based Nanodrugs

11.2.2.1  Nanocurcumin

The anticancerous activity of curcumin has been reported in different studies includ-
ing pancreatic cancer (Vallianou et al. 2015). Curcumin is of immense importance
it can not be utilized completly as medicine due to certain drawbacks such as low
bioavailabilty, solubility and stability. For enhancing its therapeutic effect, a polymeric
form of nanoparticles shows an ideal delivery method. Moreover, for improving the
192 S. Parveen et al.

potential of a drug, availability at target site, and circulation time in blood, modifi-
cations on the surface of nanocarriers by different macromolecules, such as chitosan
and polyethylene glycol (PEG), hold tremendous potential. Curcumin loaded PLGA
make it more effective by modifing the surface with chitosan and PEG can diminish
the restrictions of native curcumin delivery for obtaining a maximum therapeutic
response. In vitro studies of CNPs in pancreatic cancer showed higher cytotoxicity,
increased anti-migratory, and ability to induce apoptosis in comparison to the native
form of curcumin. Therefore, results of such studies can provide options for com-
bating pancreatic cancer (Arya et al. 2018).

11.2.2.2  Nano-ginseng

Ginseng plant product having anticancerous activity was used in nanoformulation

with ginsenoside Rb1/protopanaxadiol nanoparticles (Rb1/PPD NPs). The range of
nanoparticles was about 110 nm with high drug loading capacity and stability in
blood circulation, effective both in  vitro and in  vivo with better accumulation in
tumor tissues and less toxic to normal tissue. The process of producing “nano-­
ginseng” formulation is easy, measurable, and economical (Dai et al. 2018).

11.2.2.3  Nano-quercetin

Quercetin is a potential chemotherapeutic drug. The drug was encapsulated in solu-

plus polymeric micelles by using the film dispersion method in order to improve its
poor aqueous solubility and stability. In polymeric micelles (Qu-PMs) loaded with
quercetin, more encapsulation efficiency and narrow size distribution led to com-
plete drug dispersibility in water. Quercetin was in molecular form within the
plasma membrane and was analyzed by X-ray diffraction (XRD) (Dian et al. 2014).
Quercetin also formed intermolecular hydrogen bonding with carriers, analyzed by
Fourier-transform infrared spectroscopy (FTIR). The stable formulation Qu-PMs
exhibited significant sustained-release property. The pharmacokinetic study showed
that absorption was also improved when compared with the free form of quercetin.
Development of more appropriate formulations such as soluplus polymeric micelles
were used for encapsulation of many drugs, i.e., poorly water soluble (Dian
et al. 2014).

11.2.2.4  pH-Dependent Nanotools

siRNA-based nanotools in RISC (RNA-induced silencing complex) will undergo

many changes in pH before showing their gene silencing mechanism (Nelson et al.
2014). They flood through the circulatory system, protrude into tumor tissue
(pH  7.2–6.0), are introduced in the cell organelles such as endosomes with
pH  5.0–6.5 and lysosomes (pH  4.0–5.0), and at last evade in the cytoplasmic
11  Nano-Based Drug Delivery Tools for Personalized Nanomedicine 193

environment of the cell. Many pH-based formulations were developed by decreasing

the pH. Due to a decrease in pH, ionizable polymers like polyacids, cationic lipid,
and poly amino acids can protonate to change solubility and electrostatic interaction
or break the acid-cleavable bonds like hydrazine, ketal, ester, and nanocarriers for
the release of cargo (Zhang et al. 2018).

11.3  Disease Diagnostics

11.3.1  Magnetic and Electrochemical-Based Nanoparticles

HIV-infected cells have been detected by magnetic nanoparticles (NPs) in  vitro
(Dodd et  al. 2001). Magnetic NPs can be formulated according to target cells.
Separation of treated cells from other cells is through a magnetic separation device.
The formulation of anti-HIV drug-loaded magnetic nanoparticles is applied with
changing magnetic field. Magnetic NPs such as magnetite (Fe3O4) have been stud-
ied due to their specific characteristics like stability, biocompatibility, and sensitiv-
ity toward the magnetic field. Magnetic-based carriers for targeted drug delivery are
mostly used due to their less toxicity, biocompatibility, magnetic resonance imag-
ing, and higher magnetic saturation (Mahajan et al. 2012). Magnetic properties of
these NPs are dependent on their synthesis. Co-precipitation method was used to
synthesize Fe3O4 NPs. Size of the particles can be controlled by coating of polyeth-
ylene glycol (PEG) at the surface. Evaluation of biocompatibility of these nanopar-
ticles was done by cytotoxic assay and analysis of cell cycle in MCF-7 (human
breast cancer cell line) (Kansara et al. 2018).

11.3.2  Gold Nanoparticles

Hepatitis is a viral disease which can cause chronic syndrome and many other dis-
eases. Nanoformulation also performs a good role in diagnosing hepatitis caused by
hepatitis B and C viruses. Previous recognition tools did not yield much efficiency
and susceptibility. New detection systems were developed by researchers that are
based on the electrochemical method, with a test of gold-enhanced nanoformulation
conjugation of magnetic beads. This technique is very sensitive and specific for
recognition of the DNA sequences of hepatitis B virus (HBV) (Hanaee et al. 2007).
Electric potential of immunosensors increases with an increase in the amount of
HBV (Tang et  al. 2004). The study provides support that immunosensors can be
used in the future as a detection system for hepatitis B virus. Gold nanoparticles are
a preferred delivery system for immunosensors because of their compatibility with
antibodies. Nanosized gold protein chips were created to detect and analyze anti-
bodies of hepatitis B and C at the same time. Formulation of gold nanoparticles
194 S. Parveen et al.

provides evenness and stability. Easier detection of antibodies is a result of stronger

signals generated by gold nanoparticles (Duan et al. 2005). Significant amount of
data shows that gold nanoparticles make the analysis and detection of hepatitis virus
more successful.
Mycobacterium tuberculosis (MTB) bacteria cause the infectious disease tuber-
culosis that infects respiratory system (Shingadia and Novelli 2003) and considered
as the second deadliest disease (WHO 2010). According to WHO report 2010, one
third of the global population was infected by MTB, the strain which provides dif-
ficulty in detection and treatment. Gold nanoparticles detect MTB strands by DNA
and RNA screening. MTB can be detected within few hours by nanoparticle probe
(Veigas et al. 2010). Detection of MTB is based on pattern of color change due to
aggregation of nanoparticles. The culture of MTB was important to analyze and
detect bacterial strains. DNA fragments of MTB are broken down by electrochemi-
cal biosensors and are labeled by gold nanoparticles (Wang et al. 2013).
Nanotechnology is emerging as an advanced technique for the treatment of bone
inflammation. Acton initiates as metallic nanoparticles offer a good surface for
osteoblasts to connect to the bone. Metallic nanoparticles enable the growing of
osteoblasts in a specific time interval and are helpful in successful osteo-­regeneration.
Nanocomposite materials induced specific protein for bone regrowth.
Nanoformulated hydroxyapatite, the ceramic component of the bone, shows an
increase in production of osteoblast (Tran and Webster 2009). Nanocomposites with
carbon nanotubes also exhibit increasing osteoblast formation. Osteointegration
process is accomplished in nanotubes by preventing the competition with other
types of cells.

11.3.3  Nitric Oxide-Embedded Nanoparticles

Recently, the barrier of skin infection treatment has been overcome by nanotechnol-
ogy. Nanoformulated therapeutic drugs are able to release the drug over a time
period without any damage to the skin (Cevc and Vierl 2010). Nitric oxide-loaded
nanoparticles are used in skin treatment, and the drug is released in a controlled time
period. Different types of skin diseases were also treated by other formulations
based on the same technique (Wang et al. 2008). Nitric oxide-loaded nanoparticles
showed an improved response to treatment compared to the use of injectable nee-
dles for a skin infection (Englander and Friedman 2010).

11.3.4  Sunscreen

Ultraviolet (UV) radiation is a well-known cause of skin inflammation. The outer

most layer, stratum corneum, provides protection to the body against harmful UV
radiation. Sunscreens containing nanoparticles are used by humans to protect the
11  Nano-Based Drug Delivery Tools for Personalized Nanomedicine 195

skin from UV damage. Zinc oxide (ZnO)- and titanium dioxide (TiO2)-based nano-
formulations are mostly used in the manufacturing of sunscreens. This nanoformu-
lation reflects the harmful UV-A and UV-B radiations to the atmosphere in the form
of heat. ZnO and TiO2 inhibit UV photons from reaching the skin cells through
absorption and reflection mechanism (Popov et al. 2010).

11.3.5  Personalized Nanomedicine

Personalized medicine is a healthcare strategy that involves development of specific

treatment at the individual level on the basis of their genetic makeup, phenotype,
and environmental conditions (Ge et al. 2014). These days, use of nanomedicines is
increasing exponentially and providing a platform for the treatment of every patient
or group of patients (cohort) on the basis of a specific requirement in their genome
(Zhang et al. 2012). Nanomedicines are used as therapeutic agents for personalized
treatment, and their application is considered for a better treatment by pharma com-
panies. Different types of nanomedicines exist, i.e., liposome, polymeric nanopar-
ticles, magnetic-based nanoparticles, and micelles. All show advantages and
improve the effect of conventional therapy (Fig. 11.2). These advantages are due to
their small size, different nature, protected encapsulated material, controlled release

Fig. 11.2  Selection of patients selection after treatment with nanomedicines

196 S. Parveen et al.

for targeted delivery, increased therapeutic effect, and reduced side effects
(Fornaguera and García-Celma 2017).

11.3.6  Personalized Nanodevices

Point of care (P-o-C) provides a beneficial platform for personalized medicine. It is

useful in early diagnostic and more sensitive toward the detection of biomarkers in
treatment monitoring. The infectious diseases can be controlled by a personalized
diagnostic method by using P-o-C technologies in developing countries and envi-
ronment where resource is limited. The liability of disease diagnostic protocols can
be improved by using multiplexed assays by analyzing multiple biomarkers.
Multiplexing of assays provides the multivariate analysis of huge number of the
patient samples at one time (Romeo et al. 2016). In this way improved determina-
tion diagnosis of a particular biomarker of the disease can be achieved. The much
more diagnostic power of multiplexed point-of-care biosensors is generated which
are portable, cheap, and user-friendly devices. The first device of such kind, i.e.,
multiplexed volumetric bar-chart chip, was reported for analyzing protein bio-
marker of cancer (Song et al. 2012).

11.3.7  Microfluidic Channels on Bar Charts of Glass Chip

Channels contain covalently attached antibodies on the surface of glass walls with
dye and pre-loaded hydrogen peroxide for an enzyme-linked immune sorbent assay
(ELISA). The principle of V-chip is based on the measurement of oxygen that is
generated on the chip as a result of reaction between hydrogen peroxide and cata-
lase. The concentration of oxygen is directly proportional to the target analyte. The
excellence of this inked bar result is based on the concentration of particular ELISA
target in every well. Complete unification of the device provides results without any
data processing steps. The V-chip method is rooted in the expression of different
biomarkers such as including estrogen receptor, human epidermal growth factor
receptor 2, and progesterone receptor (Song et al. 2012).

11.3.8  Proteinticles

Proteinticles are engineered nanoscale protein particles which are very helpful in
modifying different properties based on size and surface area of many conventional
things. The detection of more than one biomarker in serum is also possible through
11  Nano-Based Drug Delivery Tools for Personalized Nanomedicine 197

multiplexed viral detection (Chen et al. 2015).The method of disease detection is

imperative in diseases like AIDS and hepatitis. This protocol is based on lateral flow
assay (LFA) for protein nanoformulation. Proteinticles have better biodegradability
and biocompatibility and are easily accessible to surface modifications (Lee et al.
2015). These nanoformulations are synthesized by using different proteins like gel-
atin, gliadin, elastin, zein, legumin, soy protein, albumin, and milk protein. Different
methods used for the formulation include desolvation, emulsification, electrospray,
and coacervation. Characterization parameters of these nanoforms comprise size of
particle, morphology of particle, their surface charge, loading of drug, entrapment
of drug, and structure of particle and drug release in vitro. Application of adminis-
tration route of protein nanoparticles through different methods has been examined
by renowned researchers (Verma et al. 2018).

11.3.9  Aptamers

The aptamer is an oligonucleotide-based nanoformulation. Advance characteristics

of aptamer show high-binding affinity and specificity with target molecules in both
intra- and extracellular environment. It works as an agonist or antagonist in a bio-
logical system. In recent years, several aptamers are used in the detection of disease,
and curative purposes are under development to identify different molecules of
HCC (hepatocellular carcinoma). The aptamer has been to increase the effect of
conventional chemotherapies and reduces the growth of HCC cells in vitro. Aptamer
induces antitumor activity and cell death in vivo. Overall data show that aptamer has
reduced toxicity levels, and it may provide safer platform in the field of personal-
ized medicine (Ladju et al. 2018).

11.4  Conclusion

Nanoscale materials allow nanodevices to enter new scientific and technological

frontiers in disease diagnosis and treatment. Advance nanoscale characteristics of
these devices especially their increased surface to volume ratio afford high-­
sensitivity and low-response times.

Acknowledgments  SP and NY are thankful to Council of Scientific and Industrial Research

(CSIR) and University Grants Commission (UGC), New Delhi, respectively, for providing finan-
cial assistance. The research grant provided to Molecular and Human Genetics Lab by Higher
Education, Govt. of UP, Lucknow, under Centre of Excellence program is duly acknowledged.
198 S. Parveen et al.

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Chapter 12
Nanotechnology as Potential
and Innovative Platform Toward
Wastewater Treatment: An Overview

Akhilesh Kumar Singh and Paras Porwal

12.1  Introduction

Clean and safe water is a prerequisite for the survival of living creatures (flora and
fauna) on earth. It is not only crucial for survival of living organisms but also drink-
ing, domestic purposes (like cooking, washing and cleaning, etc.), and industrial as
well as agricultural usages, e.g., irrigation for food production. In present scenario,
several anthropogenic activities like revolutionary industrialization and urbaniza-
tion, climate change, as well as the advanced agricultural practices have put massive
strain on water resources including significant deterioration in water quality with
increased water pollution and water crisis (Alcamo et al. 2017). Approximately, 844
million people lack basic drinking water facility, and 2 billion people drink fecal
polluted water (WHO 2017). Also, it is anticipated that world’s population will
enhance up to approximately 2.9 billion by 2050 (Rockström 2003). Scarcity of
freshwater is also because of the use of water sources toward domestic, industry, as
well as irrigation purposes globally (Rockström 2003). Pollution of surface as well
as groundwater resources is an additional reason toward decreased freshwater avail-
ability. Mostly, in developing countries, surface water is polluted by industrial and
domestic wastewater containing microbial agents (pathogenic and nonpathogenic)
with rich source of metals (toxic at above certain concentration) like plumbing (Zn,
Pb, Cu, Al, etc.), cosmetics (Fe, Cu, Zn, etc.), pesticides (Hg, Zn, Cu, etc.), deter-
gents (Fe, etc.), and pharmaceuticals (Ag, Fe, Al, etc.). Furthermore, As, Hg, Pb,

A. K. Singh
Department of Biotech and Genome, School of Life Sciences, Mahatma Gandhi Central
University, Motihari, Bihar, India
P. Porwal (*)
Amity Institute of Biotechnology, Amity University Uttar Pradesh, Lucknow Campus,
Lucknow, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 201

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_12
202 A. K. Singh and P. Porwal

and Cd are toxic for all living beings, and they have no biological functions
(Zinicovscaia et al. 2015). Pollutants in water not only cause waterborne diseases
but also result in potable water crisis. It has been estimated that relatively 50% of
the world’s population will live in water-stressed areas by 2025 (WHO 2017). Thus,
there is urgent need to develop economical as well as stable materials together with
innovative approaches by water industries so as to yield the freshwater in abundant
quantities. There are various physical and chemical strategies like chemical precipi-
tation, oxidation or reduction, filtration, ion exchange, evaporation and electro-
chemical treatment, reverse osmosis, etc., with the help of which one can get rid of
the contaminants like heavy metals present in the water. However, the majority of
these approaches turn out to be unsuccessful with heavy metals concentrations
<100 mg/l (Ahluwalia and Goyal 2007). Biological treatment systems like activated
sludge as well as biological trickling filters are not capable to eliminate vast range
of increasing contaminants. Moreover, the majority of these contaminants are found
to be soluble in the effluent (Amin et al. 2017). Considering these, it is obvious that
conventional water or wastewater treatment strategies are found to be inefficient
toward yielding sufficient harmless water owing to enhancing need of water together
with strict health guidelines as well as newly emerged pollutants/contaminants.
Therefore, nanotechnology-based multifunctional as well as extremely competent
approaches are found to come up with solutions of water or wastewater treatments,
which require no vast infrastructures/centralized systems (Amin et  al. 2017).
Nanotechnology is found to be efficient toward solving aforementioned water issues
concerning quality and quantity (Bottero et al. 2006). Among advanced water treat-
ment systems, nanoparticles like carbon nanotubes (CNTs) as well as dendrimers
are playing important role for the development of improved treatment strategies
(Porwal and Sharma 2016; Obare and Meyer 2004).
Nanotechnology is a technology-based science in diverse directions and deals
with the processing, deformation, amalgamation, and separation of materials by
molecules or atoms (Ardelean 2015). Nanotechnology has induced and heralded a
new industrial revolution mainly due to their biocompatibility (Sharma et al. 2016).
In today’s scenario, nanoscience due to the extraordinary properties of nanosized
materials has become the thirst area for researchers. These nanosized materials are
intervening macro and atomic or molecular level materials (Singh et al. 2018, 2019;
Pandey et al. 2019; Rani et al. 2020 ). The unrestricted application of these nanopar-
ticles in diverse field of science has boost their demand, and to meet the enhanced
demand in a short time, researchers have utilized various physical and chemical
methods to synthesize nanoparticles like arc-discharging liquid, lithography, laser
ablation, gas phase deposition, ball milling (Blosi et al. 2011; Kim et al. 2006a, b),
microemulsion, electrochemical deposition, coprecipitation sonochemical, and heat
decomposition process (Chatterjee et  al. 2012; Liu et  al. 2012; Ramyadevi et  al.
2012; Nakamura et al. 2007; Park et al. 2007). These methods produce metallic as
well as other nanoparticles of diverse size and shape with numerous applications
like agriculture, food processing, packaging, clinical diagnostics, wastewater treat-
ment, and environmental remediation (Shan et  al. 2009; Macaskie et  al. 2010;
Bradley et  al. 2011; Zambrano-Zaragoza et  al. 2011). But these environmentally
12  Nanotechnology as Potential and Innovative Platform Toward Wastewater… 203

unfriendly methods of nanoparticle synthesis give rise to environmental hazards and

biohazard (Singh et al. 2016, 2017; Rawat et al. 2018; Du et al. 2018). Thus, there
is an urgent need to develop alternate approaches/methods for synthesis of
­nanoparticles that are eco-friendly and cost-effective and pose negligible negative
effect on human health and can be exploited at commercial scale. Therefore, green
synthesis of nanoparticles is an attractive strategy in current scenario, which is gain-
ing huge importance owing to its nontoxicity, exploitation of renewable sources of
energy, consumption of lesser energy, and operability at low temperatures with
environment-­friendly procedures over traditional approaches (Sharma et al. 2016).
Green synthesis of nanoparticles involves biological systems like plant or microor-
ganisms (like bacteria and fungi), which are responsible for the transformation of
metal salts into nanoparticles by playing the role of reducing, stabilizing, and cap-
ping agents. The biosynthesis of nanomaterial exemplifies a link between nanotech-
nology and biotechnology. Among various applications of nanoparticles, the
treatment of wastewater/contaminated water using nanobiotechnology is gaining
tremendous attention globally in current scenario. This is owing to their simplicity,
economic feasibility, and disinfection efficacy.

12.2  F
 abrication of Nanoparticles: Physical, Chemical,
and Biogenic Approaches

Generally, the fabrication of nanoparticles can be categorized into two, i.e., “top-­
down” and “bottom-up” approaches. In top-down approach, any chemical or physi-
cal method is used to convert bulk material into nanosized particles, while bottom-up
approach utilizes any biological or chemical method to transform into nanoparticles
from atom/molecules through a series of step (Fig. 12.1). Nanotechnologist mostly
prefers bottom-up approach as nanoparticle synthesized by this is more homoge-
nous in structural and chemical composition and the chances of imperfections are
also minimized. Although the physical, chemical, and mechanical methods are the
predominant conventional methods for nanoparticle synthesis, currently the bio-
logical methods are becoming more popular because of their several advantages
over conventional methods (Fig. 12.2). Normally, nanoparticles are of two types,
i.e., organic (include carbon nanoparticles) and inorganic nanoparticles; they com-
prise of metal nanoparticles like Ag, Pt, Au, and Pd magnetic and semiconductor
nanoparticles like TiO2, SiO2, and ZnO2. Green synthesis of nanoparticles using
different biomass like bacteria, algae, fungi, yeast, viruses, actinomycetes, plants
and plant parts, pure or commercially available biomolecules, and biological waste
materials is widely employed as a potential platform for fabrication of metallic
nanoparticles (Mittal et al. 2013; Sharma et al. 2015). Mostly, a metal precursor is
involved in the biosynthesis of nanoparticles, which is reduced or transformed either
intracellularly or extracellularly using biological extract/biochemicals as a source of
reductant present in the biomass (Asmathunisha and Kathiresan 2013). The extra-
204 A. K. Singh and P. Porwal

Mechanical/Bal milling
Chemical etching
Top to bottom Thermal/Laser ablation
Sputtering

Toxic
Synthesis of Bulk
Nanoparticles Nanoparticles
Chemical/Electrochemical
precipitation
Vapour deposition
Bottom to Top Atomic/Molecular
Condensation
Sol-Gel Process
Spray Pyrolysis
Laser Pyrolysis
Aerosol Pyrolysis

Nanoparticles
Green Synthesis
Nuclei Bacteria Non Toxic
Plant Extract
Fungus

Atoms/Molecules

Fig. 12.1  Approaches for the synthesis of nanoparticles (Ahmed et al. 2016, 2017)

cellular approach exploits plant/food extracts (downstream processing) for the syn-
thesis of metallic nanoparticles that produce highly energetic and more reactive
spherical shape structure, while intracellular approach involves dissimilarities in
reducing as well as stabilizing ability of phytochemicals present in different parts of
the plants that are responsible to produce extremely disperse polymetallic nanopar-
ticles of heterogeneous morphology. So, extracellular approach is desired over
intracellular. Actual mechanism is yet to be established for the nanoparticle synthe-
sis. However, scientists have proposed a hypothetical mechanism of nanoparticle
synthesis (Fig. 12.3) based on the results obtained from specific biomass utilized
(Velusamy et  al. 2016). Furthermore, plant-mediated approach is favored over
microbial-based nanoparticle synthesis because of single-step method for biosyn-
thesis (takes less time), nontoxic, economical, and eco-friendly process (Kavitha
et al. 2013; Kumar and Yadav 2009). Due to rich biodiversity, plants are considered
as warehouse for the nanoparticles synthesis, and their potential is yet to be com-
pletely exploited (Table 12.1). At present, the scientists are working on individual
plant extracts like polyphenols, flavonoids, terpenoids, glycosides, proteins, organic
acids, etc., for the production of metallic nanoparticles to achieve more control over
size along with their promising usages in various fields as well as morphology of
nanoparticles (Seralathan et al. 2014; Tamuly et al. 2014). The waste products of
food processing and agriculture-based industries are also used for fabrication of
biogenic metallic nanoparticle synthesis like silver nanoparticles from aqueous corn
12  Nanotechnology as Potential and Innovative Platform Toward Wastewater… 205

Reduces
Waste

Economical
Nanomaterial
and time
Efficiency
saving

Advantages of
Biological
method of
NPs synthesis

Non-toxic and
Process
Environment
Efficiency
friendly

Energy
Efficiency

Fig. 12.2  Comparative account on the biological approaches of NP synthesis over chemical and
physical approaches (Hasan et al. 2018)

husk extract and carboxymethyl sago pulp waste (Villanueva-Ibáñez et  al. 2015;
Deekonda et al. 2016); gold nanoparticles from palm oil mill effluent and sugar beet
pulp (Gan et al. 2012; Castro et al. 2010); and platinum from waste peel extract of
pomegranate (Dauthal and Mukhopadhyay 2015).

12.3  Characterization Techniques of Fabricated

Nanoparticles

The characterization of synthesized nanoparticles is carried out so as to find out its

various physicochemical properties like surface area, shape, size, electrical conduc-
tivity, quantum and charge parameters, hydrophobicity indices, crystalline struc-
ture, aqueous solubility, type of coating, UV/visible absorption, fluorescence,
dermal penetration, and topological parameters (Xiao et al. 2017; Qu et al. 2017;
Tuo et al. 2013). There are ample numbers of techniques available for the detection,
measurement, and characterization of nanoparticles, but there is no single method
which can be selected as ideal method for all; rather a method is to be chosen on the
basis of sample type, information required, time taken, and economic feasibility. In
206 A. K. Singh and P. Porwal

Microorganisms Plant/food Extract

Bacteria, Fungi, Yeast Obtained from food waste/different parts of the
(cyanobacteria, actinomycetes) OR plants like flower, fruit, roots, leaves and stem.
(Plant extract may contain proteins, amino acids,
polyphenols, organic acids, polysaccharides,
terpenoids, flavonoids, enzymes etc.)

Metal Salt concentration

Biological
Reduction

Heterogeneous nanoparticles Optimization of Processing Parameters

produced with low yield like pH, temperature, aeration, mixing
ratio, incubation period

Homogeneous, stable and capped

nanoparticles produced with high yield

By modifying Processing Parameters

Controlled shape and morphology of nanoparticles are obtained

(Square, Triangular, Spherical, Rod, and Hexagonal)

Fig. 12.3  Biogenic approach for the synthesis of nanoparticles. (Modified from Singh et al. 2016;
Ghosh et al. 2017)

this context, Table 12.2 shows overview of frequently employed analytical and bio-
chemical techniques used for the evaluation and characterization of p­ hysicochemical
parameters for the fabricated nanoparticles with their strengths and limitations like
transmission electron microscopy (TEM), scanning electron microscopy (SEM),
high-resolution transmission electron microscopy (HRTEM), TEM with energy-
dispersive X-ray spectroscopy (EDS), scanning tunneling microscopy (STM),
atomic force microscopy (AFM), ultraviolet-visible (UV-Vis) spectroscopy, Fourier-
transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic or static
light scattering (DLS and SLS), Brunauer-Emmett-Teller (BET) theory, quasi-elas-
tic light scattering (QELS), nuclear magnetic resonance (NMR), Rutherford back-
scattering spectrometry, scanning mobility particle sizer (SMPS), photon correlation
spectroscopy (PCS), nanoparticle tracking analysis (NTA), multiangle light scatter-
ing (MALS), and small-angle neutron scattering (SANS). Efforts are continuously
12  Nanotechnology as Potential and Innovative Platform Toward Wastewater… 207

Table 12.1  An overview on the fabrication of plant-mediated nanoparticles

Plant part
used for NP Type of NP Size
Plant system synthesis synthesized (nm) Shape References
Cucurbita pepo Leaf extract Silver 5–40 Roughly Krishnaraj et al.
spherical (2016)
Ceropegia Leaf extract Silver 100 Spherical Muthukrishnan
thwaitesii et al. (2015)
Butea Bark extract Silver ∼35 Spherical Pattanayak et al.
monosperma (2017)
Aloe vera Plant extract Silver 35–55 Spherical and Dinesh et al.
cubic (2015)
Andrographis Leaf extract Silver 68.06– – Elangovan et al.
echioides 91.28 (2015)
Azadirachta Gum extract Silver 12.09– Spherical Velusamy et al.
indica 29.65 (2015)
Mukia Leaf extract Silver 13–34 Spherical Chitra et al. (2015)
maderaspatana
Phyllanthus Leaf extract Silver 30–60 Spherical Suresh et al. (2015)
niruri
Caulerpa Plant Silver 20–35 Spherical and Murugan et al.
scalpelliformis aqueous cubic (2015a)
extract
Gmelina asiatica Leaf extract Silver 20–64 Spherical and Muthukumaran
triangle et al. (2015)
Adhatoda vasica Leaf extract Silver 10–50 Spherical Latha et al. (2016)
Dillenia indica Fruit Silver 11–24 Spherical Singh et al. (2013)
Andrographis Leaves Silver 67–88 Spherical Suriyakalaa et al.
paniculata (2013)
Withania Leaves Silver 5–40 Irregular, Nagati et al. (2012)
somnifera spherical
Citrullus Calli Silver 5–70 Triangle Satyavani et al.
colocynthis (2011)
Galaxaura Powder or Gold 4–77 Spherical Abdel-Raouf et al.
elongata extract (2017)
Carica papaya Leaf extract Gold 2–20 Spherical Muthukumar et al.
(2016)
Citrus maxima Fruit extract Gold 25 – Yu et al. (2016)
7 ± 10
Couroupita Flower Gold 29.2– Cubic Subramaniam et al.
guianensis extract 43.8 (2016)
Mimusops elengi Bark extract Gold 9–14 Spherical Majumdar et al.
(2015)
Ziziphus Leaf extract Gold 20–40 Spherical Sadeghi (2015)
mauritiana
Chloroxylon Leaf extract Gold 18–31 Spherical Balasubramani
swietenia et al. (2015)
(continued)
208 A. K. Singh and P. Porwal

Table 12.1 (continued)
Plant part
used for NP Type of NP Size
Plant system synthesis synthesized (nm) Shape References
Sterculia Fruit extract Gold 9.37– Spherical Bogireddy et al.
acuminata 38.12 (2015)
Stevia rebaudiana Leaf extract Gold 17 Cubic Sadeghi et al.
(2015)
Cymbopogon Leaf extract Gold 20–50 Triangular, Murugan et al.
citratus spherical, and (2015b)
rod
Cassia fistula Stem Gold 55–98 Spherical Daisy and Saipriya
(2012)
Trigonella Seed Gold 15–25 Spherical Aromal and Philip
foenum-graecum (2012)
Mirabilis jalapa Flowers Gold 100 Spherical Vankar and Bajpai
(2010)
Mentha piperita Leaves Gold 90–150 Spherical MubarakAli et al.
(2011)
Prunus × Gum extract Platinum 10–50 Spherical and Velmurugan et al.
yedoensis oval (2016)
Punica granatum Peel extract Platinum 16–23 Spherical Dauthal and
Mukhopadhyay
(2015)
Barberry Fruit extract Palladium 18 Spherical Nasrollahzadeh
et al. (2016)
Euphorbia Leaf extract Palladium 30–35 – Nasrollahzadeh and
thymifolia L. Sajadi (2016)
Eclipta prostrata Leaf extract Palladium 27 ± 1 – Rajakumar et al.
3 (2015)
Catharanthus Leaf extract Palladium 38 Spherical Kalaiselvi et al.
roseus (2015)

carried out to standardize the way nanoparticles are measured for assessing occupa-
tional exposure, health, and environmental risks. As accuracy of the method varies,
comparing the results of the same sample by different techniques can provide accu-
racy indication.

12.4  N
 anoparticles: Potential Platform for the Removal
of Water Contaminants

Polluted water/wastewater can be used for synthesis of biogenic nanoparticles

(Ahluwalia et al. 2016), producing energy as well as recovering nutrients for agri-
cultural uses (Mal et al. 2016). Carbon nanotubes (CNTs) are extensively used for
treating water and wastewater as they have antimicrobial property with no side
12  Nanotechnology as Potential and Innovative Platform Toward Wastewater… 209

Table 12.2  Various approaches employed toward the evaluation of physicochemical properties of
nanomaterial (Rasmussen et al. 2017; Lin et al. 2014)
Characterization Physicochemical
technique parameter Type of material Strengths Limitations
Transmission Size and size Direct
Inorganic, organic, Costly equipment,
electron distribution, shape carbon-­based, measurement of samples required as
microscopy heterogeneity, the parameters
biological, complex ultrathin samples in
(TEM) aggregation, with higher spatial
materials (coated, nonphysiological
dispersion core-shell). resolution than condition
SEM.
Spherical, equiaxial
particles, tubes,Other analytical
methods can be
flakes, rods, fiber
united with this to
investigate
chemical
composition and
electronic
structure of
nanomaterial
Scanning electron Size and size Organic, inorganic, The size/size Dry samples,
microscopy distribution, carbon-­based, distribution and conducting sample,
(SEM) shape, biological, complex shape of or coating
aggregation materials (coated, nanomaterial is conductive are
core-shell). directly measured materials required
Spherical, equiaxial
particles, tubes,
flakes, rods, fibers
Atomic force Size and size Organic, inorganic, 3D sample surface Time taking and
microscopy distribution, carbon-­based, topography. tough sample
(AFM) shape, structure, biological, complex Sub-nanoscale preparation.
surface properties materials (coated, topographic Tip effects often
(modified AFM), core-shell). resolution. disturb
surface charge Spherical, equiaxial Direct measurements.
density (mapping) particles, tubes, measurement of Analysis in general
flakes, rods, fibers samples in dry, limited to the
aqueous, or external of
ambient nanomaterials
environment
X-ray diffraction Size, shape, and Inorganic, Well-­ Confined to
(XRD) crystal structure carbon-­based, acknowledged crystalline
for crystalline complex materials technique. materials, low
materials (coated, core-shell High spatial intensity compared
not organic) resolution at to electron
atomic scale diffraction
Electrophoretic Zeta potential Organic, inorganic, Simultaneous Very diluted sample
mobility carbon-­based, measurement of required, not very
biological, complex many particles specific method
materials (coated, (using ELS)
core-shell).
Spherical, equiaxial
particles, tubes,
flakes, rods, fiber
(continued)
210 A. K. Singh and P. Porwal

Table 12.2 (continued)
Characterization Physicochemical
technique parameter Type of material Strengths Limitations
Infrared/ Structure Organic, inorganic, Minimal or no Commonly used for
Fourier-transform molecular carbon-­based, dry powder
sample preparation
infrared composition biological, complex samples, and
requirement. Fast
spectroscopy (IR/ surface properties materials (coated, and inexpensivemolecule must be
FTIR) (FTIR) core-shell). measurement active in IR region.
Spherical, equiaxial Interference and
particles, tubes, strong absorbance
flakes, rods, fiber of H2O (IR).
Relatively low
sensitivity in
nanoscale analysis.
Detection limits
routine: 2%
Special techniques:
0.01%
Ultraviolet-­ Surface chemistry Organic, inorganic, Easy and low-cost Material-dependent
visible composition, carbon-­based, technique. Solid or technique.
spectroscopy optical properties, biological, complex liquid, both types Plasmonic samples
(UV-vis) particle size (for materials (coated, of samples can be can only be
certain materials) core-shell). Only evaluated determined for size.
for certain elements Samples in powders
require reflectance
accessory.
Only for diluted
samples (not in
powders), e.g., thin
films, dispersions,
etc.
Nuclear magnetic Structure Organic, inorganic, Sample Huge amount of
resonance (NMR) composition, size carbon-­based, preparation is easy sample is required,
(indirect biological, complex and more time-­
analysis), purity, materials (coated, nondestructive/ consuming and less
conformational core-shell). Only noninvasive sensitivity
change for certain elements method
X-ray Surface chemistry Organic, inorganic, Very sensitive for Only detects the
photoelectron composition carbon-­based, surface chemistry elements in a very
spectroscopy complex materials thin layer close to
(XPS) (coated, core-shell). surface (about
Spherical, equiaxial 10 nm), needs
particles, tubes, careful sample
flakes, rods, fiber preparation, very
sensitive, ultrahigh
vacuum
(continued)
12  Nanotechnology as Potential and Innovative Platform Toward Wastewater… 211

Table 12.2 (continued)
Characterization Physicochemical
technique parameter Type of material Strengths Limitations
Energy dispersive Composition, Organic, inorganic, Gives information Not a real surface
X-ray analysis surface chemistry carbon-­based, on elements from science technique
(EDX) complex materials beryllium to so used in
(coated, core-shell). einsteinium. combination with
Spherical, equiaxial Detection limit 0.1 TEM or SEM. Not
particles, tubes, at % suitable for
flakes, rods, fiber nonconductive
samples, low
atomic number
elements are
difficult to detect
(they overlap with
X-ray peaks)
Raman Composition, Organic, inorganic, Frequently Metals and alloys
spectroscopy surface chemistry, carbon-­based, available, easy and cannot be analyzed.
particle size (for biological, complex low-cost technique Size for certain
certain materials) materials (coated, materials can only
core-shell). be determined like
Spherical, equiaxial CNT, thickness of
particles, tubes, graphene flakes.
flakes, rods, fibers Very sensitive to
impurities. Samples
heating through
intense laser
radiation can lead
to sample
decomposition
Single particle Particle size Inorganic, complex Measures Accurate size
inductively distribution, materials (coated, individual determination
coupled plasma surface chemistry core-shell if particles. restricted to
mass contains detectable Cost-efficient, spherical particles
spectrometry element). quick, and only.
(SP-ICP-MS) Spherical, equiaxial chemically precise Can detect only one
particles method element at a time
Scanning Particle size, Organic, inorganic, On-site technique Only aerosol
mobility particle particle size carbon-­based, frequently used samples in size
sizer (SMPS) distribution complex materials for aerosols range 2.5–1000 nm
(coated, core-shell). with resolution
Spherical, equiaxial 2 nm particles need
particles to be charged
Scanning Size and size Organic, inorganic, Direct For conductive
tunneling distribution, carbon-­based, measurement. samples only
microscopy shape, biological, complex High spatial
(STM) aggregation, materials (coated, resolution down to
structure surface core-shell). atomic scale
charge density Spherical, equiaxial
(mapping) particles, tubes,
flakes, rods, fibers
212 A. K. Singh and P. Porwal

effects (Gehrke et al. 2015). The antimicrobial property of nanoparticles for waste-
water treatment is mainly used for disinfection, control over membrane biofouling,
and biofilm control on other relevant surfaces. Nanomaterials as an adsorbent are
used in several forms such as absorptive, catalytic, catalytic membrane, bioactive
nanoparticles, polymeric as well as nanocomposite membrane, etc., for treatment of
wastewater. Nanometal oxides such as iron oxides like ferrous oxide, TiO2, and
Al2O3 are used as adsorbents for heavy metals and radio nuclides (Mayo et al. 2007).
Owing to the low toxicity and chemical stability, TiO2 nanoparticles are extensively
employed as decontaminating and disinfecting agents, which remain stable through-
out the process of decontamination (Savage and Diallo 2005). Sharma et al. (2018)
reported that nanocomposite (TiO2–Fe2O3) can be used as an active microbial disin-
fectant that can eradicate E. coli through photocatalytic activity. Silver nanocatalyst
N-doped TiO2 was used for the degradation of microbial contaminants (Prachi et al.
2013). Nano iron hydroxide and zinc oxide adsorbent permit adsorption of arsenic
from drinking water and wastewater (Aredes et al. 2012). Nanotechnology also con-
tributes in the field of agriculture by protecting the plants and enhancing their
growth, e.g., colloidal solution of ZnO nanoparticles were used as a fertilizer (Sabir
et  al. 2014), silica nanoparticles (plant nanobiotechnology) as a bio-insecticides,
vector for gene delivery, pesticide delivery (mesoporous silica), protects quenching
of active reagent (Baeza et al. 2015). Nowadays, nanocatalysts are extensively being
used for treating wastewater due to their high catalytic and high surface to volume
ratio. Catalytic nanoparticles which find their application in removal of environ-
mental contaminants are semiconductor materials, metallic/bimetallic catalyst,
zero-valance metal (like zero-valent iron), etc. (Chokshi and Bora 2014). Silver
nanoparticles embedded with zeolites are used for sanitary purposes by inhibiting
the growth of microorganisms in water (Dutta 2011). Recently, a number of waste-­
derived as well as tailored waste-derived nanomaterials are being utilized in differ-
ent fields such as silica nanopowder from rice husk, sugarcane waste, bamboo culm
for energy storage (Praneetha and Murugan 2015), waste plastic-derived nanopar-
ticles for bioimaging (Hu et al. 2014), elimination of heavy metals, organic pollut-
ants, and disintegration of toxic organic materials from water/wastewater, e.g., flue
dust waste-derived catalyst has the potential to degrade 69% of the dye content from
wastewater mainly due to their catalytic properties (Amorim et  al. 2013; Buruga
et al. 2018; Sarkar et al. 2018).
Silver (Ag) nanoparticles were used in water filtration membranes (e.g., polysul-
fone) owing to their low toxicity, biofouling reduction, and strong antimicrobial
activity against gram-positive and gram-negative bacteria and viruses like
Pseudomonas aeruginosa, E. coli, Staphylococcus aureus, Klebsiella, etc. The anti-
microbial activity of Ag nanoparticles is due to the formation of free radicals that
were responsible for damaging the bacterial membranes and alter the membrane
properties by adhering to cell surfaces, DNA interactions, and enzyme destruction
(Jain and Pradeep 2005; Panahi et al. 2018). The noble metals, magnetic, and dye-­
doped nanomaterials are constantly used to check the wastewater quality by detect-
ing pathogens at a very low concentration (Chokshi and Bora 2014). The extracellular
water-soluble polysaccharides of cyanobacterial strain Nostoc commune were
12  Nanotechnology as Potential and Innovative Platform Toward Wastewater… 213

exploited toward the biogenic fabrication of silver nanomaterials after interaction

with AgNO3 (spherical shape, size 15–45  nm). The synthesized nanoparticles
depicted antimicrobial activity toward E. coli as well as outstanding antiseptic prop-
erties against pathogenic seed and grain-borne fungi (Morsy et al. 2014). Qing et al.
(2017) reported that silver nanoparticles synthesized by using waste tea extract (as
a reducing and stabilizing agent) had shown the catalytic degradation of methylene
blue and ethyl violet solution in presence as well as absence of H2O2, restrain impact
on gram-positive and gram-negative bacteria, and have the potential to be used for
industrial wastewater treatment.
Copper (Cu) and copper oxide (CuO) nanoparticles can be synthesized biologi-
cally through plant extracts like magnolia leaf extract, clove extract, stem latex of
Euphorbia nivulia, Sterculia urens extract (Karaya gum), and P. stutzeri bacteria
from wastewater via electroplating route (Varshney et  al. 2010) and Morganella
bacteria (Din and Rehan 2017). Several research studies have revealed that these
copper and copper oxide nanoparticles have antioxidant and antibacterial property
toward E. coli as well as S. aureus (Subhankari and Nayak 2013; Lee et al. 2011).
Biogenic Ag/Cu (multimetallic and combine) nanocatalysts synthesized from the
leaf extract of Carica papaya with average size of 150 nm have catalytic activity for
chlorpyrifos disintegration in water with 3,5,6-trichloro-2-pyridinol and diethyl-
thiophosphate (Rosbero and Camacho 2017).
Palladium-coated gold nanoparticles are highly efficient catalyst for the removal
of trichloroethane from groundwater than palladium alone. Palladium nanoparticles
were used for the reduction of Cr(VI) to Cr(III) (Özlem et al. 2013). Nanoparticles
were significantly used as key ingredients for makeup products like sunscreens,
fungicides, rubber processing, and wastewater treatment (Gunalan et  al. 2012).
Palladium-incorporated ZnO nanocatalyst showed high photocatalytic activity for
the removal of E. coli from wastewater (Prachi et al. 2013).

12.5  Limitations of Nanoparticle-Based Wastewater

Treatment

In the era of commercialization, the success or failure of any nanoengineered mate-

rial exploited toward the treatment of water/wastewater technology purely depends
on their impact on the aquatic flora and fauna. Presently limited evidences are
accessible toward the behavior, transport, as well as chemical alteration of nanopar-
ticles in the surrounding atmosphere as well as the mechanism of their effect on
biological systems. So, nanoparticles used for water treatment might interact with
human health and environment at any stage of product life cycle and may have
involuntary effects. The results yielded are contradictory from several studies
together with the life cycle analysis, technology assessment, toxicity test, pathways,
and dispersal of nanoparticles in aquatic bodies to evaluate health risks of particular
nanomaterial. For instance, silver nanoparticles that are used to decrease bad smell
214 A. K. Singh and P. Porwal

from socks are being released in water during washing and may destroy beneficial
effect of bacteria responsible for the breakdown of organic matter present in waste-
water (Chokshi and Bora 2014). Since no standard laws and regulations are set for
the general experimental tests, it slows down the necessary decision processes.
Different procedures of nanotechnology have shown a great potential on the lab
scale, but their promptness for commercialization varies extensively owing to tech-
nical obstacles, cost-efficacy, potential environmental, and human risks.

12.6  Conclusion

Harmless/safe water has turn out to be a competitive source worldwide because of

growing population, severe droughts, climate change, etc. Nanoparticles depict
exceptional features like large surface areas, size, shape, as well as dimensions,
which enable them as eye-catching platform toward water/wastewater treatment
including disinfection, adsorption, and membrane separations. Overall, water/
wastewater treatment exploiting nanomaterials is a potential area toward present as
well as upcoming investigations. Furthermore, some safety measures need to be
taken so as to circumvent any risk to human health and environment owing to
exploitation of these various nanoparticles for different applications including
water/wastewater treatment. However, such issue of nanoparticles can be overcome
as a result of association among research institutions, industry, as well as government.

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Chapter 13
Solid Lipid Nanoparticles

Akhlesh Kumar Jain and Suresh Thareja

13.1  Introduction

The area of Novel Drug Delivery System is getting wider day by day in expanded
area of biomedical science, bioengineering and nanotechnology (Ekambaram et al.
2012). Most of the latest delivery techniques explore nanosize-based particles, i.e.
nanocarriers having the API (Shah et al. 2011). Few important drug carriers devel-
oped using nanotechnology-based approaches are nanoemulsion, nanosuspension,
nanocrystals, nanoparticles and solid lipid nanoparticles (Jain 1997). Recent
advances in the development of nanocarriers have started a new era in Formulation
Science. Solid lipid nanoparticles (SLNs) were reported in 1991 as an unconven-
tional carrier system to typical colloidal carriers such as emulsions, microemul-
sions, self micro-emulsifying drug delivery system, micellar systems, liposomes,
polymeric microparticles and nanoparticles (Ramteke et al. 2012).
SLNs mingle advantages of the conventional carriers along with circumventing
some of their major disadvantages. SLNs showed potential applications in drug,
gene and vaccine delivery along with controlled and site-specific drug targeting.
SLNs are effortlessly made nanoparticles composed of biodegradable polymers of
high stability devoid of significant toxicity as well as commercially economic and
could incorporate wide variety of drugs for effective targeting. SLNs are novel
lipid-based formulations constituted exclusively of biodegradable lipids such as
highly purified triglycerides, monoglycerides, complex glyceride mixtures, hard
fats or even waxes, which turn solid at room temperature. Solid lipid nanoparticles
are nanometre-sized particles that range from 50 to 200  nm and made of solid
hydrophobic core which are suspended in aqueous phase containing surfactant.

A. K. Jain (*) · S. Thareja

School of Pharmaceutical Sciences, GGV Central University, Bilaspur, Chhattisgarh, India

© Springer Nature Switzerland AG 2020 221

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_13
222 A. K. Jain and S. Thareja

The drug is dissolved or dispersed in solid core contains the solid high melting fat
matrix. Both kinds of lipophilic or hydrophilic therapeutics and diagnostics could
be incorporated into the SLN (Shah et al. 2011). SLNs not only unite the advantages
of emulsion, liposomes and solid polymeric nanocarriers together but also eliminate
few of their disadvantages. Major advantages included are biocompatibility and
biodegradability, avoidance of drug leakage, stability against coalescence, nontox-
icity, hydrolysis, physical stability and being an excellent carrier for lipophilic drugs
(Cavalli et al. 2002). Lipid emulsion and liposomes are entirely different. Oil core
made of a neutral lipid, covered by monolayer of amphiphilic lipid, makes lipid
emulsion, whereas liposomes are bilayer lipid vesicles made of amphiphilic phos-
pholipid having an interior aqueous cavity (Jain 1997). On the other hand, SLNs are
designed from solid lipids and stabilized with an aqueous suspension of emulsifying
agents. They look a lot like nanoemulsion; the only difference is that liquid lipid is
replaced with a solid lipid, hence providing an outstanding opportunity for con-
trolled drug release as solid lipid lowers the movement of encapsulated drug drasti-
cally compared to liquid oil phase (Martins et al. 2007). Also, encapsulation in solid
lipids improves the stability of incorporated chemically sensitive lipophilic ingredi-
ents in contrast to liquid lipids of nanoemulsion. These prospective benefits of phys-
icochemical properties associated with the physical state of the lipid phase are as
follows:
(i) Movement of reactive radicals in solid material is slower compared to liquid
medium and hence limits the degradation pathways.
(ii) Phase partition of the API and lipid phase into the solid lipid thus prevents
leaching of drugs at the surface of SLN.
(iii) Enhanced absorption of inadequately absorbed drugs is reported after admin-
istration using SLN.
Large-scale production of SLNs could be achieved out in a cost-effective and rela-
tively simple manner using high-pressure homogenization technique. Another
approach for the production of SLNs is microemulsions or simply suspending liquid
lipid in a solution of surfactant with stirring and sonication. SLNs made using vari-
ous methods are present in suspension form; hence storing for prolonged period of
time showed instability due to hydrolysis reactions. However conversion of SLNs
into dry powder which can be reconstituted in order to improve stability of SLNs,
with the help of lyophilization or spray drying, is an excellent way (Sinha et  al.
2010). SLNs provide an excellent opportunity as an advanced drug carrier for oral
delivery, topical administration, pulmonary administration, parenteral administra-
tion, gene delivery and potential adjuvant for vaccines. In a nutshell, they propose
an extremely versatile platform for second- and third-order targeting of drugs.
The major advantages associated by SLNs are as follows:
(a) Suitable for controlled drug release and drug targeting.
(b) Suitable for delivery of both hydrophilic and lipophilic drugs.
(c) Reduced toxicity compared to polymeric nanoparticles as SLNs are made of
biocompatible lipids.
13  Solid Lipid Nanoparticles 223

(d) Provide protection to labile drugs from chemical, photochemical and oxidative
degradation.
(e) Water-based technology (organic solvents can be avoided).
(f) SLN could be administered through various routes such as oral, pulmonary,
intravenous, ophthalmic and dermal (Rabinarayan and Padilama 2010).

13.2  Composition of Solid Lipid Nanoparticles

Common ingredients used for preparation of solid lipid nanoparticles are solid
lipid(s), stabilizers mainly surfactants and water. The word lipid is having broader
sense here and also inclusive of fatty acids (e.g. stearic acid), steroids (e.g. choles-
terol), triglycerides (e.g. tristearin), partial glycerides (e.g. Imwitor) and waxes (e.g.
cetyl palmitate). All the varieties of emulsifying agents, irrespective of their molec-
ular weight and net charge, could provide the desired stability to the SLN suspen-
sion. Sometimes, single surfactant unable to stop particle agglomeration effectively
hence the combination of emulsifiers might be required for proper stabilization. The
selection of emulsifiers is generally made as per the application and mode of admin-
istration of SLN. An obvious benefit of SLN is that the lipid mixture contains physi-
ological lipids and hence limits the toxicity. Most of the additives used for
preparation of SLNs are not harmful and falls in the generally recognized as safe
(GRAS) category list of the Food and Drug Administration (FDA). SLN is com-
posed of lipids and of stabilizers.

13.2.1  Lipids

In the last two and half decades, SLN proved to be a runaway success among nano-
carriers because SLN not only “combine the few benefits of fatty emulsifying
agents, liposomes and polymeric nanoparticles, but also have the ability to over-
come major drawbacks of these carriers” (Muller and Runge 1998). Few problems
associated with SLNs such as crystallinity and low entrapment have been overcome
by nanostructured lipid carriers (NLC) (Patlolla et al. 2010). Lipids composed of
mainly oily or waxy materials (fatty acids, their alcohols, their glycerol esters, i.e.
phospholipids, glycolipids and sphingophospholipids) are having low solubility in
polar solvents and freely miscible in organic solvents. The core of the SLN com-
prises of the lipid; this core itself determines pharmaceutical properties of the par-
ticles such as drug stability and drug release.
Generally, two or more lipid combinations are useful because it allows manipula-
tion of encapsulation efficiency and release kinetics and also the physical character-
istics, i.e. melting point, crystallinity and polymorphism. A list of various types of
lipids can be chosen for development of SLN, and NLC is reported in Table 13.1.
224 A. K. Jain and S. Thareja

Table 13.1  Commonly used lipids in the preparation of SLN and NLC
S. Free fatty
no. Triglycerides Free fatty acids alcohols Waxes Miscellaneous
1 Glyceryl tristearate Behenic acid Stearyl Cetyl Castor oil
alcohol palmitate
2 Glyceryl Palmitic acid and Cetyl Beeswax Hydrogenated
tripalmitate palmitoleic acid alcohol castor oil
3 Glyceryl Oleic acid Myristyl Carnauba Hydrogenated
trimyristate alcohol wax palm oil
4 Medium chain Myristic acid Lauryl – Anhydrous milk
triglycerides alcohol fat
5 Glyceryl trioleate Stearic acid – – Cacao butter
6 Tricaprylin Arachidic acid and – – Goat fat
arachidonic acid
7 Tricaprin Lauric acid – – –
8 Trilaurin Linoleic acid or – – –
linolenic acid

13.2.2  Surface-Active Compounds (SACs)

Once two phases are immiscible into each other (e.g. oil and aqueous) and mixed
together, one phase is dispersed into the other phase, and an interfacial boundary is
formed. Surface-active agents reduce this interfacial tension and stabilize the dis-
persion. Nevertheless, surfactant properties are associated by their chemical struc-
ture, and they could reduce the surface tension only up to a specific level which is
sometimes not enough to stabilize the dispersion. Additional decrease can be car-
ried out by the addition of cosurfactants (Solans and Sole 2012). The climbing of
temperature diminishes the surface tension and hence could be utilized to manufac-
ture hot emulsions with small energy involvement (Webster and Cates 2001). In
addition to main constituents, a variety of other additives can also be required to be
added such as cryoprotectants (trehalose, sorbitol) (Soares et al. 2013) and stabiliz-
ers which act through other mechanisms (polyvinyl alcohol) (Xie et  al. 2011).
Table 13.2 shows a list of excipients used for preparation and stabilization of SLN.

13.3  Techniques Used for Preparation

13.3.1  High-Pressure Homogenization

The basic method used for production of SLN is high-pressure homogenization

which is a consistent and dominant practice, first of all explored for synthesis of
SLNs. High-pressure homogenization can be carried out at higher temperature (hot
HPH technique) or at under room temperature (cold HPH technique) (Muller and
Lucks 1996). In both techniques, the lipid and drug are melted approximately
Table 13.2  List of various excipients used for preparation and stabilization of SLN
Nonionic
Polyoxyethylene
S. sorbitan fatty Polyoxyethylene
no. esters alkyl/aryl ethers Poloxamers Others Anionic Cationic Amphoteric Cosurfactant
1 Polysorbate 20 Tyloxapol Poloxamer Polyglyceryl-6 Sodium lauryl Dimethyldioctadecy- L-α-­ 1-Butanol
407 distearate sulphate lammonium bromide phosphatidylcholine
2 Polysorbate 60 Polyoxyethylene Poloxamer Polyglyceryl-3 Sodium Cetrimonium bromide Egg lecithin Diethylene
(20) stearyl ether 188 methylglucose dehydrocholate glycol
distearate monoethyl ether
3 Polysorbate 80 Polyoxyethylene – PEG caprylic/capric Sodium DOTAP Soya lecithin Low molecular
(20) cetyl ether triglycerides taurocholate weight PEG
4 Polysorbate 85 Polyoxyethylene – Macrogol Sodium Chlorhexidine salts – Propylene
(20) isohecadecyl (15)-hydroxystearate cholate glycol
ether
5 – – – Polyoxyethylene Sodium DOTMA – Sorbitan
glyceryl glycocholate monostearate
monostearate
226 A. K. Jain and S. Thareja

5–10  °C above the melting point of the lipid. High-pressure homogenizers push
liquid through a narrow gap at high pressure (100–2000 bar) which accelerates the
liquid particles to extremely higher speed (over 1000 km/h). Such higher forces and
cavitation stress break the lipid droplets to the nanometric level. Usually, 5–10%
lipid ratio is good enough to prepare the SLN, but up to 40% lipid content can be
processed using this technique.

13.3.1.1  Hot Homogenization

In hot homogenization technique, the lipid melt containing the drug is dispersed
under stirring in aqueous solution of surfactant at similar higher temperature to the
melt. The resulted pre-emulsion is homogenized through a temperature-directed
high-pressure homogenizer; usually three cycles (500 bar) are sufficient, followed
by cooling of hot O/W nanoemulsion to room temperature, which leads to recrystal-
lization of lipids in the form of solid lipid nanoparticles. Figure  13.1 provides a
graphical illustration of SLN production using hot homogenization method.
Generally, hot homogenization method can be used for hydrophobic and poorly
soluble drugs. As the exposure period to elevated temperature is comparatively low,
hence, majority of thermolabile drugs could be encapsulated into the SLNs before
being degraded. However, this technique is not suitable for hydrophilic drugs
because higher partitioning of drugs in to the aqueous phase during homogenization

Lipid phase Pre-emulsion

Lipid + Drug

Emulsion

Ultrasonication

Dispersing lipid Homogenization

melt in aq. phase

Aq. phase
Cooling
Heating lipid
and aqueous phase

Solid lipid nanoparticles Colloidal emulsion

Fig. 13.1  Schematic depiction of various steps involved in the hot homogenization technique
13  Solid Lipid Nanoparticles 227

process results in low entrapment efficiency (Gohla and Dingler 2001; Schwarz
et al. 1994).
The properties of the final product are affected by the conditions at which pre-­
emulsion is processed, and it is desirable to obtain droplets in submicron range.
Usually, higher temperatures produce smaller particle size because of the reduced
viscosity of the internal phase. Nevertheless, elevated temperatures fasten up the
degradation process of the drug as well as of matrix. Also, homogenization process
can be repeated several times. In majority, 3–5 homogenization rounds at
500–1500 bar are enough to obtain the desired size. It should be remembered that
the high homogenization pressure or greater number of cycles often results in an
increase of the particle size because of the occurrence of particle coalescence due to
high kinetic energy of the particles. Moreover, high-pressure homogenization pro-
duces a rise in the temperature of the sample (approximately 10 °C for 500 bar).

13.3.1.2  Cold Homogenization

The cold HPH is a suitable technique for processing temperature-sensitive drugs

and/or hydrophilic drugs. During cold homogenization method, the lipid mixture
containing the drug is cooled down to the melting temperature of the lipids; there-
fore, the solid lipid ground to lipid microparticles which are dispersed in a cold
surfactant solution yield a pre-suspension. Pre-suspension of microparticles is
homogenized at or below room temperature; the cavitation forces produced by the
homogenization process are strong enough to rupture the particles into solid lipid
nanoparticles. Strict control of temperature is required in order to make sure that
the lipid remains in the unmolten state even after increase in temperature during
homogenization. Initial step is similar to hot homogenization that comprises the
dispersing or solubilization of the medicament into the lipid mixture. Second step
is rapidly cooling of the melt which leads to uniform pattern of API in the lipid
particles. Also, reduced temperatures enhance the delicateness of the lipid and
ultimately particle comminution. Figure  13.2 provides a stepwise production of
SLNs using cold homogenization method. Another way to minimize the loss of
hydrophilic drug to aqueous phase is to replace water with other suitable media in
which the drug is having low solubility (e.g. oil or PEG 600) (Rabinarayan and
Padilama 2010).
Cold homogenization process has an edge over hot homogenization as it
eliminates or limits the three major problems associated with the hot homogeniza-
tion technique.
(a) Heat-induced drug degradation.
(b) Partitioning of the drug into the aqueous phase during homogenization.
(c) Crystallization step of the nanoemulsion leads to complexity and several
modifications.
228 A. K. Jain and S. Thareja

Rapid cooling
Milling into a Dispersion of
fine powder fine powder

Heating
lipid phase
Homogenization

Solid lipid nanoparticles

Fig. 13.2  Schematic depiction of various steps involved in the cold homogenization technique

13.3.2  Ultrasound Dispersion/Ultrasonication

Ultrasonication depends on the cavitations in hydrophilic phase that break down

lipid matrix into finer particles. The acquired hot microemulsion is allowed to cool
to solidify the droplets. The drug is added to the melted lipid; the heated aqueous
phase is added to the melted lipid and subjected to high-speed stirring to prepare a
nanoemulsion. Pre-emulsion of liquified lipid and heated surfactant mixture is
formed, and ultrasound is supplied through probe which is in direct touch of the
liquid. SLNs of lower size are formed using ultrasonication and high-speed homog-
enizer techniques. This technique has the possibility for scale up with flow cells,
without moving elements (ease in cleaning), and allows to manage the procedure by
changing the energy supplied by sonication. Major shortcoming is the chances of
metal adulteration that goes higher with prolonged sonication times and physical
instability due to growing solid particles while stirring the SLNs.

13.3.3  Solvent Emulsification/Evaporation

In this technique, water-immiscible organic solvents like cyclohexane, dichloro-

methane, toluene and chloroform are used for dissolving the hydrophobic drug and
the lipid components. Further, the mixture is emulsified with a hydrophilic solution
using a high-speed homogenizer. In order to get smaller-sized SLN, the coarse
13  Solid Lipid Nanoparticles 229

Organic solvent-in-
-water emulsion

Solid lipid nanoparticles

Organic solvent

To pump
Evaporation of solvent
(under reduced pressure)

Aq. phase
Mixing organic
Solubilizing drug and and aq. phases
lipid in organic solvent

Fig. 13.3  Schematic depiction of various steps involved in the solvent evaporation technique

emulsion is immediately processed through the microfluidizer which produces

nanoemulsion. Later on, this nanoemulsion was mechanically stirred at room tem-
perature using rotary evaporator which evaporates the organic liquid evaporation
under reduced pressure (40–60  mbar) and leaves lipid precipitates of SLNs
(Siekmann and Westesen 1996). Figure 13.3 provides a stepwise demonstration of
various aspects involved in the solvent evaporation method. The particle size of the
SLNs can be modified by varying the concentration of lipid in organic phase.
Generally, finer particle size could be obtained by keeping the lipid load below
(Pinto and Muller 1999). Avoidance of high heat during the method is advanta-
geous, and the produced SLN suspension can be centrifuged to collect the SLN.

13.3.4  Microemulsion-Based Technique

This method is based on the dilution of microemulsions. Microemulsions are clear

or transparent biphasic liquid composed of a lipid phase and aqueous phase which
are made stable using surfactant and also a cosurfactant in most of the cases. They
are made by mixing optically transparent mixture composed of fatty acid (i.e. stea-
ric acid), an emulsifier (i.e. polysorbate 20), co-emulsifiers (i.e. butanol) and water
at 65–70 °C. The lipid chosen should have a low melting point. Additives like buta-
nol are less preferred with respect to regulatory aspects. The microemulsions show
properties of emulsions as well as a real solution. Addition of a microemulsion to
water leads to the formation of fine particles and hence could be exploited as method
of preparation of SLN (Gasco 1993). Because of the involvement of a dilution step,
230 A. K. Jain and S. Thareja

Hot
microemulsion

Lipid phase
Solid lipid
Lipid + Drug
nanoparticles

Dispersing lipid melt in aq. phase Dispersion in

cold water
Aq. phase
Heating lipid
and aqueous phase

Fig. 13.4  Schematic depiction of various steps involved in the microemulsion-based technique

noticeably inferior concentration of SLN has been produced compared to HPH

method. First of all, a hot microemulsion is prepared by stirring 10% molten solid
lipid, 15% surfactant and up to 10% of cosurfactant with water. This hot microemul-
sion is diluted with cold water (1:50) through an especially designed thermostated
syringe. The mixture is kept on stirring while dilution which leads to nanoprecipita-
tion of lipids. Figure 13.4 provides a stepwise illustration of production of SLNs
using microemulsion-based method. Large-scale production of SLN is possible
using microemulsion technique. The microemulsion is produced in a large tank
which is heated through a temperature-controlled device. Later on, microemulsion
is diluted by transferring it to a cold water tank where lipid precipitation takes place
(Carli 1999). Excess water could be taken by ultrafiltration or by lyophilization in
order to make concentrated SLN. Also, microwave-assisted technique for formation
of microemulsion is another way of preparing SLN based on microemulsion tech-
nique (Fig. 13.5).

13.3.5  Double Emulsion Method

So far, numerous methods have been developed to prepare SLN, for example, high-­
speed homogenization, ultrasound divergence and high-pressure homogenization.
In the last few years, microemulsion method has emerged quickly due to its simple
operations and so on, compared to previous method. Nevertheless, SLNs prepared
13  Solid Lipid Nanoparticles 231

Solid lipid
nanoparticles

Microwave heating of drug, lipid Dispering the microemulsion

and aqueous surfactant solution from microwave into cold water

Fig. 13.5  Schematic depiction of various steps involved in microwave-assisted technique of

microemulsion formation for SLN production

by microemulsion method have few disadvantages, particularly limited loading

capacity of some water-soluble drugs because water-soluble drugs diffuse out from
oil phase to aqueous phase while in emulsification process (Shi et al. 2011). The
double emulsion technique was established to solubilize agents having high aque-
ous solubility in the internal aqueous phase of a W/O/W emulsion, with the aid of a
stabilizer to prevent partitioning of the aqueous soluble drug to the external aqueous
phase during solvent evaporation.
In this method the drug is dissolved into an aqueous solution which is emulsified
with melted lipid mixture in order to form primary W/O emulsion stabilized with
suitable excipients (e.g. gelatin, poloxamer 407). Further, the primary W/O emul-
sion is re-emulsified with hydrophilic solution of emulsifying agents to produce a
double W/O/W emulsion. Stirring of W/O/W emulsion allows formation of SLNs
which are isolated by filtration. Using this method, relatively large particles are
produced, however, allow incorporation of higher quantity of hydrophilic molecules
and also provide the opportunity of surface alterations (e.g. with PEGs). Double
emulsion method can also keep away the need of melting the lipid for the develop-
ment of peptide/protein-loaded lipid particles.

13.3.6  Membrane Contactor Technique

This method based on simple step of passing lipid through pores of a membrane
with pressure at above the melting point of the lipid leads to formation of small
droplets. The holes in the membrane work as parallel capillaries for entrance of the
lipid phase. Simultaneously, hydrophilic phase is stirred constantly and flows tan-
gentially inside the membrane module and brush off the droplets being produced at
the hole openings. SLNs were produced by the cooling of the formulation at the
RT.  Initially, materials were kept in the thermostated bath to uphold the desired
temperature, and N2 was purged to generate the pressure for the liquid phase.
Figure 13.6 provides a stepwise graphical view of SLN production using membrane
232 A. K. Jain and S. Thareja

Pressing of melted lipid melted lipid under high presser

Through membrane pores pores

aq. phase Membrane containing

Micropores/nanopores
Membrane with pores
Lipid Globules

Aq. Phase tangentially flow

Passage of aq.
phase tangentially Membrane contactor

Collection of solid
lipid nanoparticles

Fig. 13.6  Schematic depiction of various steps involved in the in the membrane contactor-based
technique

contactor. The various process parameters (aqueous and lipid phase temperature,
the lipid phase pressure, aqueous phase cross flow velocity, lipid phase amount and
membrane pore size) affect the size of SLN formed.
The membrane contactor method can also be used for the preparation of poly-
meric nanoparticles, by methods involving a polymerization of dispersed monomers
(interfacial polymerization method) or a dispersion of preformed polymers (nano-
precipitation method). The advantage of membrane contactor method is to manage
the size of SLN by a suitable selection of membrane pore size and process param-
eters as well as it’s scaling-up ability (Rabinarayan and Padilama 2010). Higher
lipid content not only increases the mean particle diameters but also deteriorates
membrane performance. The temperature and flow speed of the hydrophilic phase
affect the diameter of SLN (Charcosset et al. 2005). The selection of emulsifying
agents and their concentration influences the lipid flux and the diameter of SLNs
(El-Harati et al. 2006).

13.3.7  Supercritical Fluid (SCF) Technology

Supercritical fluid (SCF) technique is a comparatively novel method used for prepa-
ration of SLN and however has been used for preparation of microparticles and drug
powder (Yasuji et al. 2008). It has been proved to be useful alternatives for drying
protein formulations as it has major advantage of solvent-less processing in addition
to its low toxicity, relatively low critical temperature as well as cost-effectiveness. A
fluid is considered as supercritical at the stage once its temperature and pressure go
13  Solid Lipid Nanoparticles 233

above their correspondence critical value. A gas does not liquefy by increasing the
pressure above the critical temperature. Upon increasing the pressure, the density of
the gas raises lacking any noteworthy enlargement in viscosity, whereas the capabil-
ity of the fluid to solubilize the agents too enhances.
The gas which has minute solubility property to dissolve a compound under
ambient condition can behave as super solvent for no. of compound under super-
critical state. Various gases, i.e. CO2, ethane CH2FCF3 and ammonia, were inves-
tigated and tried, but CO2 has proved itself as the best for SCF technique. The
principle behind SCF technology is precipitating out of drug or particles by com-
pressed anti-solvent, i.e. supercritical carbon dioxide (Yang and Ciftci 2016). The
lipid and drug are dissolved in a solvent; the supercritical fluid, selected to act as
anti-solvent to the solutes, is completely immiscible or incompletely soluble with
the solvent. The dissolved solid in solvent is sprayed into the flowing SCF and leads
to precipitation of solid solute particles (Byrappa et al. 2008).
Another method of SLN production using SCF method is considered as “super-
critical extraction of emulsions” (SFEE) (Chattopadhyay et al. 2007). The lipoidic
substances and the drug are solubilized in an lipophilic liquid like chloroform. The
organic solution containing surfactant is suspended with a hydrophilic solvent con-
taining cosurfactant. The resultant product is subjected to high-pressure homoge-
nizer in order to produce O/W emulsion which enters from the top of the extraction
column at a steady speed, and countercurrently the SCF is entered at a steady flow
rate. Solid lipid nanoparticles are produced as dispersion into the SCF.

13.4  Characterization of Solid Lipid Nanoparticles

As discussed previously, SLNs are generally produced by homogenizing a suspen-

sion of lipids and aqueous phase. Characterization of SLN is a challenge due to the
smaller size of the particles and the complexity of the system. Many important
aspects have to be considered which might affect the stability and drug release
kinetics of SLN. Particle size, size distribution and components of the nanocarriers,
morphology and minute structure are vital characteristics of SLNs which affect
encapsulation efficiency, stability and release pattern. All these factors point out that
the performance of lipid nanoparticles—drug incorporation, release and stability—
is influenced by particle size, shape and structure.

13.4.1  Physical Properties

13.4.1.1  Size and Its Distribution

Particle size is a main factor which ensue the in vivo fate of SLNs. Particles larger
than 5  μm are restricted for parenteral route as these might block capillary and
ultimately can cause embolisms. Clearance of particles from the circulation by the
234 A. K. Jain and S. Thareja

reticuloendothelial organs is also a size-based phenomenon (Wu et  al. 2012).

Formulation-related variables (lipid nature, dispersing medium, surfactant, cosur-
factant and other additives) as well as process variables (preparation method, extent
of homogenization and sonication, temperature, equipment) are generally referred
to as quality constraints. Size determination study of SLNs is carried out by
scattering-­based sizing techniques like photon correlation spectroscopy and/or laser
diffraction. Particle size and morphology, therefore, may affect the entrapment and
release kinetics of the therapeutics from the lipid nanoparticles.

Photon Correlation Spectroscopy

Photon correlation spectroscopy (PCS) or dynamic light scattering (DLS) is the

mostly preferred technique to study the particle diameter of solid lipid nanoparti-
cles in a suspension (Obeidat et al. 2010). It measures the fluctuation of the inten-
sity of the scattered light which is caused by particle movement. PCS generally
requires a tiny amount of sample, and that does not require any laborious sample
preparation. It is nondestructive, faster technique which can determine the size
range from 3 to 3000  nm approximately. PCS analyses the Brownian motion or
random thermal of the particles in the suspended state in a dispersion medium.
Particles in dispersion are irradiated by a laser light, and the changes in the inten-
sity of scattered light are measured after multiple collisions of particles as a func-
tion of time. The PCS device has a laser source, which falls on the dispersion in a
sample cell (temperature controlled), and scattered light is detected using a photo-
multiplier. Smaller particles cause high-intensity fluctuations compared to larger
particles, because of their high diffusion coefficient. A statistical relationship is
applied to correlate the scattering intensity vs time curve to obtain particle diame-
ter and its distribution.
The technique gives the particle size, in terms of z-average diameter and poly-
dispersity index (PDI) that is an indicative of the total length of the particle size
distribution. The lower PDI is considered to be narrow particle size distribution,
i.e. monodisperse suspension. Higher PDI values indicated poor uniformity of size
distribution pattern. Most of the scientists recognize PDI values less than 0.3 as
optimum values; however, 0.5 value of PDI is also sometimes accepted. Even
though PCS is the extensively established technique, it is based on the transla-
tional diffusion coefficient D of the particles; hence it is an indirect method for
measurement of particle size. Although PCS is a consistent method for analysing
particles having tight distribution pattern, it is not recommended for multimodal
size distributions. As presence of larger aggregates or microparticles may hinder
the movement of nano range particles hence have a noteworthy effect on measure-
ment process. SLN suspension is generally diluted in order to decrease manifold
scattering effects. In addition PCS assumes that all the particles are of spherical
shape; however, this is of least importance for SLNs but is a matter of concern for
other colloidal carriers.
13  Solid Lipid Nanoparticles 235

Laser Diffraction (LD) Spectroscopy

LD is an effective tool which has a broader detection range (20 nm–2000 μm). Laser

diffraction (LD), which is also known as laser light scattering, can be used alone or
in combination with PCS to obtain an entire population of particle size from tiny
ones to large particles. LD is depending on the composite phenomenon of Fraunhofer,
Mie and Rayleigh scattering from an illuminated particle in dispersion state.
Principle behind LD is that once a laser light falls on a sample having suspended
particles, the bigger particles scatter light at narrow angles whereas the minor ones
at broader angles (Stoye et al. 1998). Nevertheless the technique deficient in preci-
sion for particle dispersions has drastically smaller diameter compared to laser
wavelength.
In addition, laser diffractometer provides a good estimation of polydispersity of
particles; hence LD covers a broader size range from nanometre to 100 micron. The
main limitation of this theory is that its application to SLN demands knowledge
refractive index at the measurement wavelength as results are strongly dependent on
these optical parameters. The development of PIDS technology (Polarization
Intensity Differential Scattering) greatly enhanced the sensitivity of LD to smaller
particles (Jores et  al. 2004). This technique merges wavelength dependence and
polarization effects together and hence significantly increases the accurateness of
LD towards tiny nanoparticles.

13.4.2  Microscopic Methods

13.4.2.1  Shape and Surface Morphology

Microscopic techniques such as electron microscopy (EM) and atomic force micros-
copy can also be used to get information on particle size in the nanometric range. In
contrast to light scattering-dependent method, individual particles are measured by
the Coulter counter and microscope techniques; hence these provide the benefit of a
closer straight analysis. In addition, the results generated by PCS and LD could be
affected by the anisometric morphology of the particles. Therefore, the data pro-
duced by PCS and LD could be corroborated with EM to determine the real size of
the SLNs.
Morphology usually narrates to the external structure and surface pattern of the
particle, while ultrastructure narrates to the internal structure of the particle.
Ultrastructure indicates the existence and orientation of the different portions of the
formulation and nanoparticle as a whole as well as associated structures like
micelles, a core-shell structure which may or may not coexist. Generally, spheres
have the minimum likely surface area out of other possible shape and, hence, could
be stabilized with minimum quantity of surfactant. In addition, sphere particles have
the greatest diffusion length and allow the opportunity of sustained and predeter-
mined release of encapsulated therapeutics. In contrast, anisometric shape desires a
236 A. K. Jain and S. Thareja

larger quantity of surfactant for stabilization. It is highly required that the drug is to
be entrapped into the surfactant layer or adsorbed onto outer layer.

Electron Microscopy

Electron microscopy provides the direct information on the particle shape. However,
special concern is possible artefacts which may arise by the sample preparation
procedures. For example, solvent removal may influence the particle shape. These
techniques utilize the electron beam as an alternative of light to visualize
nanoparticles.
Scanning electron microscopy (SEM) measures electrons sprinkled from the
outer layer of the sample to largely create the surface structure, whereas transmis-
sion electron microscopy (TEM) measures electrons transmitted through the sample
and allows to look beyond the surface. Both techniques have some drawbacks asso-
ciated with processing conditions (e.g. vacuum, heating) as well drawbacks associ-
ated with sample preparation, i.e. dehydration, conductive coating staining, etc.;
sometimes changes can be induced within the nanoparticles, while sample prepara-
tion and analysis might produce invalid results.
TEM is also being used to determine the morphology and ultrastructure of SLNs
(Friedrich et al. 2010). Sample preparation steps involve negative staining, freeze-­
fracture and vitrification to study the nanocarriers by TEM.  Negative staining is
carried out by utilizing heavy metal salt solutions on to the colloidal lipid disper-
sions (Blasi et al. 2013; Silva et al. 2011). A tiny droplet of SLN dispersion is kept
on a TEM, grid stained with osmium tetroxide, phosphotungstic acid or uranyl
acetate. Also, the resulting TEM photomicrographs generally may not be fair repre-
sentations of the whole SLN population. Mainly TEM techniques provide informa-
tion of two-dimensional projection of SLN; hence in order to get three-dimensional
anisometric particles and to get additional information on the ultrastructure, freeze-­
fracture technique is utilized. The TEM micrographs of SLN after coating with
uranyl acetate is shown in Fig. 13.7, which shows that SLNs have spherical shape
and size from 80 to 200 nm (Li et al. 2006).

Atomic Force Microscopy

Atomic force microscopy is a superior method which can be used to study the real-
istic shape and surface morphology of the SLN. AFM offers few additional advan-
tages compared to TEM and SEM. As vacuum is not required, the sample needs not
to be coated by a conductive substance; however, the sample should be immobilized
prior to scanning which can be easily done by removal of the aqueous media from
SLN dispersion. Precaution needs to be taken as process of water removal can bring
13  Solid Lipid Nanoparticles 237

Fig. 13.7  Transmission electron microscopy photographs of solid lipid nanoparticles after stain-
ing with 1% uranyl acetate solution. (a) 5-FU loaded Cetyl palmitostearate SLNs (CP) (b) 5-FU
loaded glyceryl monostearate (GMS) SLNs (Reprinted from Shenoy et al. (2013), with permission
from Springer)

alterations linked with shrinkage, clustering and crystallization of the lipid

(Shakesheff et al. 1994). Another strong benefit of AFM is that it can also provide
the important details about soft surfactant layering surrounding the particles that is
not possible with other similar techniques (Gref et al. 1994).

13.4.3  Surface Charge

The measurement of electric charge permits forecasting the long-term storage sta-
bility of SLNs. Generally, particle clustering occurs slightly for charged particles
(high zeta potential) because electrical repulsion takes place between them. Though
it is not tightly followed by the systems stabilized with steric stabilizers as adsorp-
tion of steric stabilizer around the particles diminishes the zeta potential but pre-
vents aggregation (Müller 1996), zeta potential provides an idea about the amplitude
of the electric attraction, or repulsion takes place among SLNs. Generally, greater
zeta potential (e.g. more than +30  mV or less than −30  mV) stabilizes the SLN
dispersion (Saupe et  al. 2006) which prevents the contact between the particles.
Particle cell interactions can also be affected by surface. However, colloidal ­particles
having zeta potential closer to zero can express good long-term stability if they are
sterically stabilized with the help of stabilizers (Okonogi and Riangjanapatee 2013).
Zeta potential is affected by the pH, type and concentration of ions present; hence,
the effect of pH and electrolyte on the stability of SLNs has been studied (Choi
et al. 2014).
238 A. K. Jain and S. Thareja

13.4.4  Drug Encapsulation and Loading Capacity

Huge varieties of drugs have been incorporated into the SLN.  The most critical
parameter to analyse the appropriateness of a drug carrier is its loading capacity
which is generally expressed in percent related to the lipid phase. The various fac-
tors which influence the loading capacity of drug in the lipid are drug solubility in
melted lipid, mixing efficiency of lipid and polymorphs.
The precondition to attain a considerable drug encapsulation is an adequate solu-
bility in the lipid matrix, and drug solubility should be greater than desired as it
diminishes upon cooling down the lipid matrix and could be lesser in the solid lipid.
To encourage drug solubilization, solubilizers can be added to the lipid melt. More
complex lipids rather simple mixtures of mono-, di- and triglycerides and also con-
taining fatty acids of various chain lengths produce crystals with many imperfec-
tions allowing space to accommodate the drugs (Westesen and Siekmann 1997).
Crystalline structure although property of the chemical nature of the lipid is of vital
importance in determining whether a drug will tightly incorporate for the long-term
or expel out easily.

13.4.4.1  Determination of Incorporated Drug

Quantity of encapsulated agents in SLNs manipulates the release kinetics; therefore

it is of utmost crucial importance to determine the encapsulated agents. The quan-
tity of drug entrapped per unit wt. of SLN is estimated after removal of the free
drug. Separation of free drug can be carried out by ultracentrifugation and extensive
dialysis. The concentration of drug after separation of free drug is determined by
using standard analytical technique such as spectrophotometer, spectroflouropho-
tometry or HPLC. Alternatively, encapsulation efficiency can be assessed by dis-
solving the SLN in a suitable solvent followed by measurement using respective
analytical method. Another way to determine encapsulation efficiency is by extrac-
tion of the drug into appropriate solvent (Huang et al. 2008). EE is calculated in %:

Amount of drug into the particles

EE% = ×100
Amount of drug added to the formulation

13.4.5  Drug Localization and Drug Release

A major concern with lipid nanoparticles is the burst release observed with these
systems. A prolonged drug release was first obtained when studying the incor-
poration of prednisolone. Even it is possible to alter the release profiles as a
13  Solid Lipid Nanoparticles 239

function of lipid matrix, stabilizer concentration and production condition (e.g.

temperature) (Muhlen and Mehnert 1998). It is possible to achieve in vitro drug
release up to 5–7 weeks with SLN. Moreover, release profiles could be altered
to avoid any burst release; however this burst effect could be useful as load-
ing dose.
Even though the drug is place inside the SLN but not always distributed homog-
enously throughout the matrix (Ren et al. 2013) and can be discreted in different
regions of SLNs as well as in associated structures i.e. micelles, liposomes, drug
nanocrystals. Methods used to find out the release can inherently manipulate the
in vitro drug release pattern of SLN/NLC; hence critical consideration of method-
ologies should be performed. Regrettably, release experiments are carried out
through several ways such as separation by centrifugation and dialysis; hence it is
difficult to make comparison. The SLN dispersion is filled in pretreated dialysis bag
and immersed in an appropriate dissolution fluid at RT under sink or nonsink condi-
tions with gentle stirring. In vitro release profiles of carvedilol from SLN composed
of various lipids (Compritol, lecithin) are shown in Fig. 13.8 and found that SLN
made of higher lecithin concentration has shown a faster drug release compared to
SLN made of Compritol (Aboud et al. 2016).

70
S1
60
S2
% Carvedilol released

50
S3
40
S4
30
Carvedilol
solution
20

10

0
0 2 4 6 8
Time (h)

Fig. 13.8  In vitro release profiles of carvedilol from various SLNs made from different lipids.
(Reproduced with kind permission from Springer, Aboud et al. (2016))
240 A. K. Jain and S. Thareja

13.5  Applications of Solid Lipid Nanoparticles

13.5.1  Parenteral Delivery

SLNs are originally discovered to sort out few inherent difficulties of the parenteral
nanoemulsions. During last two decades, SLN was explored for a diversity of novel
applications and has been shown very useful to solve the problems associated to the
faster drug leakage from the parenteral nanoemulsion. Modification of SLN surface
of poloxamer- or poloxamine-stabilized SLN showed in  vivo sustained and con-
trolled effect (Scholer et al. 2001). Also, in vivo chemical stability of camptothecin
increased after its encapsulation into the SLN (Joshi and Muller 2009). Many of the
side effects of docetaxel have been reduced by parenteral administration of SLN-­
encapsulated docetaxel compared to plain drug (Liu et al. 2011). SLNs have proved
to increase cellular uptake and targeting potential and ultimately improved the can-
cer therapy after encapsulation of cytotoxic drugs into the SLN (Liu et al. 2011).
Also, SLNs have potential to overcome the challenges linked with parenteral admin-
istration of major diseases like malaria by increasing poor solubility of antimalarial
drugs, for example, artemether and primaquine, after encapsulation in NLC by
reducing haemolytic potential and increasing antimalarial response (Nayak et  al.
2010; Mosallaei et al. 2013; Omwoyo et al. 2014). SLN increased drug levels in the
lung, spleen and brain compared to plain drug solution which leads to higher distri-
bution into the liver and kidneys.

13.5.2  Oral Delivery

Although the oral route is the most natural choice of drug administration, low solu-
bility and bioavailability of diversity of therapeutics restrict its use. After orally
administered, triglycerides (one of the components of SLN) are broken into mono-
and diglycerides. These simple glycerides interact with bile salts present in the GIT
and form micelles containing the drug which absorbed via chylomicron into the
lymphatic system (Patil et al. 2012). Additionally, SLN may be taken up by M-cells
of Peyer’s patches (He et al. 2005). SLN may be administered orally as aqueous
dispersions as well as traditional dosage forms such as tablets, pellets or capsules.
Also, presence of food greatly affects SLN behaviour in GIT. The atmosphere of the
stomach favours particle aggregation because of the presence of acid and high ionic
strength. Improved bioavailability and sustained blood concentration of cyclospo-
rine were found through lipid nanodispersions after per oral administration (Martins
et al. 2007). In a latest study, SLNs have protected insulin against in vitro proteo-
lytic enzymes upon encapsulation into the SLN (Almeida and Souto 2007). Also,
SLNs have demonstrated the improvement in the bioavailability and protect the
proteins against degradation after oral administration (Aungst 2000; Basu
et al. 2010).
13  Solid Lipid Nanoparticles 241

13.5.3  Transdermal and Topical Use

The use of SLN for transdermal and topical purpose expanded great attention. SLNs
present higher chemical stability of the drugs, easily make film on skin surface,
greatly hydrate skin and modulate drug release. Also, as they are made of nonirritant
and nontoxic lipids, they can be applied to damaged and inflamed skin (Attama
et al. 2009). Enhanced safety and therapeutic effectiveness after entrapment into the
lipid particles have been reported for coenzyme Q10 (Lin et al. 2010), celecoxib
(Del Pozo-Rodriguez et al. 2010), ketoprofen (Obeidat 2012), vitamin A (Cirri et al.
2012) and many more. Also when systemic absorption is undesired after dermal
application, SLN achieved epidermal targeting of podophyllotoxin which was con-
firmed with fluorescence microscopy (Dingler et al. 1999). Moreover SLN decreased
the irritation effect of retinoic acid and also enhanced its stability (Chen et al. 2006).
Additionally, SLNs have its application in the cosmetics as the incorporation of
novel technologies has led to successful marketing. Various anti-ageing creams,
sunscreen products and many more cosmetics have been using SLN and NLC and
found that lipid particles in the form of cream formulation did not have irritant pro-
spective with a greater hydration compared to traditional creams (Junyaprasert et al.
2009). Generally, smaller particle SLNs are more useful for dermal application. In
the majority of cases, the SLN dispersion is added to an ointment or gel in order to
design a formulation which can be easily applied to the skin. Enhancement of the
SLN quantity in to the suspension comes out in a semisolid, gel-like consistency
that is suitable for direct application on the skin surface (Farboud et al. 2011).
The greater advantage of using SLNs for topical products is that they protect the
labile drugs against degradation, for example, retinol or vitamin C, which cannot be
added directly into the creams because of the chemical instability which can be
overcome by using SLN (Siddiqui et al. 2014).

13.5.4  Pulmonary, Nasal and Ocular Administration

SLNs are appropriate delivery system with excellent acceptability and higher safety
for pulmonary treatment (Pardeike et al. 2010). However, SLNs as dry powders are
not suitable for delivery to the lungs as the particle size is too small to be retained
inside. Simple approach of aerosolization of aqueous SLN dispersions provides as
an attractive approach. Also, tiny size of SLNs facilitates their incorporation into the
microparticles and drops which can deliver the content to the alveoli. In this regard,
SLN and NLC have improved the pharmacokinetic parameters of itraconazole
(Pardeike et  al. 2011), phenethyl isothiocyanate (Pilcer and Amighi 2010), cele-
coxib (Patlolla et al. 2010) and thymopentin (Jaafar-Maalej et al. 2011), after pul-
monary administration (Pardeike et al. 2010). Also, incorporation of antituberculosis
drugs into the SLN showed convincing findings after pulmonary administration
(Liu et al. 2008).
242 A. K. Jain and S. Thareja

Nasal administration is also proved to be promising using SLNs for variety of

drugs, i.e. ropinirole (Chavan et  al. 2013), alprazolam (Pardeshi et  al. 2013) and
budesonide (Joshi et  al. 2012). Brain targeting is also reported using SLN after
intranasal administration for risperidone and demonstrated enhanced brain bioavail-
ability after nasal administration to the mice (Li et al. 2009). The major limitation
of ophthalmologic formulation is low retention time into the eye cavity. Diclofenac
encapsulated into the SLN demonstrated prolonged release and greater transloca-
tion to artificial corneal surface (Attama et al. 2008). Also, SLN-based tobramycin
formulations proved to be more effective in the treatment of ocular infections
(Zhang et al. 2006).

13.6  SLNs as a Carrier for Site-Specific Delivery

13.6.1  Application in Gene Delivery

In recent time, lipid-based nanocarriers have received greater interest in the area of
gene therapy as convincing substitute of positively charged lipids as of protection
ability of the incorporated agents against chemical degradation and their faster
uptake by cells. In addition production method of SLNs requires low mechanical
force; hence processing steps do not degrade DNA and RNA strands. However,
cationic charge is a prerequisite for the efficient contact with the anionic cell surface
and could be easily induced by incorporating suitable cationic surfactants into lipid
matrix. Cationic lipid carriers have been investigated for transfection efficiency in
African green monkey kidney fibroblast-like cells (Cos-1) and human bronchoepi-
thelial cell (Olbrich et  al. 2001) and found that SLNs efficiently bind and trans-
fected plasmid DNA for the first time using solid lipid nanoparticles. In the recent
past, several reports about successful incorporation of genetic materials such as
DNA, plasmid DNA and other nucleic acid into the SLN have been published
(Zhuang et al. 2010). Gene delivery of a diametric HIV-1 HAT peptide (TAT 2) by
incorporation into SLN is demonstrated. Nucleic acid-encapsulated nanoparticles
were prepared from a liquid phase composed of aqueous phase containing DNA and
a water-miscible organic solvent containing lipid. The obtained particles are called
genospheres (70–100 nm) which targeted specifically by insertion of an antibody-­
lipo polymer conjugated in the particle. Cationic SLNs have shown comparable
in vivo transfection efficacy to the liposome made of similar cationic lipids. Recently
Carrillo and coworkers used cationic SLN gene delivery to the brain (Carrillo
et al. 2013).
13  Solid Lipid Nanoparticles 243

13.6.2  SLN as Carriers for Peptides and Protein Drugs

Exception to most polymeric micro- and nanocarrier production techniques used for
SLN does not require highly toxic organic liquids, which might be harmful for pro-
tein bioactives. Moreover, SLNs can be made to accumulate hydrophobic or water-­
soluble drugs for parenteral and non-parenteral routes.
SLN production is based on solidified emulsion (dispersed phase) methodolo-
gies; hence due to hydrophilic nature of proteins, they are expected to be poorly
microencapsulated into the hydrophobic matrix of SLN. A large number of proteins
and peptides, e.g. calcitonin, insulin, LHRH, somatostatin and protein antigens,
have been studied for drug release kinetics, protein stability and in  vivo perfor-
mance after incorporation into the SLNs. Peptide ligand-modified SLNs are evalu-
ated to increase oral bioavailability of proteins and found that absolute bioavailability
of peptides was increased by 2.45 to 1.98 times compared to unmodified SLNs,
indicating the scope and effectiveness for the improvement of the oral bioavailabil-
ity of proteins (Fan et al. 2014). Another research group has prepared peptide-loaded
SLNs by solvent diffusion method. The gonadorelin (a model peptide) was incorpo-
rated and evaluated for various parameters. The average diameter and zeta potential
of SLN were found to be 421.7 nm and −21.1 mV, respectively. However, in vitro
release followed biphasic pattern with slow release of gonadorelin (Hu et al. 2004).
SLNs were prepared by solubilizing lysozyme (a model peptide) into the melted
lipid phase. Results revealed solubility-dependent entrapment efficiency of the pep-
tide in the lipid phase of the finished preparation.

13.6.3  Lipid Nanoparticle as a Carrier for Vaccine

Adjuvants are of great importance in vaccination in order to elicit enhanced immune

response. Safer new subunit vaccines have poor immunization potential when used
alone, and hence effective adjuvants are required (Copland et al. 2005). Improving
the quantity of antigen transported is not a resolution as it enhances the vaccination
cost drastically particularly for the developing countries. Conventional adjuvant
such as alum is to be employed; however they suffer many disadvantages and have
limited immunization to boost up potential. Alternatively various biodegradable
polymeric microparticles, niosomes, liposomes and nanoparticles have been
explored as an adjuvant for parenteral or mucosal administration routes (Eyles et al.
2003). However, most of the additives used for production of these colloidal carriers
as well as manufacturing conditions have deterioration effect on vaccine stability.
PLA/PLGA microspheres have shown potential as useful antigen delivery systems
(Storni et al. 2005). Advantages of SLN as adjuvant compared to traditional adju-
vants are the excellent tolerability by the body and biodegradation. The lipid portion
of SLN degrades gradually allowing an extended contact of antigens to the immune
244 A. K. Jain and S. Thareja

cells. Also, degradation of the antigen by the enzyme complexes is restricted due to
steric stabilization by the surfactants which hamper the direct exposure (Olbrich
and Muller 1999). First report of SLN as adjuvant displayed 43 and 73% effective
protection (antibody levels) (Muller et al. 2000). Malaria protein antigen R32NS1
was incorporated into lipospheres and demonstrated increased specific IgG response
in serum after intramuscular injection which extended for a minimum of 12-week
period after primary immunization (Amsteel et al. 1992). Proteolytic degradation at
various mucosae makes peptide or protein vaccines less effective for mucosal deliv-
ery; formulation into SLNs is a documented approach to enhance mucosal immuni-
zation. Intranasal administration of particles showed deposition of the particles into
the lungs, and its lung mucosal layer takes a crucial part in generating immune
response (Eyles et al. 2003).

13.7  Stability

SLN stability can be improved by removal of the water as the powder form is usu-
ally more stable than the suspensions. Lyophilization is a preferred and appropriate
technique used to get rid of the water in the formulation. However, while in lyophi-
lization the protection efficiency of the surfactant might be transformed as a result,
the lyophilized SLNs may lead to bigger particles after redispersion (Del Pozo-­
Rodriguez et  al. 2009). Drug leakage and modification in the surface charge are
likely during lyophilization. Therefore, addition of appropriate cryoprotectant such
as mannose, maltose and trehalose (10–15%) is essential before lyophilization
(Cavalli et al. 1997). The properties of the redispersed powder are largely affected
by the selection of the cryoprotectant.
Alternatively, spray drying is also another approach used to form powders from
SLN dispersions. As heat is required in the process, hence lipids are preferred
which have melting points higher than 70 °C. Sometimes it results in particle aggre-
gation. Spray drying cannot be used for more diluted SLN dispersions. An addi-
tional method, of stabilizing SLN dispersions, is to make it viscous, as viscous
dispersions have reduced rate of sedimentation and collision of the particles (Freitas
and Muller 1998). In spite of all these problems observed during stabilization and
storage of SLNs, these systems might be stable up to 3  years in dispersion state
(Freitas and Muller 1999).

13.8  Conclusions

SLNs unite the advantage of polymeric nanoparticles, fatty emulsions as well as lipid
vesicles. Moreover, possibility of accumulation of hydrophobic and aqueous soluble
agents, enhanced stability, economy and simplicity of large-scale production process
13  Solid Lipid Nanoparticles 245

makes them attractive carriers for drug delivery. Production techniques based on
commercial production of emulsions and nutrition parenteral was p­ rimarily used for
large-scale production of SLNs because necessary set of instrument simply existed
and can be engaged at both lab and industrial scale. The scalability of methods of
preparation of lipid nanoparticles leads to no difficulty in commercialization. In addi-
tion site-specific delivery and prolonged effect of drug could be healthier attained
with SLNs. The other aspects of SLN related to commercial production such as ster-
ilization, freeze drying and shelf life have already been developed to good standard.

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Chapter 14
Nanotechnology Applications
and Synthesis of Graphene
as Nanomaterial for Nanoelectronics

Anil Bhardwaj, Gaurav Sharma, and Sumeet Gupta

14.1  Introduction

At present the tremendous development in the field of integrated circuit t­ echnology

(IC technology) is based on the continuous scaling of silicon-based CMOS transis-
tor devices (Roberts 1984). The scaling helps to maintain the law proposed by
Moore in 1965, which states that “the number of devices or transistor per square
inch on the integrated circuit doubles every year.” The scaling in the nanometer
(nm) region is posing serious problems in the integration of devices and maintain-
ing performance of the device’s parameters (Kilby 2000; Mollick 2006). At the
nanometer (nm) scale level, the effect of quantum tunneling is very much prevalent
as it makes device fabrication difficult (Horowitz et al. 2005; Wu et al. 2013).
At nanometer (nm) scale region, the secondary effects come into existence.
There is more power dissipation in the system along with subthreshold leakage
current flow, which mainly affects the performance of the whole system.
Therefore, the problem that arises due to scaling has made researchers search for
alternative materials. Hence, carbon nanotubes (CNTs) and graphene are the
prime contenders that can potentially replace silicon (Si) in various conventional
devices. This will also be helpful in the electronics industry in the near future.
The various properties of these devices include thermal, mechanical, optical, and
electrical properties which are very much effected by using the nanometer
designs.
In this chapter the detailed study of various properties of graphene as well as carbon
nanotubes (CNTs) which are useful in the present day-to-day scenario in the nanotech-
nology regime has been reported. This chapter will also illustrate the implementation
and the conceptualization of the term nanotechnology (nm) in numerous number

A. Bhardwaj (*) · G. Sharma · S. Gupta

Shri Mata Vaishno Devi University, Katra, Jammu and Kashmir, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 251

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_14
252 A. Bhardwaj et al.

of fields like electronics, medical, chemical, robotics, mechanical, aeronautics, and

information technology along within the computers.
The term nanotechnology has its origin from the two Greek words “nano” and
“technology.” The Greek prefix “nano” means “to a billionth of any entity,” and the
word “technology” implicates the concept of innovation and also the art and science
which thus investigate the manipulation of the matter at nanoscale (Roberts 1984;
Kilby 2000; Mollick 2006). Because of which, nanotechnology or nanotech or
nanoscaled technology is customarily weighed below 0.1 um or 100  nm (so nm
scale is equivalent to 10−9 m). Nanoscale science (or nanoscience) investigates the
phantasm and properties and also measures the varied responses of materials at vari-
ous scales including atomic, molecular, and macromolecular levels along with the
sizes falling universally in the range of 1–100 nm.
In the current scenario which is nowadays preeminently under 5 nm, the materi-
als properties diverge incomparably (i.e., vital role being played by quantum-scale
effects) vis-a-vis a bigger particulate scale. Nanotech involves various aspects
which include design, manipulation, building, production, and application, which is
achieved by regulating the shape and size, formulating the properties, responses,
and performance of devices and systems up to < than 100 nm.
Nanotechnology being a branch of science and technology deals with the materi-
als having the dimensional size of the order of nanometer scale. The term nanometer
means that the scale unit is having 10−9 m value. These materials have the size less
than 100 nm. Nanotech also denotes the manipulation of the matter on supramo-
lecular scale, atomic scale, and molecular scale (Ganji and Kachapi 2015).
Another more authenticated and generalized definition of nanotech is imparted
by the National Nanotechnology Initiative (NNI) where it includes the manipula-
tions of the element dimensions by measurably varying one of the dimensions from
1 to 100  nm. The basis of the above fact is that the quantum mechanical effects
become significant in the quantum realm scale.
To conceive this idea of nanotechnology, one should observe the nail of the little
finger. The dimensional width of the nail on the little finger is round about 10 mil-
lion nm; another live example of the nanotechnology is the strand of human hair
which is of the range 75,000–100,000 nm in diameter. This term was first coined in
the late 1950s of the twentieth century especially around 1959. Being an umbrella
phrase that beset all the fields of Science & Engineering at nanometer scale.
Nanotech is immensely distinct and multidisciplinary field extending from the novel
addendum of conventional physics devices to absolutely a new approach planted on
the molecular self-assembly.
Nanotechnology being new was mainly talked by the then physicist and Nobel
laureate Richard Feynman in which he stated that “There is plenty of room at the
bottom” (Feynman 1992).
Nanotech being an enabling technology is expected to revolutionize the major
portions of the industrial sectors. The earliest widespread description of nanotech-
nology was primarily focused on the particular goal of precise manipulation of
atoms and molecules which is required for the fabrication of macroscopic products.
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 253

The NNI states any material to be in the nanotechnology state only if the con-
cerned material fulfills all the conditions as [EPA, US 2007]:
• Research and technological evolution centered at the atomic, molecular, or
macromolecular levels ranging approx. from 1 to 100 nm
• Creating and using systems, structures, and devices containing innovative
properties and functions due their small or intermediate size
• Manipulation and control ability at atomic scale
Nanotech being an appearing technology because of feasibility of put forwarding
through going materials and to forge state-of-the-art materials having utterly unique
features and functionality instilled with colossal abilities for wider spectrum of
applications. Supplemental to its utility in industrial arena, pioneering innovations
can be forecasted in various fields like ICT, medical and allied technology, metrology,
etc. (Seeman 2003).
Symbolic utilizations of nanosciences and nanoengineering field can be seen in
various arenas like pharmaceuticals, cosmetic products, canned food, chemical
engineering, materials with high performance, electronic items, precision mechanics,
light energy models, energy generation, and environmental sciences.
Nanoscience (nanotechnology) is the most energized discipline of science and
technology as it promises superior health, wealth, defense, and closing ranks
between science and fiction. It has grown rapidly over the years and has already
gained considerable international and national interest. It has abeyance for making
enormous impact on the society, humanity, and ecology apart from their immediate
uses in hardware and electronics system (Kumar 2006; Phillips 2006).
Their direct and indirect impact would be widespread, and it would give a new
boost to various emerging technologies such as information technology, data storage,
semiconductor technology, sensors and actuators, pharmaceutical, biomedicine,
biotech, chemical industry, aerospace, and automotive industry.
As the particle size reduces and reaches the nanoscale regime, the surface area
to volume ratio of the particle rapidly increases. The number of atoms on the sur-
face of the particle in this size range will dramatically increase compared to the
atoms within the particle. A particle of 5  nm in diameter has nearly 50% of its
atoms on the surface compared to the 100 nm particle where less than 5% are sur-
face atoms. This affects the internal structure of the particle including the arrange-
ment of atoms and the electronic configuration, and quantum effects dominate
(Ferrari 2007).
In the 1980s era, two major discoveries stimulated the growth of nanotechnology
in modern era:
• The first comprised of scanning via tunneling microscope discovery in the year
1981 which put forward the visualization of individual atoms along with their
bonds. In year 1989 the above said technique was successfully put into action to
maneuver distinctive atoms. Gerd Binnig and Heinrich Rohrer who were the
developers of the microscope at IBM’s research lab at Zurich got Nobel Prize in
254 A. Bhardwaj et al.

the field of physics in 1986 (Meyyappan 2004; Novoselov et  al. 2004).
In the same year, the discovery of analogous atomic force microscope made by
them led to the revolution in the field of nanotech.
• The second comprised of the discovery of fullerenes in 1985 by Kroto, Smalley,
and Curl for which they won the Nobel Prize in the field of chemistry in 1996.
C60 was initially not considered in the nanotech field but was then considered
with the discovery of graphene tubes (called carbon nanotubes and every now
and then known as the buckytubes) with numerous utilizations in the field of
electronics (Meng et al. 2012).
The nanotech field during the 2000s called for upsurge in scientific, political, and
commercial attention that resulted in development and controversy at the same time.
The major skepticisms were related to the definitions and utilities of nanotech. In
2001 and 2003, apprehensions surfaced about the feasibility of applications fore-
casted by supporters of molecular nanotech, which ultimately ended up with a pub-
lic discussion between Drexler and Smalley. Further the profit-oriented products
started to appear with the progression of nanotech in the world. These materials are
narrowed down to a wide-scale usage of these nanomaterials without the inclusion
of any atomic control of matter (Wang et al. 2012).
Various instances of these encompass the usage of nanoparticles of silver as anti-
biotics, sunscreens composed of nanoparticle components, silica nanoparticles to
strengthen carbon fiber, and clothing made of CNTs with stain resilience properties.
Governments nowadays have started promoting nanotechnology and invested
funds in the research field of nanotech; for example, the USA started with the NNI
that gave a size-dependent description of nanotech and facilitated monetary support
for explorations and analysis on the nanoscale. Similarly the European Framework
Program was established to give a boost in the development of nanotech. The
mid-­2000s saw the prospering of innovative and serious scientific concerns in
these fields.
Various projects evolved for making nanotech road maps based on meticulous
maneuvering of matter with discussions on both present and future capacities
and goals.

14.1.1  Types of Nanomaterials

The nanomaterials are the foundations on which nanoscience and nanotechnology

are based.
In the past few years, nanostructure science-based technology is recognized as an
interdisciplinary area for researchers to collaborate. This leads to the development
activity in the worldwide researcher’s fraternity. Nanotechnology is having potential to
revolutionize the methods in which the materials and other products are created. There
are some nanomaterials that occur naturally to be utilized in various applications.
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 255

The various types of nanomaterials which have been manufactured and devel-
oped are:
• Nanotubes: Being a tubelike structure in nm scale, nanotubes are the kind of
nanoparticles within which other smaller nanoparticles can be channeled with a
property of an electric conductor as well as insulator. The various kinds of nano-
tubes are (Lakhtakia 2012):
–– BCN nanotubes
–– Boron nitride nanotubes
–– CNTs
–– DNA nanotubes
–– Gallium nitride nanotubes
–– Silicon nanotubes
–– Inorganic nanotubes
–– Tunneling and titania nanotubes
• Nanorods: Physiology here refers to branching (part of particular field) one
physiology of nanoscale particle with each comprising the structural range from
1 to 100  nm after being synthesized from the metals or the semiconductors.
They have standard aspect ratio to be in the range of 3–5. They are manufac-
tured through chemical synthesis after the combination of ligands which are
acting as shape-controlling agents bonding to obtain different facets of nanorods
of varying strengths. They are majorly implemented in MEMS-based devices
and accelerometers (Lakhtakia 2012; Respaud et al. 2016).
• Nanocomposite: These are the multiphase solid materials in which one phase is
provided with one, two, or three dimensions of less than 100 nm. In some cases
more than one phase dimensional size is in nm range, and they are thus embed-
ded in the metal, ceramic, or polymer matrix.
• Nanocoatings: These are the nanosized thin films which are applied to the sur-
face of various materials so as to enhance the various characteristic features of
the materials such as the corrosion protection, protection against the degradation
caused by the water and ice element, frictional minimization, antifouling and
antibacterial properties, self-cleaning property, and resistance to heat and radia-
tions along with thermal management. Nanocoatings are used for aerospace,
defense, medical, oil, marine, and metallic industries (Kolyadina et al. 2016).
• Graphenes: They are nowadays a very attractive material for post-CMOS or
silicon electronics because of their high carrier mobility and planar structure,
thereby making the integration with the standard technology easier than that of
CNTs. Moreover, nowadays the 2D material systems have gained a great amount
of attention among various global research communities. They are majorly 2D
material with only one-atom thickness (Imperiale et al. 2010).
• Thin films: These comprise of the layers of materials having thickness in the
range of few nm to several mm.
256 A. Bhardwaj et al.

14.1.2  Applications of Nanotechnology

Nanotechnology may be defined as the technique to manipulate matter at atomic

level or molecular level. The design obtained is utilized for a particular application.
The structures developed are worked in the range between 1 and 100 nm in size.
This technique refers to development of structures by selection either of top-down
or bottom-up design processes for individual components (Wu et  al. 2008;
Shahabadi et al. 2016).
From the definition, it acts on the emerging technologies associated with the
novel classes of therapeutics. Using the improved technology of nanotechnology, it
may be possible to improve upon targeted drug delivery (Hu et al. 2012), detection
(Goenka et al. 2014), medical instrumentation (Goenka et al. 2014), and other spe-
cific areas. Many materials will be acted upon where the nanomaterial being used
has a large surface area to volume ratio and is size dependable for many applications
as stated above. Before extensively discussing about the advantages of the
Nanotechnology, there should be discussion about why the nanotech is becoming
the most favored technology among the researchers. The nanotech is the most
widely illustrated field because of the following:
• Engineers: Development of processes and techniques to handle materials at
nanoscale and fabrication of devices
• Electronics: Development of new types of semiconductor materials having
enhanced features

14.1.3  Advantages of Nanotechnology

Among the engineers it is most widely privileged because of the following factors:
• Materials manufactured are stronger, lighter, cheaper, durable, and precise.
• With the help of nanotech, the computers manufactured can become billion times
faster and million times smaller. The manufacturing cost is also negligible.
• Nanotechnology is having great impact on various electronics products; thus
they refashion/remodel their procedures and applications. The areas which are
benefitted most include diodes, nanotransistors, OLED, quantum computers,
plasma displays, etc. (Yeole and Padole 2015).
• Nanotech is also profitable for the energy sector. With the advancement of
smaller and energy-efficient products, especially the energy-absorbing and the
energy-storing devices, the energy consumption and wastage have been reduced
dramatically. Production of solar cells, fuel cells, and hot solar cells has revolu-
tionized the energy sector.
• Materials like nanotubes, aerogels, nanoparticles, etc. are very much stronger,
durable, and lighter than some of the conventional tools and equipment like steel,
aluminum, and other heavy earth metals (Prokhorov and Botsula 2010).
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 257

• With the advent of nanotech in the medical sector, smart drugs have been cre-
ated for faster, side effect-free, and effective treatment of human ailments like
diabetes and cancer and for tissue regeneration along with bone repair (Jelicic
et al. 2015).
• In the defense sector, this technology is mainly useful for the development of
weapons of mass destruction with ease and with less cost.

14.2  Graphene as Nanotechnology Material

The demand for fast response time devices is increasing tremendeously in the past
few decades. With the reduction in the area of devices, the conventional semicon-
ductor devices are not suitable because they tend to exhibit the second-order effects.
This leads to the technology scaling of the devices. This leads to shift in the technol-
ogy and made researchers to search for alternative materials to be used in electron-
ics industry. Out of many materials, graphene and CNT have commanding presence
in the electronics industry.
There are several areas for applications of graphene due to its properties such as
high conductivity. Its large surface area makes it a promising material for batteries
and for energy storage applications (Bae et al. 2010), while its transparency, conduc-
tivity, and flexibility make it an interesting material for flexible displays and touch
screens (Novoselov et al. 2004). Other applications include the use of graphene as a
conductive ink, chemical sensor, barrier layer, or heat spreader. Yet, the initial interest
in graphene was sparked by its potential for post-silicon optical and electronic appli-
cations, due to its high intrinsic mobility, scalability, and observed electric field effect
(Novoselov et al. 2004; Schwierz 2010).
There is limitation while looking forward for miniaturization of the devices there
is limitation for scaling of device technology while following the Moores law
(Schaller 1997). The time limit for reaching the limit has been postponed with more
innovations in structures and architectures utilized by researchers throughout the
world. The limit is about to reach its full restriction when the length of the transis-
tors becomes less than 10 nm.
At this duration the potential of graphene as electronic material can be utilized.
Thus the research on improving and modifying various techniques related to gra-
phene need to be improved. Since the last decade, there is tremendous research
related to problems associated with graphene-based electronics reported by
researchers across the globe. There is definitely some more time requirement in the
future to fully develop graphene-based transistors so as to replace silicon-based
electronics.
The structures developed using graphene for logic transistors are probably
different than the contemporary MOS structure. This is attributed to the difference
in properties of graphene and silicon.
258 A. Bhardwaj et al.

Because of its high mobility, graphene is considered to be an important mate-

rial for devices that require ultrahigh speed such as analog and digital logic cir-
cuits. Use of devices in RF applications with graphene is nowadays very much
prevalent. As graphene possesses remarkable optical property of linear dispersion.
This property of Dirac electrons drives the use of graphene-based optoelectronic
devices in broadband applications. Graphene is known to exhibit high optical
damage threshold, and high third-order optical nonlinearities of graphene devices
are also implemented in photonic devices. The application of graphene can be
further extended to interconnect and to achieve that there is requirement of tech-
niques so as to realize various applications as reviewed. Graphene being an
extraordinary material used in the channel of devices is very much useful in high-
frequency RF applications. On the basis of available facts, it can be clearly stated
that graphene possess ultrahigh mobility that leads to ballistic transport at mm
scale, along with large saturation velocity. In addition to high-frequency applica-
tions, they are also used in the design of LNA (low-noise amplifier). As it is well
known fact that the RF transistors have maximum frequency of oscillation (fmax)
and the cutoff frequency (fT). Currently the highest reported cutoff frequency for
graphene MOSFET is 427 GHz, and the maximum fT is 45 GHz (Wu et al. 2016).
Figure  14.1 describes the cutoff frequency for graphene transistors and other
competing transistor types.

Fig. 14.1  Cutoff frequency of graphene MOSFETs, Si MOSFETs, and III-V HEMTs versus gate
length in um (Schwierz 2011)
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 259

Table 14.1  Advent of high-frequency GFET devices (Hua-Qiang et al. 2013; Lin et al. 2010)
Achievement FT/GHz Gate length/nm
Field effect in graphene – –
1st top-gated GFET – 500
1st GHz GFET 14.7 500
1st GFET (submicrometer gate length) 26 150
1st epitaxial (GFET on SiC) 4.4 2000
1st 100GHz (epitaxial GFET on SiC) 100 240
1st nanowire gate GFET 300 144
1st CVD GFET with deep-submicrometer gate 155 40
length
1st 427 GHz GFET with transferred gate stacks 427 67

Table 14.2  Comparison of different material characteristics

InAlAs/ AlGaAs/ AlGaN/
Characteristics Si SiC InGaAs InGaAs GaN Graphene
Peak electron velocity 1.0 2.0 1.0 1.3 1.3 5–7
(×107 cm/s)
Electron mobility at 300 K 1500 700 5400 8500 1500–2200 >100,000
(cm2/V-s)
Thermal conductivity 1.5 4.5 0.7 0.5 >1.5 48.4–53
(W/cm-K)

The various improvements in the cutoff frequency are depicted in Table 14.1.

The comparison analysis of various characteristics is shown in Table 14.2.
Another material that has also found numerous applications in the field of electron-
ics is carbon nanotubes (CNTs). Because of the rapid scaling of electronic devices, the
energy consumption is a major cause of concern for researchers (Lin et  al. 2011).
Most of the researchers are now focusing their concern onto the ultralow-power sen-
sors. Out of most of the sensors, gas sensors for air quality detection c­ onsume maxi-
mum power when used, so CNTs are used instead for ­ energy-­
saving process.
CNT-based gas sensor devices can detect NO2 with power consumption of less than
50 nW. CNTs are innovative devices with good transistor scalability with growth in
performance, and CNTFETs have outstanding current capability. CNTFETs have
been extensively used at 32 nm technology and also below 28 nm. As it is well-known
that the modern-day wireless receivers have to support a variety of wireless standards
working at different frequency bands, thus there is an immediate requirement of power
conservation devices. The perfect solution to these problems is the CNTFETs which
have transit frequency (fT) in the range of terahertz (THz). The CNT model parameter
description is illustrated in Fig. 14.2.
260 A. Bhardwaj et al.

W
S T
CN
Source DCNT CNTs
kex Gate
Source Tex Drain
Lgate Gate

Substrate
Drain
Parallel CNTs) (a) (b)

Fig. 14.2  (a) CNTFET as Channel (b) CNTFET structure

14.3  Graphene and Its Future Aspects

The structure of graphene can be described as a 2D honeycomb lattice of carbon

atoms having thickness of one atom. Graphene being an allotropic form of carbon
is 2D (two-dimensional). It has a hexagonal lattice packing at the atomic scale. Its
structure is similar to other allotropes of carbon, namely, CNTs, graphite, charcoal,
and fullerenes (C60 buckminsterfullerene). The aromatic molecule is considered to
be of indefinitely large size. The combination of the words graphite and “ene” was
first coined by scientist Hanns-Peter Boehm in 1962. It was discovered by Konstantin
Novoselov and Andre Geim in 2004 at the University of Manchester (Hancock
2011). Graphene is a layered material with single-atom-thick layer of graphite
(McClure 1956; Slonczewski et al. 1958; Wallace 1947). Although its existence is
theoretically known for many years, single-atom layer is considered as thermody-
namically unstable.
Novoselov et al. were the initial researchers who experimentally identified the
single-atomic-layer structure of graphene. The findings are not in contradiction to
the theory as the layer was well supported on the substrate (Novoselov et al. 2004).
Also demonstration of high mobility is done experimentally during examination of
electrical properties.
In 2010, Nobel Prize in physics was awarded for revolutionary experiments on
2D graphene materials. Graphene is a flat monolayer of carbon atoms which are
tightly packed in order to achieve honeycomb structural lattice. One carbon atom is
covalently bonded with three adjacent carbon atoms as shown in Fig. 14.3 through
sp2 hybridization, while the rest of the pz carbon orbitals form an extended electron
system (Thakur and Thakur 2015). Due to the unique electronic state of graphene,
it possesses appreciable electrical properties.
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 261

Fig. 14.3  Graphene atomic structure

Graphene has been known for excellent properties that include high mobility
(105 cm2 V−1 s−1 at room temperature), high current density (109 A/cm2), high thermal
conductivity, and good mechanical properties.

14.3.1  Properties of Graphene

Graphene falls under the category of zero-gap semiconductors having high electrical
conductance. The charge carriers in these materials consisting of several layers are
confined naturally in plane. This results in a weak van der Waals interaction between
the nanomaterial and its surroundings (Mas-Balleste et al. 2011).
Due to this reason, 2D nanomaterials are sometimes classified as van der Waals
materials. This weak interaction of graphene aids in the isolation of single-layer
materials, with thickness of single atomic layer. The single-layer thickness of 2D
nanomaterials like graphene makes them a suitable option to help meet the scaling
demand requirement of future technology scenarios. These unique properties of
graphene have attracted researcher’s interest throughout the research community,
thus elevating graphene’s status to that of a true wonder material.
Graphene is being considered as a wonder material nowadays because of its
exhibition of remarkable properties (Burtscher 2005):
• Electronic properties: Electron mobility possessed by graphene materials is sur-
prisingly very high; the value of mobility reported at room temperature is noted
to be around 15,000 cm2 V−1 s−1.
• Optical properties: Graphene possess high value of opacity in the case of atomic
monolayer; in the initial stages, it is capable of absorption with πα ≈ 2.3% fraction
of white light, the portion which is incident on its surface.
• Thermal properties: The thermal conductivity of graphene at room temperature
is in the range of 4.84 ± 0.44 × 103 to 5.30 ± 0.48 × 103 Wm−1 K−1 (Burtscher
2005).
• Mechanical properties: The breaking strength of graphene as compared to that of
steel is 200 times more, with a reported tensile modulus (stiffness) of 1 TPa
(150,000,000 psi).
262 A. Bhardwaj et al.

• Graphene is lighter, harder, stronger, and more flexible than steel. Graphene can
also be recycled and is considered a sustainable, eco-friendly, cost-effective
product.
• Containing single-layer carbon atoms, graphene is the thinnest material known
and is stronger than diamond.
• Used for storing H2 gas used as fuel cells in powered cars.
• Being highly chemically sensitive material, it is capable of detecting
explosives.
• Containing nanometer-sized particles, graphene is helpful in removing ions in
the desalination of water.

14.3.2  D
 ifferent Types of Nanostructures and Methods
of Graphene Preparation

Researchers have to deal with very fine structures during synthesis of nanomateri-
als. This characteristic of nanomaterials led researchers to come up with approaches
for its synthesis. The two approaches used for the synthesis of nanomaterials can
be bottom up or top down. In these approaches, atoms are either assembled together
or disassembled. Bulk solids can be converted into finer pieces till there are few
atoms remaining. The various techniques for the fabrication of different types of
nanostructures are (Prokhorov and Botsula 2010):
• Nanoprocessing
• Nanotooling
• Nanomachining
• Surface engineering
In the field of electronics, the various materials fabricated are (Kolyadina et al.
2016; Yeole and Padole 2015; Prokhorov and Botsula 2010):
• NEMS and MEMS devices: These are basically the sensor and actuator circuits
implanted at the nano- and microscale, thus offering opportunity for integration
into application that requires high performance as well as high precision but at
the same time containing some space constraints.
• Nanosensors, actuators, and displays: CNTs are used for the design of actuators,
thereby leading to greater strength. SWNTs (single-walled nanotubes) are used
for sensor applications as well as for the development of FED (field emission
displays).
• Double electron layer tunneling transistors (DELTTs): The most influencing
quantum effect in transistor-like devices is tunneling which signifies that the
particle plunges into the barrier which would not have been possible in the real
world. They are built with a planar process using conventional semiconductor
deposition. DELTT has an insulating barrier between two 2D walls. In this device
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 263

the operation is accomplished by the modulation of 2D-to-2D tunneling between

the two coupled quantum wells and doesn’t require lateral depletion or lateral
gating.
• Resonance tunneling devices (RTDs): These devices are specifically two-­terminal
devices comprising very high switching speed. RTDs for logic applications
include resonant tunneling diode and hybrid devices in which resonant tunneling
diodes are incorporated with single- or multi-FETs (RTD-FETs). Although they
are not strictly transistor devices as they don’t have a third terminal, these devices
are used in addition with transistors to increase the performance of conventional
circuits.
• Single-electron transistors (SETs): These devices are three-terminal switching
devices that transfer the electrons from source to drain. SETs include quantum
dots, small conducting materials, as basic building material.
• Spin logic devices (SLDs): The category includes a novel device, spin metal-­
oxide-­semiconductor field-effect transistor (spin MOSFET). The device pos-
sesses a MOS gate structure and contacts having half metallic ferromagnetic
(HMF) property for the source and drain. The other variations of the device
include property called spin-torque transistor which provides new devices that
include spin gain transistor (SGT) and magnetoresistive element (MRE) hybrid
hall effect (HHE) devices (Hua-Qiang et al. 2013).
• Hybrid hall effect (HHE) devices: This particular class of devices includes sin-
gle- or multiple-input wires passing over a region consisting of ferromagnetic
material. The magnitude of the current in the direction of the input wire is large,
and the magnetic field thus generated results in the magnetization of the ferro-
magnetic element, in right- or left-hand side direction. This direction absolutely
depends on the direction of the current flow.
• CNT-based field emission devices (FEDs): Field emission devices are basically
electron emitters, which emit electrons on application of high electric field.
Conventional cathode-ray tube and other electron emitters employ thermionic
emission process. In the preceding process, the electron overcomes the work func-
tion barrier by thermally heating the cathode. But the field emission is different
from the thermionic emission as in this process a very high electric field is applied
at the tip of the emitter due to which the surface potential becomes very narrow and
the electron tunnels through the barrier potential (Yeole and Padole 2015).
Graphene being a wonder material can be manufactured with the help of well-­
equipped and highly advanced environment instilled with the world’s most advanced
technology. The synthesis and application of graphene oxide nanosheets for the
removal of toxicants from water is as shown below (Khurana et al. 2018):
From the above method shown in Fig. 14.4 for the formation of the graphene
material, we define the following steps:
Step 1: Take some amount of graphite which is a composite of carbon, and add a few
ml of sulfuric acid, i.e., H2SO4. A little amount of nitric acid, i.e., HNO3, is also
added to the mixture.
264 A. Bhardwaj et al.

Slow
Graphite H2SO4 HNO3 addition
(few gms) (some ml) (a little) of KMnO4
Stirred
≤5°C
Addition of Stir for
D.W., ≤ 24 hrs
80°C at RT Thermal
Add Wash exfoliation
Graphene
50% with Graphite Oxide
HNO3, D.W. till Oxide Nano-
Heating nearly sheets
for 30 min. neutral pH

Fig. 14.4  Preparation method for graphene formation (Khurana et al. 2018)

Step 2: Afterward the slow addition of potassium permanganate, i.e., KMnO4, in the
mixture is accomplished which is followed by stirring done at a temperature less
than 5 °C, i.e., temp ≤5 °C.
Step 3: Continuously stir the mixture for 24 hours at room temperature, and then add
140 ml of distilled water at a temperature of less than 80 °C.
Step 4: Add 50% of HNO3 and subsequently heat for 30 min or half an hour.
Step 5: The mixture thus obtained is washed with D.W. till the pH returns to its
neutral value of 7. This then leads to the formation of graphite oxide.
Step 6: After the formation of the graphite oxide by performing thermal exfoliation,
graphene oxide nanosheets can be formed.
Outcome of the process yields 15 g/batch with optimization and ease.

14.3.3  Characterization of Graphene Material

The characterization of graphene material is a vital part of graphene research, and it

involves measurements that are based on various spectroscopic and microscopic
techniques. The process of characterization is required for the determination of lay-
ers and chemical purity of sample. The entire information is obtained by getting
information about the absence and presence of defects. The simplest and most effec-
tive method that is mostly used for the identification of the number of graphene
layers is optical contrast method. Characterization of the graphene material can be
described through FTIR response (Fig. 14.5), Raman shift (Fig. 14.6), and X-ray
diffraction (Fig. 14.7).
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 265

FTIR
Graphene oxide
Graphite oxide
85 Graphite
80
Trancemitance(%)

75
70
65
60
55
50
45
40
35
30
4000 3000 2000 1000 0
Wave number (Cm-1)

Fig. 14.5  FTIR response of graphene (Khurana et al. 2018)

Fig. 14.6  Raman shift vs intensity in graphene using Raman spectroscopy (Khurana et al. 2018)
266 A. Bhardwaj et al.

20000 26.57
18000
Graphite
16000
14000 Graphite oxide
12000 10.12
Intencity

Graphene oxide
10000
8000 23.58 XRD (X-ray
6000 Diffraction)
4000
2000
0
-2000
5 10 15 20 25 30 35 40 45
2q

Fig. 14.7  X-ray diffraction method (Khurana et al. 2018)

14.3.4  P
 otential Applications of Graphene (Hua-Qiang et al.
2013; Awano 2009; Lam and Liang 2011)

• Single-molecule gas detection

• Sensors/solar cell
• Room temperature distillation of ethanol for fuel and human consumption
• Graphene nanoribbons
• Graphene optical modulator
• Graphene transistors
• Integrated circuits
• Electrochromic devices
• Transparent conducting electrodes
• Ultra-capacitors

14.4  CNT and Its Growing Demand

A number of nanomaterials are being developed for structural application; out of

those nanomaterials, CNTs have been extensively researched around the world.
They have numerous remarkable properties such as exceptionally high specific
mechanical properties and physical strength with remarkable thermal properties
(Dai 2001).
14  Nanotechnology Applications and Synthesis of Graphene as Nanomaterial… 267

Fig. 14.8  Single-walled and multi-walled CNTs (Dai 2001; Saito et al. 1998)

The various types of CNTs (shown in Fig. 14.8) are:

• Single-walled carbon nanotubes (SWCNTs): CNTs exist as single-walled
(SWCNTs) or multi-walled structures (MWCNTs) which are composed of the
concentric SWCNTs. Single-walled carbon nanotubes can be shown as a sheet of
graphene rolled onto a cylindrical tube with the ends closed by the hemispheres
of fullerene. In other words they can be considered as a structure obtained by
elongating fullerenes along one axis. The strength and the stiffness of CNTs are
derived from the C-C SP3 bond, the strongest bond in nature. The result is the
strongest and the stiffest material ever known. The diameters of SWNTs range
from 0.5 to 3 nm (Dai 2001; Saito et al. 1998).
• Multi-walled carbon nanotubes (MWCNTs): They are made up of concentric
SWCNTs with different diameters. The equilibrium separation distance between
them is considered to be equal to that of the equilibrium separation distance of
graphene sheets which is 0.342  nm. The diameter of MWCNTs ranges from
approximately 2–20 nm with the upper bound poorly defined. While MWCNTs
are as stiff as SWCNTs, they are not as strong as SWCNTs due to the defects
produced during the growth of the outer cylinder.

14.5  Conclusion

Nanotechnology because of its smaller size and unique properties has immense
potential in the field of electronics, health care, and many other branches of sci-
ence and technology. Nanotech being an emerging technology has a vast variety of
futuristic applications in the day-to-day scenario of human life. It brings new
aspects of various inert materials by modifying various optical, chemical, mechan-
ical, and electronic properties at nanoscale. The degree of influence of nanotech
on the daily lifestyle of humans depends on the humans entirely. Nanotech is the
unavoidable future of humanity. Various nano-by-products such as graphene and
CNTs are analyzed; these are wonder materials that have revolutionized entirely
the electronics industry.
268 A. Bhardwaj et al.

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Chapter 15
Efficiency Enhancement of Renewable
Energy Systems Using Nanotechnology

Neelu Raina, Preeti Sharma, Parvez Singh Slathia, Deepali Bhagat,

and Atin Kumar Pathak

15.1  Introduction

In keeping with some expert evaluations, the world population will escalate to 9
billion by 2050 (Zekić et al. 2018). With the increase in population, universal energy
use is expected to escalate in the succeeding 20  years by approximately 40%
(Fig. 15.1) and almost two-fold by 2050 (Brinker and Ginger 2011). The worldwide
energy demand is expected to remain roughly around 30 TW (terawatt) by the year
2050 and 46 TW (terawatt) by the year 2100 (Sahaym and Norton 2008; Hussein
2015). The most urgent and primary technological challenge our society is encoun-
tering these days is meeting the energy needs of the world’s growing population in
a geopolitically and environmentally sustainable manner (Lewis and Nocera 2006;
Lewis 2007). Since there is a substantial worldwide competition for these limited
energy resources, it is likely to have significant social and geopolitical conse-
quences, making energy a security issue for every nation. Energy powers our life.
Thus, life requires energy. An essential approach of all life forms is to retain energy.
Therefore, subconsciously, every living being always opts for the ways and means
of least resistance to energy (Ghernaout et al. 2018).
Today, the greatest attention in the world is devoted to energy sources because
their use is irrevocable. In the present times, the fundamental energy supply for
human survival comes primarily from fossil fuels (natural gas, crude oil, and coal).
The supplies of traditional fossil fuels are running out at a very rapid pace. The
overall potential of fossil fuels accessible on earth is measured at approximately
5.500 MTOE (million tons oil equivalents) with 60% credited to coal, nearly 30%

N. Raina (*) · P. Sharma · P. S. Slathia · D. Bhagat

School of Biotechnology, Shri Mata Vaishno Devi University,
Katra, Jammu and Kashmir, India
A. K. Pathak
School of Energy Management, Faculty of Engineering, Shri Mata Vaishno Devi University,
Katra, Jammu and Kashmir, India

© Springer Nature Switzerland AG 2020 271

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_15
272 N. Raina et al.

Fig. 15.1  Worldwide energy consumption from 1990 to 2030 in quadrillion BTUs (Brinker and
Ginger 2011. Source: http://www.eia.doe.gov/oiaf/forecasting.html)

to natural gas, and approximately 10% to crude oil (Luther et al. 2015). It is stated
that the current petroleum spending is 105 times quicker than that nature has the
capacity to generate. Therefore, at this enormous speed of spending, the global fossil
fuel reserves are likely to shrink before 2050 (Hussein 2015; Satyanarayana et al.
2011). One of the most imperative concerns for countries world over is dealing with
the degrading environment combined with the rising economic baggage of feeding
expanding populations. Excessive greenhouse gas (GHG) emissions in addition to
the insufficient fossil fuel supplies are the current global energy problems resulting
from increased fossil fuel consumption.
Oil price troble, environmental worries emerging out of the upsurge in global
warming, exhausting economies, and dropping reservoir of non-renewable resources
have put alternative sources into the limelight. With the aim of enabling an overall
sustainable development, there is an urgent requirement to look for alternative,
clean energy sources which are renewable and can replace fossil fuels (Deng et al.
2016). Because of the huge energy demand and low future availability of fossil
fuels, there is a worldwide drift toward sustainability which is believed to rely
heavily on renewable energy resources. Absence of fuel requirement decreases the
release of carbon dioxide (CO2) from renewable energy sources. Renewable energy
can endow us with light, heat, and electricity devoid of environmental contamina-
tion. Solar energy, wind, tide, geothermal energy, etc. are potential renewable
resources as they do not get exhausted with continuous usage and are environmen-
tally benign (Deng et al. 2016; Bruce et al. 2008; Panwar et al. 2011).
“Energy efficiency” fuels the universal sustainable energy domain by incorporat-
ing technologies which fulfill the global energy outburst. Many technologies have
made handsome strides in notable discipline/s of sustainability era. Nanotechnology
is one of them. It is one of the topical technologies worldwide that is drawing
immense research by scientists universally. These technologies comprise discover-
ing sustainable energy sources, reducing pollution, furnishing unpolluted drinkable
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 273

water (Anjum et al. 2016), withdrawing the use of pesticides and herbicides, and
improving agricultural outputs to nourish an escalating population and variations in
world climate ensuing from global warming (Ghernaout et al. 2018). However, few
have made exponential gains in enhancing energy efficiency. Among them, promi-
nent breakthroughs are still in pipeline in the renewable energy sector that will
allow us to sustain our rising desire for energy in order to fulfill growing demands
of the ever-increasing world population.
The twenty-first century presents mankind with an immense technical challenge
which has been the expansion of technologies related to renewable energy result-
ing from some grave problems related to the utilization of energy and creation of
energy from substrates. Renewable energy is poised to play a significant part in the
global electricity mix by the year 2030. Going by the Alternative Policy Scenario,
renewable energy sector will be supplying over two-thirds of the total electricity
globally by that time (IEA 2007). Hence, nanotechnology can be viewed as a novel
candidate for clean energy applications since it holds the key for several techno-
logical developments within the energy sector especially storage and transmission.
Nanotechnology and nanoscience have the competence to offer resolution to quite
a lot of these worldwide challenges (Ghernaout et al. 2018; Poinern 2014; Hussain
et  al. 2017; Hussein 2016; Quandt and Özdoğan 2010; Santos et  al. 2015). The
implementation of nanoscience to “practical” gadget/apparatus is called “nanotech-
nology” (Kandil 2016). It has the potential to be the basis of the next industrial
development. It deals with some of the distinct mechanical, chemical, electrical, and
physical parameters that arise due to restructuring matter at the nanometer scale.
Materials can present diverse chemical, physical, and biological properties at the
“nano” phase than they do at larger dimensions (Mathew et al. 2018). As a mat-
ter of fact, every individual present on earth has come across nano-sized particles.
Every individual has been vulnerable to nanometer-ranged foreign elements. We
draw them in with every breath and consume them with every gulp.
It is the science of investigating and exploring the distinctive properties of matter
by fabricating new structures at an atomic scale of 1–100 nm. Mathematically, it is
the billionth part of a meter (10−9  m) (Alkahtani 2018) in most classifications
(Fig.  15.2). It deals with clusters of atoms of 1  nm at least in one dimension.
Nanoscience gives materials distinctive properties such as size, nature, and perfor-
mance, all due to change in their scale.

Fig. 15.2  Understanding the nanometer scale in comparison to the length of real materials (Abdin
et al. 2013; Serrano et al. 2009)
274 N. Raina et al.

15.2  O
 rigin of Nanotechnology: The Science of Small Where
Small Is Effective

Etymologically, the prefix “nano” is derived from the Greek word “nanos” implying
“dwarf” (Booth and Baker 2017). “Nano” is currently a popular feature for the
present-day science. The science of nanotechnology revolves around the basic idea
of carrying out nanoscale manipulations and creating nanoscale objects. The origin
of the concept is usually related to a discourse at the December 1959 congregation
of the American Physical Society by world renowned Nobel laureate and physicist
Richard Feynman. Feynman, during his well-known 1959 speech at California
Institute of Technology (Caltech) entitled “There’s Plenty of Room at the Bottom”
(Feynman 2012; Khan et al. 2017), asked “What would happen if we could arrange
the atoms one by one the way we want them?” (Goddard III et al. 2012; Buzea et al.
2007). His discourse described various stimulating experiments and the infinite pos-
sibilities afforded by “tininess.” Since then there have been diverse groundbreaking
expansions in this domain such as homeland security, medicine, information tech-
nology, energy, environmental science, food safety, transportation, and many others.
The term “nanotechnology” was first brought up in history in the late nineteenth
century (1867) when James Clerk Maxwell published his primary remarks about
this technology and offered potential of maneuvering distinct particles (Zekić et al.
2018; El Saliby et al. 2008). A Japanese scientist of the Tokyo University of Science,
named Norio Taniguchi, was the first to use the term “nanotechnology” at a confer-
ence in 1974 (Kandil 2016; Aviram 1988). He used the term for describing semicon-
ductor processes (for instance, ion beam milling and thin film deposition) which
displayed characteristic control over the nanometer array. He defined “nanotechnol-
ogy” as mainly consisting of the processing of separation, consolidation, and defor-
mation of materials by one atom or “one molecule”. However, in 1980, Eric Drexler
in his first paper on nanotechnology again used the term “nanotechnology” being
totally unaware of Taniguchi’s prior use of the same term (Kandil 2016).
Many “nano” words have showed up in glossary, for instance, nanogram, nanome-
ter, nanorobotics, nanoscience, nanosecond, nanostructure, nanotechnology, nano-
tube, nanowires, and many more. Some more uncommon words consist of
nanoantenna, nanoarrays, nanocavity, nanocrystal, nanoelectronics, nanoencapsula-
tion, nanofibers, nanolithography, nanomagnet, nanoprecursor, nanopatterning, nano-
porous, nanoseparation, nanovalve, nanosequencing, nanoscaffolds, etc. Numerous
words that are not broadly perceived are used in some esteemed publications.

15.3  R
 ise of Nanomaterials and Its Applications in Diverse
Areas

The world of nanotechnology is ever-evolving. It is showing enormous possibilities

in countless fields of science and technology by functioning at an elementary level.
It is creating a lot of vigilance nowadays. It is not just a catchphrase but the future
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 275

Fig. 15.3  Classification of nanomaterials (Raghav and Dinesh 2016)

of technology since it impacts every sector. It is the combined study of engineering

and chemistry fields and is classified as the arrangement, assembly, and application
of resources and appliances whose dimensions have been engineered at the
nanoscale. Widely, the word “nano” is employed as prefix to illustrate matter, struc-
tures, or processes with characteristics coming from nano-sized structures. On the
basis of overall shape, these materials can be classified as 0D (quantum dots, nano-
clusters, and nanoparticles), 1D (nanotubes and nanorods), 2D (nano-sized thin
films), or 3D (nanomaterials) (Khan et al. 2017; Tiwari et al. 2012) (Fig. 15.3).
Nanoscience creates an enormous prospect not only within the intellectual society
but also among sponsors, administration, and industry due to its unique ability to
engineer elements at an atomic scale. It has created novel equipment/devices with
potential relevance in an extensive number of disciplines. Nanoscience and nanotech-
nology facilitate vast array of technologies that attain abundant and low-cost alterna-
tive energy production, efficient energy use, transmission, and storage. This section
demystifies the topic for anybody engrossed on how nano-sized molecules and the
nanotechnology involved affects our everyday lives. The relevance of nanomaterials
is rising in diverse zones (Fig. 15.4), together with public health, agriculture, cloth-
ing, medicine, cosmetics, and food owing to their exceptional capability to boost
bioavailability and solubility and to safeguard bioactive compounds while they are
being prepared and then stored for use (Bajpai et al. 2018). Nanoparticles as coat-
ing materials have been the center of attraction over the previous few decades with
their exceptional relevance in different spheres (Khezri et  al. 2018). The study of
these nanoparticle materials is an important element of nanoscience. It is regarded
worldwide as the key technology for innovations and technological advancement in
nearly all domains of economy (Table 15.1). Some of the improvements using sci-
entific conception regarding the benefits of controlling materials at nanoscale have
resulted into commercially viable products and technologies based on nanomaterials
as given below:
1. Influence of nanotechnology on transportation and sports equipment: Increase in
the toughness of lightweight sporting instruments/gadgets, extending from base-
ball bats, tennis and badminton racquets, hockey sticks, racing bicycles, golf
balls/clubs, skis, fly fishing rods and archery arrows, etc. are some of the sporting
276 N. Raina et al.

Fig. 15.4  Applications of nanotechnology

equipment, whose performance and durability are being enhanced with the
­assistance of nanotechnology (Nano werk 2013). In automobile sector, nanop-
olymers are used in paint coatings, lightweight body parts, self-cleaning nano-
films, scratch- and abrasion-resistant coatings, tires, mirrors and glasses,
nanofilters for air cleaning, exhaust emission reduction, cooling systems, and
many more. In aerospace, it is being applied to engines (improves heat transfer,
lubrication) and tires (reduced friction, durability). In marine transport, nano-
structured coatings are scratch resistant, and body parts made of nanoclay are
light and tough (Mathew et  al. 2018). Nanoscale sensors and instrument may
possibly provide cost-effective constant monitoring of the structural integrity
and functioning of bridges, tunnels, rails, parking structures, and pavements in
due course (National Nanotechnology Initiative 2012).
2. Food safety and as cleaning agent: Nanotechnology has come to light as a scientific
development tool to transform the agrifood sector, with the potential to improve
global food production, in addition to the nutritional use, quality, and safety of
food (Peters et  al. 2016; King et  al. 2018). Nanomaterials have been used to
eradicate contaminants (Sun et al. 2013; Zhu et al. 2012), as antimicrobials (Kim
et al. 2007; Morones et al. 2005) and as antioxidants (Deligiannakis et al. 2012).
Besides being used in sensors for detection of pesticides, chemicals, heavy met-
als, foodborne pathogens and toxins, preservation, and food packaging (Gestal
and Zurita 2015; De Francisco and GarcÍA-Estepa 2018), nanotechnology is also
used in the removal of pesticides (Yu et al. 2017; Yu and Yang 2017; Krishna
et  al. 2018). Food industry includes food nano-preservation (encapsulation,
humidity treatment), food nano-functionality (enhancement of physical qualities
and nutritive value), and food nano-packaging (intelligent sensing/active antimi-
crobial/bio-based edible packaging) (Bajpai et al. 2018). Nanomaterials are used
as cleaning agents in industrial solvents to remove groundwater c­ ontamination
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 277

Table 15.1  Nanomaterial particles commonly in use as coating materials

Feature Nanomaterials commonly in use Nanoparticle supplier/s
Antimicrobial activity/ Fe3O4, NO, CuO, TiO2, ZnO Creative Diagnostics
therapy
Polymeric systems as gas Polyimide (PI) nanotubes (silica, Southern Clay
barrier (decrease in gas clay)
permeability)
Corrosion control Li2TiO3, Al2O3,Cr2O3, Nanoclays Altairnano
(hydrotalcite, montmorillonite, etc.),
boehmite nanofillers
Electrical conductivity, SnO2, indium tin oxide (ITO), iron, Ishihara (ISK)
static charge dissipation antimony tin oxide (ATO), cobalt
Fire retardant Carbon nanotubes, nanoclays Nanocor
IR absorption/reflection C, ITO, Pt, ATO, SnO2 Nanophase
Magnetic Fe2O3,Fe3O4 TurboBeads
Mechanical, scratch TiO2, Al2O3, ZnO, SiO2, ZrO2 Nissan Chemical
resistance
Photocatalytic/self-cleaning Fe3O4,TiO2/SiO2, ZnO Nanoscale
technology
UV stability Montmorillonite, SiO2, TiO2, ZnO, Antaria
BaSO4, CeO2
Nanotubes Carbon, silica, cellulose Adnano technologies,
Cheap Tubes, EMFUTUR
Technologies
Diesel additive to reduce Cerium oxide Energenics
fuel consumption
Targeted delivery of drugs Gold nanoparticles CytImmune
to tumors
Nanoparticles to treat Iron nanoparticles SiREM
groundwater pollutants
Fabric treatments Silver nanoparticles NanoHorizons

(Yunus et  al. 2012). Inexpensive, portable water purification systems using
nanoscience can provide universal access to safe water (Pulizzi and Sun 2018;
Jassby et  al. 2018). Commonly used materials using nanotechnology in water
purification systems have been documented (Suthar and Gao 2017). Nano-based
films that can be applied to countertops or windows makes it much easier to keep
those surfaces clean. Decontamination of industrial sites through environmental
remediation by removal of numerous contaminants is another field where nano-
technology is working wonders (Guerra et al. 2018).
3 . Medicine and cosmetics: Glucose-sensing tattoos, contact lenses, and skin
patches examine diabetics’ blood sugar levels and cautions when its level reaches
upper or lower extreme (Aslan et al. 2005). In drug delivery systems, nanopar-
ticles are effective due to site-specific targeting, high drug loading, side effect
reduction, controlled and sustained drug release, manipulation of drug particle
size, and surface characteristics (Simonazzi et  al. 2018). In healthcare sector-
inexpensive flexible and durable “electronic skin” sensors are used in robotic
278 N. Raina et al.

systems and prosthetic limbs. Also nanotechnology helps in the field of visual
realities, professional sports and entertainment sector to detect changes in pres-
sure, humidity, and temperature thus enhancing experience (Lu et al. 2018). In
wound dressings, nanotechnology-based drug delivery systems improve wound
healing (Kalashnikova et al. 2015). In bandages, nanopolymers aid in increasing
the surface area available to kill the germs, thus increasing the ability of the
wound to absorb drug more effectively. New nanoscience-based prevention,
detection, and treatment technologies could substantially reduce death and suf-
fering from cancer and other deadly illnesses (National Cancer Institite 2017).
Nanomedicine covers a range of uses, including nanomaterials, nanoelectronic
biosensors, and molecular nanotechnology (Tan et al. 2016). Sunscreens provide
protection from UVA and UVB rays without leaving a white residue on the skin
(Lohani et al. 2014). An article “Cosmeceuticals market to 2018” projected that
the worldwide cosmeceutical market will get to $42.4 billion by 2018 (Lohani
et al. 2014; GBI Research 2013). Cosmetic products that have been successfully
used are moisturizer, anti-wrinkle and antiaging creams, and face mask (Khezri
et al. 2018). A large number of patents have been filed in this domain, and the
income generated out of these market products has been bountiful.
4. In fabric protection, safeguarding wood, paints, and varnishes: Nanoparticles
act as protective shield in fabrics against microorganisms and flammability and
robustness against ultraviolet radiation (Rivero et al. 2015). Clothing that pro-
tects against toxins and pathogens (Bajpai et  al. 2018; Rivero et  al. 2015;
Guardian 2014, February 14), seaweed capped zinc oxide nanoparticles having
antibacterial and UV protection have been made having antibacterial and UV
protection have been made (Pandimurugan and Thambidurai 2017).
Nanotechnology-based protective coatings on wood have antimicrobial (Teng
et al. 2018), fire-resistant, and chemical-resistant properties saving time, effort,
and money. Paints and varnishes avert corrosion and microbial expansion as well
as provide insulation (AZo Nano 2017).
5 . Areas where nanotechnology has left an indelible mark: High-memory density
devices are capable of storing the entire Library of Congress collection on a
device of the size of a sugar cube. It improves banknote security with
­polymer-­based ferroelectric memory (Nano Werk 2013). Nanomaterials enhance
definite mechanical, physical, and chemical properties in addition to serving as
carriers for some active substances, for instance, antioxidants and antimicrobial
agents (Amirabad et al. 2018).
6 . Electronics and energy sector: It aids in making integrated circuits with features
that can be measured on nanometer (nm) scale, thus allowing companies to man-
ufacture computer chips containing billions of transistors that are smaller,
cheaper, and faster therefore consuming less power. Currently, flash memory
manufacturers use nanolithographics to assemble memory chips as small as
20  nm (UnderstandingNano 2013). Nanotechnology develops clean, inexpen-
sive, renewable power through energy creation, storage, and transmission tech-
nologies (Eureka 2018). Energy-efficient, low-emission systems help in reducing
energy emissions (Abdin et al. 2018). Nanomaterials as catalyst in cost-effective
chemical manufacturing save energy and minimize waste products (Boysen and
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 279

Muir 2011). Using nanoparticles in soap makes it work better while producing
environmentally less harmful by-products. It is moreover being related to oil and
gas withdrawal using nanotechnology-­empowered gas lift valves in seaward activ-
ities or to the application of nanoparticles to sense infinitesimal down-well oil
pipeline breaks (National Nanotechnology Initiative 2012). Applied nanotech-
nology enhances the functionality of traditional construction materials, reduces
material carbon emissions, and increases infrastructure durability in addition to
numerous other benefits bestowed by nanoscience technology (Oke et al. 2017).

15.4  Nanotechnology: The Future of Renewable Energy

Ranging from solar power to supercapacitors, nanotechnology has the capability to

help resolve a large number of vital energy hurdles. This chapter focuses only on the
efficiency enhancement of renewable energy systems using nanotechnology.

15.4.1  B
 enefits and Applications of Nanotechnology
in the Renewable Energy Sector

Energy has become a major challenge in the present times since universal energy
requirement is rising constantly. Energy is possibly influenced in a countless number
of means by the spur of nanotechnology which thus has the chance to contribute in
several ways to the heterogeneous array of hurdles in this sphere (Ramsden 2018).
Replacing leading non-renewable energy sources by renewable forms of energy
depends on the expansion of competent technologies. In consistent with prediction by
the International Energy Agency (IEA), it will escalate from currently approximately
12,000 MTOE up to more than 18,000 MTOE till 2030 (Luther et al. 2015). Going by
the current speed, the yearly consumption of energy will be twice of the present
demand (Ampelli et al. 2014) by the year 2050 (Pandey 2018). It has thus established
as the mainstream and cost-competitive technology in the renewable energy arena.
Renewable energy sources, for instance, solar power, hydropower, bioenergy, and
geothermal power/heat, have not remained untouched by the spur of nanotechnology
boom. Especially, nanomaterials are progressively playing a dynamic role either by
enhancing the efficiency of the energy storage system and conversion route or by
upgrading the device design and performance (Chen et al. 2015).

15.4.2  Solar Energy

Energy from sun is a paramount renewable energy source. Since the sun is a change-
able energy source which produces energy in a diffused form, therefore organizing
incident solar radiations is not an easy task. Given that the solar energy is completely
280 N. Raina et al.

natural, it is believed to be a clean energy source (Chen 2015). Its creation is quickly
becoming an essential source of renewable energy, being evolved as an alternative
to conventional supply of energy. Energy sector especially solar energy storage and
generation have therefore been significantly benefitted. Decreased manufacturing
costs and improved material effectiveness are precisely two of the possible eco-
nomic advantages that nanotechnology brings to these sectors (Raghav and Dinesh
2016). The most commonly used semiconductor material in generating energy
using solar energy is silicon, and some other semiconductor materials are the basic
substances of solar energy. At present, roughly 90% of the globally installed solar
cells are made using silicon. There are four generations of PV cells which include
(a) first-generation crystalline silicon PV (b) second-generation called thin-film PV,
(c) third-generation – these are emerging PV, and (d) fourth generation – called
high-efficiency PV (single and multi-junction concentrator). Third-generation PV
devices are based upon nanocomposites, i.e., nanostructured semiconductors,
organic-­inorganic hybrid assemblage, as well as molecular assemblies. In addition
to these, there is the field of solar thermal energy where the focus is on solar thermal
technologies for electricity generation (Ralph Seitz et  al. 2013). Solar thermal
energy uses silicon as nanoparticle. Silicon is used in constitution with heavy metal
alloys. This segment takes on the application of nanotechnology in the energy-asso-
ciated processes that deals with the use of radiations from the sun as the source of
energy. It can be proficiently used for many practical purposes such as solar cells,
solar power plants, solar collectors, seawater desalination, etc. (Hussein 2015).
Dye-­sensitized solar cells, fuel cells, and solar photovoltaic cells are some other
devices under the broad spectrum of systems using solar energy.

15.4.3  Solar Photovoltaic Cells

In this contemporary period of global awareness for sustainable energy develop-

ment, countries are searching for viable solutions for energy crisis. Electricity
formed from photovoltaic (PV) cells is one such example. These cells allow us to
exploit the enormous quantity of energy in the form of radiations that the sun sends
toward our planet earth (Wong et al. 2014). A solar photovoltaic cell is a device that
converts photons from solar radiations by electrons into electricity (Lewis 2007).
By solar photovoltaic (PV) electricity, we mean electricity created through the pho-
tovoltaic route, i.e., by the straight conversion of photons from solar radiation into
electrical current using semiconductor tools (solar cells). It is a combined physical
and chemical phenomenon. However, solar cells are termed photovoltaic whether
the supply of light is coming from the sun or an artificial source. The surface of
photovoltaics consists of an oxide layer which is conducting and a catalytic plati-
num layer that straightaway converts light from the sun into electricity. Although,
solar energy is abundantly available and is free of cost. Still, just near about 0.04%
of the fuel energy out of world’s total primary energy supply is made available by
the photovoltaic technology (IEA 2007). Photocatalysis studies are gaining consid-
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 281

erable attention among researchers these days due to the prospects of higher energy
savings and less environmental pollution. Near about 40 million tons of carbon
dioxide emissions may be saved per  annum, if a distributed solar grid is able to
fulfill 1% electricity requirement of the world (Hussein 2015). Also, solar photovol-
taic is anticipated to have a lesser LCOE (levelized cost of electricity) compared to
coal or natural gas-fired generation world over by 2020 (Bleich and Guimaraes
2016). Among other elements such as silicon or additional material systems like
selenium/copper/indium, further development is required in alternative cell types,
for instance, polymer solar cells, thin-layer solar cells, or dye solar cells.
There are a number of applications making use of energy from sun; photovoltaic
(PV) application is the most common one among them. PV market has stretched out
considerably since the 1990s. The first-generation PV devices are based upon single
or multiple, crystalline p-n junction silicon cells. Presently, PV market is founded
on crystalline silicon wafer-based thick solar cells measuring ~150–300 nm. These
cells are categorized as the first generation of photovoltaic cells which encompass
greater than 86% of the world solar cell market. Current leading market technology,
which employs monocrystalline or multicrystalline silicon wafers, scarcely leads to
cost decrease through technological development and bulk production. Introducing
a thin film layer of 1–2 nm size made of a semiconductor material leads to the intro-
duction of second generation of photovoltaic substances. a-Si has a comparatively
higher absorption rate in comparison to crystal silicon making it a viable option for
thin film technology in P-V cells. Second generation of solar cells constitutes thin
film-based solar cells. The high cost of the conventional photovoltaic cells is the
main elementary obstacle to their widespread use. Inkjet printing technology incor-
porated with devices integrated with particles (e.g., dye-sensitized solar cells or
Grätzel cells) present possibly much lower manufacturing price (Bella et al. 2015;
Ramsden 2018).
Nanocoatings favor their relevance in PV applications. Multiple reflections thus
attained lead to an amplification of the absorption path in turn leading to reduced
recombination loss due to decreased absorber layer width. Thus, the energy band-
gap of solar cells can be modified. Nanocoatings have valuable self-cleaning fea-
tures too (Ralph Seitz et  al. 2013; Kadırgan 2006). Gold nanoparticles boost the
efficiency of PV cells. Fullerenes are widely used as electron acceptors in organic
PVs (third generation). Novel fullerene acceptors (e.g., C60 including various
organic acceptor materials) are projected to extend to elevated efficiencies.
Nanoparticles (e.g., metal particles, metal oxide particles, or carbon-based nano-
structures) if added to base fluids like propylene glycol, water, ethylene glycol, etc.
augment the thermal conductivity. Crystalline silicon is a brilliant conductor, but it
is expensive. The efficiency of energy conversion of roughly 25–30% in a photovol-
taic cell is supplied by the crystalline silicon. Alternative conducting materials like
titanium oxide are affordable to manufacture. However, in comparison to crystalline
silicon, they have even lower conversion efficiency. Nanotechnology can be of
immense use in manufacturing complex nanostructured lenses and mirrors to aug-
ment collection of solar energy. Aerogels containing nanopores are helpful as ther-
mally insulating and transparent substances to be used as cover materials for solar
282 N. Raina et al.

collectors. The nanocomposite technology can be seen in numerous energy sector

applications and is vital to both energy harvesting and storage market. In silicon-­
based solar cells, nanocomposites contribute in capturing energy generally in the
form of nanowires. Predominantly, nanocomposites can be found in photovoltaic
technology (inorganic polymer PV cells or as polymer gel electrolyte in dye-­
sensitized solar cells (DSSC); nanostructured solar cells or quantum dot-sensitized
solar cells (QDSSC)) (Schueler 2011; Hashim 2011; Kamat 2007). Nanocomposites
can also be sited in higher solar transmittance layers on collector glazing (e.g.,
Ti-Si-O films) and antireflection casing. In solar energy making and transformation,
nanocomposites are applied to overcome interaction of electrons and chemicals
(catalyst engineering), limits of single materials in solar spectrum (bandgap engi-
neering), and passage of electrons in the material (defect engineering) as well as to
trim down prices. These features result in better charge separation and as a result in
improved photovoltaic efficiency (Hashim 2011; Kamat 2007).

15.5  Nanofluids for Solar Energy Applications

PV technology is a combination of conducting polymers or mesoporous metal

oxides in addition to an enlarged surface area to augment internal reflections using
nanoparticles and therefore makes a solo multi-spectrum layer. One of the economi-
cal techniques is to substitute the working fluid with a liquid which includes
nanometer-­sized molecules called nanofluid. A nanofluid is a colloidal mixture of
nanometer-sized substances such as nanofibers, nanotubes, nanoparticles, nanorods,
nanowires, or nanosheets in a fluidic system. The base material is a liquid phase,
whereas the solid phase contains the nanomaterial. They are used to enhance the
heat transfer coefficients, thermal conductivity, viscosity, and diffusivity resulted
due to convection. The function of nanotechnology in focusing solar energy like
parabolic dish, solar tower, or parabolic trough is because of advanced and novel
heat transfer fluids for absorber tubes, e.g., nanocoatings for tubes especially antire-
flective coatings for collectors (Ralph Seitz et al. 2013). The total market of emerg-
ing PV technology involving organic dye cells, CIGS (copper indium gallium
selenide) solar cells, and PV cells is expected to jump by 2021 to 7.7 billion US$
illustrating that nanotechnology-based PV market is powerfully associated with the
upcoming PV technologies (Ralph Seitz et al. 2013). Better thermal conductivity
was reported by Choi in 1995 (Choi et  al. 1995) by using nanofluids on adding
nanometer-sized particles to a fluid. According to literature study, the improved ther-
mal conductivity of nanofluids is the chief basis of efficiency rise in solar systems
(Raghav and Dinesh 2016). Nanometer-sized electrodes enhance electrical conduc-
tivity by lithium inclusion and augment the elevated rate potential. It assists in
increasing lithium-ion battery’s capacity, energy and power density, life cycle, and
protection. It decreases the specific current density of active elements. It also reduces
the volumetric variations and lattice stress and permits high rate of discharge. In case
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 283

of anode, nanocomposite materials (e.g., Si- or Sn-based nanomaterials dispersed in

a carbon-based matrix) as well as nanostructures (3D porous matter, nanowires,
nanotubes, and nanorods) are currently looked into. As regards cathode, nanostruc-
tures are explored frequently as polyanion-based complexes or as transition metal
oxides. Nanomaterial cathode electrodes present superior energy storage capacity
along with discharge kinetics, superior cyclic stabilities due to an extensive surface
area, small distances for mass and charge dispersal, and added liberty for volume
alteration along with lithium intercalation and release (Ralph Seitz et al. 2013).

15.5.1  Solar Cells

In addition to the employment of electrodes for energy storage, electrodes are also
exercised in photovoltaic sector in the solar energy quarter. In this area, indium tin
oxide (ITO) commonly used as a transparent electrode can be replaced by several
nanoscale materials like metal oxide nanoparticles, CNT, graphene, etc. In solar
cells, flat screens, etc., ITO has an additional benefit to be employed as a transparent
as well as conductive substance. However, indium is considered as a significant raw
material in the solar cell market. Thus, the technologically sound industries are
strongly researching for materials in order to substitute indium tin oxide (Ralph
Seitz et al. 2013). Dye-sensitized solar cells (DSSCs) chiefly put to use nanocoat-
ings, for instance, over transparent (carbon nanotubes/graphene) electrodes
(McWilliams 2010). Ductility, wear and tear resistance, and defense against corro-
sion and erosion are some of the properties bestowed by thermal spray coatings
such as chrome oxide, alumina/titania, tungsten carbide, yttria-stabilized zirconia,
and nanoceramics (McWilliams 2010). In addition, titanium nanonets containing
Li-ion batteries are coated with SiO2 or silicon particles in order to prevent reaction
of TiVO2 with Ti+ (Zhou et al. 2011). Ultra-black nanostructured, surface coatings
utilized in the solar thermal sector are metal containing nano-sized oxide materials.
Solar PV cells are nowadays coated with antireflection surface layer and are known
to decrease the surface reflection drastically from 40% to 1% (Ralph Seitz et  al.
2013; McWilliams 2010). Metal oxides in solar cells are nowadays substituted by
ITO nanoparticles in the medium. Nanocarbon materials (third generation) like car-
bon nanotubes and graphene are used to enhance the counter electrodes in dye-­
sensitized solar cells by substituting platinum. The effectiveness of photovoltaic
cells can be enhanced drastically by employing an intermediary band in between the
conduction band and the valence band within the semiconductor. In this manner,
energy levels which don’t get placed in the energy bandgap can still be absorbed and
converted into current. To achieve desired properties, the energy levels/bandgap of
the semiconductor may be reframed by constructing quantum dots to be used in
solar cells. Hybrid solar cells (organic-inorganic cell structures) use ZnO nanostruc-
tures as electron acceptors. Bad light absorption in thin-film solar cell absorption
layers can be resolved by plasmonic metal nanoparticles that use light-scattering
284 N. Raina et al.

and absorption-enhancing layer. Solar cells having nanoparticles made of gold

embedded in the plasmonic layer are projected to boost absorption and therefore the
efficiency of the cell.
Nanostructures, such as quantum dots, optimally regulate bandgaps of semicon-
ductors to the incident light radiation or emit numerous charge carriers per photon,
thus enhancing conversion efficiency. Also this results in better light entrapment, for
instance, by averting reflection loss at the front cover from nanostructured anti-­
reflection layers or by up- or down-conversion of light wave lengths via special
nanostructures, which could facilitate better exploitation of the light spectrum.
The phenomenon of solar thermal (conversion of solar energy into heat such as
steam and power generation) is commonly used to provide decentralized heat sup-
ply in buildings through roof-mounted solar collectors by using parabolic mirrors.
The impact of nanotechnology is evident in spheres such as anti-reflection coatings
for enhanced energy produce, optimized phase-change stores, and heat exchangers/
carbide layers of collectors, which expand energy incorporation plus thermal and
mechanical stability.
Contrary to the silicon wafer technology, thin-layer solar cells provide possibil-
ity for savings in the solar cell manufacturing because of material savings, low-­
temperature procedures, integrated cell insulation, and an elevated mechanization
level in series production. Besides silicon, combination of elements such as copper/
indium/gallium/sulfur/selenium (CIGS cells) as well as III–V semiconductors (e.g.,
gallium arsenide) is employed, which allow productivity of up to about 20% (Luther
et al. 2015).
Different solar cell types can be summarized as below.

15.5.2  D
 ye-Sensitized Solar Cells (DSSC/DSC/DYSC/Grätzel
Cell)

An electron transfer sensitizer (photo-sensitized electrode) is employed to take up

the visible light and introduce charge carriers in the juncture between semiconduc-
tor and an electrolyte containing a wide and stable band width substrate. In the year
1991, this idea led to the emergence of a dye-sensitized solar cell (DSSC) (Hashim
2011). Dye-sensitized cells employ a sensitized semiconductor element connecting
another strongly absorbing material (dye) and multi-junction solar cells to enhance
the absorption of solar irradiation by using a layer of thin film semiconductors having
bandgaps of variable energies. Thus, this combines a dye sensitizer (light absorb-
ing matter) by using wide bandgap semiconductor (made up of a nanocrystalline
structure) as the photo anode enabling the process of optical absorption and charge
separation (Fig. 15.5). Semiconductor films such as TiO2, ZnO, SnO2, CdSe, etc.
are formed of an interconnected range of small crystals (amounting to a couple of
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 285

Conducting
Glass/FTO TiO2 Dye Electrolyte Counter electrode

e- injection

S+/S* (Excited state)

CB

light
Maximum e-
Voltage
E (V)

e-
I- I3-
Redox
e- potential

S+/S (Ground state)

e- e-

Fig. 15.5  Diagrammatic representation and working of a nanocrystalline dye-sensitized solar cell.
(Sharma et al. 2018)

nanometers) in order to permit the process of electronic conduction. Compared to

an unstructured electrode, this structure provides an enhanced surface area (nearly
more than thousand times) accessible for dye chemisorption. An increase of 103–104
times in photocurrent and a total power conversion efficiency of 10.4% has been
recorded when the sunlight passes using a single crystal into a nanocrystalline elec-
trode for DSSC (Green et al. 2009).

15.5.3  Dye-Sensitized Nanocrystalline Solar Cells

The transport of charge carrier is completely separated from the absorption material
in these types of cells. Fluorine-doped tin oxide (FTO) and tin-doped iron oxide
(ITO) glass are some of the conducting transparent substrates. To these, a mesopo-
rous nanocrystalline TiO2 film with a monolayer of the charge transfer dye attached
to its surface is pasted. A redox electrolyte is kept in contact to the film. Using pho-
toexcitation, electrons in the TiO2 conduction band can be introduced from the dye
and carried onto the outer circuit in order to push the load and create electricity
(Chen et  al. 2012). This increases the percentage of energy from the sun
(Hussein 2015).
286 N. Raina et al.

15.5.4  Organic Polymer-Derived PV Solar Cell (OPV)

Polymer solar cells make use of organic semiconductors intended for energy trans-
formation. In this type of solar cell, excitons are split into free electrons and hole
pair by the effective electric field. This field is formed throughout the expanse of
heterojunction called as the “acceptor” and “donor” molecules. Ascending require-
ments for low-cost renewable energy sources have enabled OPV solar cells to be
utilized as a viable option for the production of energy from light at a minimal cost
(Hussein 2015; Hussein and Reviews 2015). They can be used to engineer cost-­
effective, lightweight, large-area, and adaptable solar cells using economical paint-
ing. Hybrid polymer-type PV devices comprising of a conjugated polymer (p-type
semiconductor) and an inorganic semiconductor (n-type) have captivated interest
as potential option for future PV devices, as they join the distinctive properties of
inorganic semiconductors such as high electron mobility and stability with fine
film-­forming qualities pertaining to conjugated polymers.

15.5.5  Hot Carrier Solar Cells

A highly energetic photon is used to knock a free d-electron higher in the conduc-
tion band, thereby raising the electronic temperature to a reasonably high scale, i.e.,
~3000  K.  However, within some hundred femtoseconds, the hot electron reverts
back to the base of the conduction band, in the process passing on the heat energy
to the lattice (Hussein 2015).
Nanoparticles present the following advantages to solar power plants (Hussein
2015; Taylor et al. 2011):
1. Small-sized nanoparticles make their way easily using pumps and plumbing of
the particles without harmful effects.
2. Nanofluids have the capacity to absorb energy straightway which is greater than
the energy lost in the intermediate steps.
3. Nanofluids are capable of being optically selective, that is, low emittance in the
infrared band and high absorption within the solar scale.
4. An added, even temperature of the receiver may be attained within the solar
collector.
5. Better transfer of heat using elevated thermal conductivity and convection can
increase functioning of the receiver.
6. Nanoparticle dimensions may be enhanced to the required function for improv-
ing the absorption competence.
Nanomaterials significantly modify the characteristic features of the materials,
i.e., biological, physical, and chemical properties. In comparison to macroscopic
substances, nanocluster electrons can only assume specific “quantisized” states of
energy affected by the quantity of atoms interacting in the process. Metal nanoclu-
sters (e.g., Cu, Ni, Fe, etc.) comprised of a minute quantity of atoms are composed
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 287

Fig. 15.6  Evolution of the solar cells (Raghav and Dinesh 2016)

either of multiple or a single element and measure characteristically fewer than

2 nm. They exhibit attractive optical, chemical, and electronic properties in com-
parison to their larger counterparts. The result is a distinctive fluorescence which
differs strongly with the cluster size. A 2-nm-sized cadmium telluride particle fluo-
resces in green light and in red when an element is of 5 nm size. These quantum dots
chiefly let a major improvement in the quantum yield and the conversion efficiency
of solar cells (Luther et al. 2015).
Some of the benefits of 1D nanomaterials for enhancing solar cell efficiencies are
summarized as follows (Yu and Chen 2009):
1 . Charge transport follows a direct path.
2. The shape of the nanoparticles provides large surface area for maximum light
yield.
3. In 1D nanomaterials, the movement of electrons is typically quite greater than
the semiconductor films.
The evolutionary path of solar cells as revolutionized by nanotechnology is pre-
sented in Fig. 15.6.

15.6  Hydrogen Energy

15.6.1  Fuel Cells

Fuel cells transform chemical energy with a high effectiveness straightaway into
electric current. In addition to pure hydrogen, natural gas, methanol, benzene, or
biogas may be utilized to run fuel cells. Hydrogen is not as such an energy source
but the carrier of atomic energy. Hydrogen fuel cell technologies transpired as the
288 N. Raina et al.

Fig. 15.7  Hydrogen fuel cell. (Hussein 2015; Danilov et al. 2008)

top promising solutions to sustainable energy and environment (“Bud” Peterson

et al. 2010). Nanocoatings as titanium-coated nanotubes are used in hydrogen tanks
(Ralph Seitz et al. 2013).
In a typical fuel cell, the union of hydrogen (Fig. 15.7) and oxygen molecules
produces water. In this process, heat and electricity are released as by-products.
This process takes place in an environment-friendly manner, without the release of
any detrimental carbon dioxide (CO2) emissions. However, fuel cells can also be
produced using methane and methanol. Operability concerns, high cost, and
­resilience issues are some of the issues if using fuel cells in spite of their enormous
utility. Nanotechnology comes to the rescue of fuel cells by resolving some of their
limitations. Fuel cells, catalysts, and electrode membranes may be constructed by
incorporating nanomaterials. One of the most proficient applications of nanotech-
nology in the hydrogen energy sector is concerned to the economical storage of
hydrogen fuel since storing large volumes of hydrogen fuel is either highly priced
or too immense. Nanoblades have been discovered by scientists to be having the
capacity of possibly holding huge volumes of hydrogen fuel (G. 2008). In addition
to this, it has the possibility of being put inside a nanomaterial, for instance, carbon
nanofibers and carbon nanotubes (CNTs) (Matteo et al. 2012; Ye et al. 1999; Züttel
et al. 2002; Nikitin et al. 2008; Gao et al. 2001; Danilov et al. 2008). These days,
carbon nanotube fuel cells are being used to collect hydrogen gas which is consid-
ered to be environmentally safe. Since hydrogen gas has the best energy-to-weight
ratio in comparison to any other fuel, therefore hydrogen energy is still being used
widely in the space vehicles (Hussein 2015). Nanocomposite technology has a high
potential to be used in devices for carbon dioxide conversion to hydrocarbon fuels
like methanol (Kamat 2007), and nanocomposite sheets make available fresh type
of merged hybrid device (Ducharme 2009; Pushparaj et al. 2007).
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 289

Proton exchange in membrane fuel cells has been enhanced using TiO2/SnO2
nanoparticles in the composite nafion membranes. This has augmented the ability of
the modified fuel cell in comparison to conventional fuel cell with a nafion mem-
brane predominantly at elevated temperatures (Abbaraju et  al. 2008). Using
­photocatalysis, nanotechnology could be used as a probable tool for the economic
production of hydrogen gas using solar energy in an environmentally friendly,
clean, and economical manner (Jang et al. 2008). In fuel cells, carbon nanotubes
(CNTs) due to their large surface area and thermal conductivity can be inducted into
their components and in electro catalyst support system to upgrade its functioning
and cut down its cost (Hussein 2015; Zhang et al. 2011).

15.6.2  Diesel Engine

In an internal combustion engine, clean water vapor is released utilizing hydrogen

as the fuel. Nanofluids possess an important property of having a high capacity to
absorb radiations. Therefore, nanofluids come handy in the way that they can be
used ably in decreasing the release of radiations in the combustion process
(Hussein 2015).

15.6.3  Biomass/Bioenergy

Biomass consists of all organic materials derived from plants. Biomass is currently
projected to supply about 10–14% of the total energy reservoir present in the world
(Hendriks and Zeeman 2009). With the stake of roughly 10% universally in the
energy supply sector, biomass is presently a major vital renewable energy resource.
On one hand, biomass assists in the production of heat and energy and on the other
hand the supply of fuels. However, the segment of biofuels in the world fuel market
is only approximately 1%, with bioethanol representing the most significant one.
Nanotechnology might play an active role in the optimization of efficient biomass
utilization by developing catalysts and new conversion protocols in addition to the
nano-optimized development of bioresources, e.g., economical use of fertilizers and
pesticides using nanoencapsulation and nanosensors (Luther et al. 2015).

15.6.4  Bio-oil

Nano-sized cerium oxide molecules as a supplement in biodiesel fuel significantly

lower the release of NOx constituents and several hydrocarbon compounds into the
environment (Sajith et  al. 2010). SWCNTs, i.e., single-walled carbon nanotubes
having iron oxide nanoparticles imbedded in them, led to the rise of magnetic
290 N. Raina et al.

single-­walled carbon nanotubes. This established the route for better efficacy in
carbon nanotube-based enzyme bioreactors, thus decreasing economic expenses in
industry-related enzyme systems and enhanced productivity of biofuel production
(Goh et al. 2012).

15.6.5  Bio-diesel

The nanomaterial oxide-based magnetic catalysts such as strontium oxide, calcium

oxide, titanium oxide, magnesium oxide, etc. are being applied for the preparation
of biodiesel fuel. This gives an excellent possibility of the fuel being more economi-
cal (due to easy separation strength and reuse) by incorporating nanocatalysts hav-
ing high efficiency, durability, and stability. Therefore, this paves the way for biofuel
sector to achieve higher quality and optimal product yield for further development
and application purposes (Hu et al. 2011). Mesoporous and carbon-based nanocata-
lysts like carbon nanofibers, biochar, carbon nanotubes, and graphene oxide have
excellent potential for biodiesel production using an extensive range of feedstocks,
specially nonfood substrates (Nizami and Rehan 2018).

15.6.6  Wind Energy

Wind energy uses wind as the source of energy. A wind turbine transforms kinetic
energy of wind into electrical or mechanical energy which can be exploited for vari-
ous application purposes. Turbines which run using wind energy don’t require burn-
ing down the fuel for obtaining energy. As a result, they are considered
environmentally friendly. Also, the wind is linked to the presence of sun; so long as
the sun shines on this planet, the wind subsists on this planet. World wind power
market is evaluated at approximately 27 bn $ (billion USD) (Luther et al. 2015).
Nanotechnologies can play a determined part in the enhancement of wind power
consumption owing to the presence of tribological coatings in addition to wear pro-
tection coat of gearboxes and bearings, conducting nanomaterials for superior light-
ning shield which permit added economic supply of wind power to the grid, and
high-strength lightweight equipments for nanocomposite material-derived
rotor blades.
Nanocomposite materials aid in the creation of longer and stronger blades since
they have an outstanding capacity to handle stiffness and carry load to weight
proportions very effectively. Tribological matters such as scuffing, micro-pitting,
gearbox spalling, and wear hold a key aspect in terms of energy loss which can
be alleviated using nanotechnology, thus enhancing the wind turbine efficiency.
This can be executed via low-friction surface coatings and nano-lubricants
(NanoConnectScandinavia 2018). A wear protective tribofilm is created using nano-­
colloid particle-based boron nitride lubricant additives, a corresponding technology
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 291

in which it reacts with the boronized surface (Hussein 2015). An epoxy contain-
ing carbon nanotubes is utilized to make more grounded and lower-weight wind-
mill sharp edges subsequently longer, and sharp edges enhance the measurement
of power produced by every windmill (National Nanotechnology Initiative 2012,
January 10). Wind turbine rotor blades are made lightweight, thereby increasing con-
ductivity and strength of the blades by the use of carbon nanotubes (Pandey 2018).

15.6.7  Geothermal Energy

Geothermal energy is described as the heat energy dug out from inside the earth’s
surface which differs to an extent of 5–10 km in length. The temperature is extremely
soaring deep within the earth’s interior. Consequently, nanofluids may be employed
in the form of a cooling agent to chill out electronic gadgets used in drilling machines
such as sensors and pipes operating under extreme temperature and friction condi-
tions. Energy sources derived from the earth’s core can be defined in terms of a range
of temperature. For example, temperature as low as ˂100 °C to a medium range of
100–150  °C and as high as ˃150  °C can be found when taken out by employing
ground heat exchangers (Kalogirou 2005). Nanofluids act as working fluid to mine
energy from the earth’s interior and transfer it to a power plant system to g­ enerate
huge amounts of workable energy (Nagar and Agrwal 2013). Nanofluids can absorb
substantially higher amount energy in comparison to normal thermal fluids. This
observation puts forward an array of future research projections by means of shallow
borings to employ geothermal energy (Hussein 2015; Ganguly et al. 2012).

15.6.8  Tidal Energy

Waves are produced by the wind driving over the ocean surface. Moon causes the
earth to pass through the course of ocean tidal projections when the earth rotates on
its own axis. On earth, all throughout the sea coast, the impact of moon causes the rise
and fall of tides almost at a regular interval of 12.5 h. This process goes on consecu-
tively every day, thus making energy driven from tidal waves a prominent resource
of renewable energy (Gillett 2002). Wave- powered devices obtain energy from the
surface motion of ocean waves or from pressure oscillations below the surface.
Usually, energy from water may be regarded as a major resource of renewable
energy due to some rational causes. One reason is that slightly more than two-thirds
of the land area of the surface of the earth is surrounded with water. The other is that
the world is capable of producing approximately 10,000–15,000TWh wave energy
on an annual basis. The energy derived from sea waves can be utilized for producing
hydrogen. It can also be used for mining ocean reserves, water purification, synthe-
sizing liquid and solid state fuels, and in several other areas. A recent review (Qu
et al. 2012) gives detailed discussion about how nanotechnology presents a future
292 N. Raina et al.

prospect for producing clean and affordable future water supply systems. This is
due to many amazing features of nanotechnology like photosensitivity, antimicro-
bial and catalytic activity, high surface area; magnetic, electrochemical and optical
properties thus offering valuable features like specialty adsorbents, high-perfor-
mance membranes and sensors for monitoring water quality and solar decontamina-
tion. The authors also deduced that in order to build up a sustainable water
management system, the expansion of nanotechnology must go hand in hand with
the environmental safety and issues related to research in health sector (Hussein 2015).

15.7  Conclusions

History shows that science and technology has a profound impact on a society.
Nanotechnology is the latest wonder of science whose arrival has created major
buzz these days. It brings astonishing benefits to our everyday life. It is a rapidly
evolving field and is making long strides in every discipline. Nanotechnology is
touching lives through a wide spectrum of areas and is reshaping the future of man-
kind. It reduces materials to a very small (10−9) scale with improved properties
thereby enhancing its applicability. We are bound to see many nanotechnological
wonders within the scientific world in the near future. But no one knows certainly
what is in store for nanotechnology in the coming times.
Since the official commencement of the universal nanotechnology pursuit, it is
one of the most quickly rising fields of technology in every sector. Renewable
energy, in particular, is supposed to participate prominently in the contribution
toward the energy sector world over in the coming hundred years as the society
drifts against the use of fossil energy fuels. Renewable sources lead the way toward
a sustainable economy by entering energy markets as a result of R&D. However,
nanotechnology should focus more on using renewable energy as the primary
energy source in an environmentally friendly manner for the advancement and
development of humankind’s bright future. These will unquestionably increase the
value of life of our society. In an effort to enhance device efficiency and attain com-
mercialization, additional research should be done in order to tailor the nanostruc-
tures, to manage charge separation and transport, to effectively utilize cost-effective
co-catalysts, and to examine the reaction kinetics and their completion at a
larger scale.
The utilization of nanotechnology-based materials in the renewable energy dis-
cipline can perform the pivotal task of escalating the effectiveness of renewable
energy sources such as wind turbine engines, fuel cells, and solar cells for satisfying
the growing appetite of the world for energy. This in turn reduces the hazardous
effect of extracting fossil fuels in order to generate the huge amount of energy. It is
also a key enabler of prominent decline in the expenditure of costly machinery of
energy use and its storage. Additional investigations are therefore required to find
out the prospective applications of nanotechnology in geothermal area as well as in
15  Efficiency Enhancement of Renewable Energy Systems Using Nanotechnology 293

the wind energy and tidal energy sector, with potential impacts on other types of the
renewable energies.

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Chapter 16
Wastewater and Industrial Effluent
Treatment by Using Nanotechnology

Sourav Maity, Debopriya Sinha, and Angana Sarkar

16.1  Introduction

Human activities are known to affect the quality of potable water. Any water whose
quality has been degraded due to human use is wastewater. Wastewater is basically
the water that has been already used for domestic purposes, industrial use and com-
mercial or agricultural activities. It can also be a result of run off from surface or
storm water or may be inflow from sewer and/or sewer infiltration. Wastewater char-
acteristics depend on its source. Wastewater can be classified as – domestic, munici-
pal and industrial wastewater having its source from households, communities and
industrial activities, respectively. The pollutants present in wastewater can be physi-
cal, chemical (both organic and inorganic) or biological in nature.
The physical pollutants will mainly include the suspended solids, whereas the
chemical pollutants will include heavy metals such as lead; mercury; chromium;
soluble organic materials like drugs, fruit sugars, soluble proteins, etc.; insoluble
organic materials (ammonia, hydrogen sulphide); and emulsions like paints, adhe-
sives and emulsified oils. Biological pollutants may include yeast surplus (from
breweries), tissues, skin, hair (from tanneries), etc.
The rapidly increasing industrial growth has led to the formation of huge amount
of industrial water loaded with toxic pollutants that are hazardous for the environ-
ment as well as human health. Industrial wastewater is one of the most important
sources of water pollution (Sethi 2018). In this book chapter, we will primarily
focus on industrial wastewater. There are a number of industrial activities that are

S. Maity · D. Sinha
National Institute of Technology, Rourkela, Odisha, India
A. Sarkar (*)
Department of Biotechnology & Medical engineering, National Institute of Technology,
Rourkela, Odisha, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 299

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_16
300 S. Maity et al.

responsible for generating industrial wastewater. Some of them include industrial

site drainage, cooling waters used in industries such as heat slime, industrial pro-
cessing waters, water used in hydraulic fracturing, emulsions from paper mills, etc.
Battery manufacturing units release heavy metals such as cadmium, chromium,
mercury and lead along with oil, grease, silver and zinc. The pollutants discharged
by organic chemical manufacturers differ from plant to plant depending upon the
variety of products produced. The most common organic compounds released from
these units include benzene, chloroform, naphthalene, phenols, toluene and vinyl
chloride (Ebrahiem et al. 2017). They may also release metal pollutants like chro-
mium, copper, lead, nickel and zinc. Electric power plants particularly coal-based
power stations release metals like mercury, cadmium and lead as well as compounds
of nitrogen, arsenic and selenium of significant levels. At times, the wastewater
stream may contain fly ash, bottom ash and flue gas (which are transferred from the
polluted air to water via means of wet scrubbers). Food processing units may con-
tain certain dissolved organic matter along with high loads of particulate matter and
some surfactants (Britz et al. 2006). The cooling waters of iron and steel industries
are contaminated with ammonia, cyanide, benzene, naphthalene, anthracene, phe-
nols, cresols and complex organic compounds collectively known as polycyclic aro-
matic hydrocarbons (PAH). Pollutants in the wastewater may also include hydraulic
oils, tallow and even particulate solids. Discharges from paper and pulp manufactur-
ing units include dioxins, furans and phenols. Apart from these, the discharged
water also contained lots of sugars and lignocelluloses. Textile dyeing industries
effluents contain synthetic and natural dyestuff, guar, wetting agents and dyes
(Robinson et al. 2001). Effluents from soap and detergent industries contain com-
plex chemicals, and they also had high levels of zinc and iron in them along with oil
and grease. Thus, the industrial wastewater was treated using methods such as dis-
solved air floatation, chemical coagulation and finally activated sludge process.
The characteristics of effluents generated from different industries and manufac-
turing units differ and so do their treatment technologies. Thus, many treatment
technologies had been designed and developed in the past for removal of pollutants
from industrial wastewater such as distillation, adsorption, chemical immobiliza-
tion, aerated lagoons and so on. The characteristics of oil (droplet size, suspension
state) are very important to effectively remove it from wastewater. API separators
and hydrocyclones can be used in many industries to remove oil. For removal of
biodegradable organic materials, methods such as trickling bed filter or activated
sludge process were used. If wastewater contains synthetic organic compounds
(from paint factories or pharmaceuticals), the advanced oxidation processing, distil-
lation and vitrification can be applied. For wastewaters rich in acids and alkalis,
neutralization is the preferred method of treatment. With modernization the type of
waste being generated is changing day by day, and so the treatment technologies
need to be advanced and efficient enough to effectively remove contaminants from
wastewater. Advanced wastewater treatment is comprised of several processes such
as reverse osmosis, membrane filtration, chemical coagulation and chemical pre-
cipitation depending upon the particular type of effluent produced by the respective
industry. Earlier the conventional methods mainly aimed at removing the suspended
16  Wastewater and Industrial Effluent Treatment by Using Nanotechnology 301

materials present in wastewater and treatment of organic pollutants in it. Recently

the focus has shifted to other important contaminants in wastewater such as dis-
solved solids, heavy metals, toxicants, volatile compounds, solvents, radioactive
wastes, etc. so that finally the discharged water after proper treatment can be reused
for some other purpose and should not have any negative effect on human health or
on the ecosystem.
Wastewater treatment involving traditional methods has become increasingly
challenged due to the identification of various other contaminants, rapid population
growth and increasing industrial activities. Thus the need for switching toward
advanced treatment technologies is the need of the hour, which can remove various
probable harmful organic or inorganic compounds or microbial contaminants that
cannot be removed effectively and efficiently by using conventional treatment pro-
cesses. Advanced treatment processes include membrane filtration, nanotechnol-
ogy, advanced photo-oxidation process, automatic variable filtration (AVF)
technology, microbial fuel cells, natural treatment systems, coke oven by-product
treatment and many more.

16.2  E
 xisting Pollutants and Their Traditional Treatment
Technologies

The nature and characteristics of pollutants released in industrial wastewater depend

on the type of products manufactured by the industries. Most of the industries and
manufacturing units produce wastewater which has to be treated to reduce the pol-
lutant load in water. This water after treatment can be reused for some other pur-
poses or if released into the environment will have less chances of pollution.
Industrial wastewater treatment includes numerous processes that render the waste-
water (an undesirable by-product of industries) less polluting. The treatment tech-
nology to be used depends on a lot of factors, such as  – composition of the
wastewater, type of pollutants in the wastewater, operation costs, etc. The wastewa-
ter from textile industries contains impurities that are present in suspended form.
They are first coagulated and precipitated in order to generate micro-flocs, and then
these micro-flocs were removed by filtration. For removal of COD and colour, sim-
ple aerobic treatment is carried out. The dyes present in the wastewater are very
difficult to treat by this method because they are organic molecules which are recal-
citrant. Hence, they show resistance to aerobic treatment. For colour removal, the
technologies developed are classified as physical, chemical and biological (Robinson
et al. 2001). The most preferred wastewater treatment technology is biological treat-
ment because it is economical when compared to other methods. Biological treat-
ment methods include fungal decolouration, microbial degradation and adsorption
by microbial biomass. Chemical methods involve coagulation, flocculation, floata-
tion, filtration, electro-floatation, electro-kinetic coagulation, conventional oxida-
tion and electrochemical processes. Out of all the existing physical methods,
302 S. Maity et al.

adsorption is the most preferred method because it does not form any harmful sub-
stance. The spent grains released by the breweries usually undergo membrane filtra-
tion. Highly suspended solids, bleaching agents and solvents released from paper
and pulp industries are subjected to adsorption, sedimentation chemical coagula-
tion, reverse osmosis and advanced coagulation.
The wastewater from food industries contains surfactants, dissolved organic mat-
ter and particulate load which are treated by dissolved air floatation and gravity oil
separators (Britz et al. 2006). Activated sludge treatment method is used to remove
oestrogenic hormones that are given out in wastewater from pharmaceutical indus-
tries. For most of the biodegradable organic wastes present in wastewater, either
activated sludge treatment or trickling bed filter method is used. Heavy metals like
iron, lead and zinc, paints and cyanide can be removed by ion exchange or by chem-
ical precipitation. Advanced oxidation process is usually used to treat industrial
effluents where they transform toxic organic compounds into biodegradable sub-
stances. It is used for treatment of synthetic organic materials like solvents, paints,
etc. It can also be used to remove micro-pollutants from wastewater. At times sonol-
ysis has been used to remove chemical contaminants from wastewater which
involves acoustic cavitation (Shah 2016). The most widely used adsorbent is acti-
vated carbon due to its extensive micro-porous structure and high surface reactivity
and adsorption capacity. Membrane separation technologies are used to remove
dyes and paints from wastewaters. Simple sedimentation techniques are used to
remove most of the solids present in industrial wastewater with the solids obtained
as slurry or may be sludge. Oils that float in the industrial effluent can be removed
via skimming devices, which is a cheap and dependable method to remove oil,
grease and hydrocarbon from wastewater. The effluents from the dairy industry
include dissolved sugars and proteins, fats and other additive residues, and it may
also contain pathogens from production processes (Britz et al. 2006). The colour
and odour from dairy wastewater can be removed by activated carbon treatment.
Fats, oils and grease can be removed using enzymatic hydrolysis (Cammarota
et al. 2001).
The application of traditional and conventional methods of treatment to indus-
trial wastewater is becoming a challenging task since the type and nature of con-
taminants in the wastewater are changing day by day, and thus their effectiveness
and efficiency have become restricted. Thus, new technologies for treatment of
industrial effluents must be developed that will have satisfactory efficiency in
removing pollutants from wastewater.

16.3  Advanced Technologies for Wastewater Treatment

Wastewater treatment involving traditional methods has become more and more
challenging with the identification of increasing variety of contaminants (let it be
toxic or non-toxic), increasing industrial activities and rapid population growth. So,
advanced wastewater treatment technologies are the need of the hour to remove
16  Wastewater and Industrial Effluent Treatment by Using Nanotechnology 303

various probable toxic compounds that could not be removed effectively and effi-
ciently by using traditional (or conventional) wastewater treatment processes.
Some of the new advanced technologies that have been introduced for wastewa-
ter treatment are as follows (Shah 2018; Sethi 2018).

16.3.1  Membrane Filtration

This technology is of very much importance for the development and designing of
advanced, new and improved water reclamation systems. A wide variety of dis-
solved contaminants could be removed by using micro and ultrafiltration mem-
branes, which provide an excellent wastewater pretreatment process. Membrane
bioreactor filtration technique is being used extensively for advance treatment fol-
lowed by RO and UV treatment to produce non-potable water.

16.3.2  Nanotechnology

The evolution of nanotechnology has remodelled the wastewater treatment process.

The most important feature of nanotechnology is that it can be incorporated with
any other existing technologies to modify and/or clarify the concept with ease.
Ongoing researches focus for production of fabricated membranes from nanomate-
rials to break down the toxic compounds from the wastewater during the treat-
ment itself.

16.3.3  Automatic Variable Filtration (AVF) Technology

AVF technology used for wastewater treatment works on the principle in which the
upward flow of the influent is rinsed by the downward flow of the filter media. The
main advantage of this process is that there is no necessity for any further filter
media cleaning or fresh water since during the treatment process itself, the filtered
influent clears the filter media.

16.3.4  Advanced Photo-Oxidation Process (APOP)

APOP is a simple system used for wastewater treatment for disinfection and for
removal of endocrine disruptors and other hazardous compounds.
304 S. Maity et al.

16.3.5  Microbial Fuel Cells

It’s the technology which involves the extraction of electrical energy from the
organic matters existing in the wastewater stream directly by electron transfer to
acquire the energy produced by microorganisms.

16.3.6  New Urban Sanitation Technology

This is the treatment which aims at reusing of energy and minerals from wastewater
with unification of anaerobic digestion and electroflocculation (Elflox)
technologies.

16.3.7  Natural Treatment Systems (NTSs)

NTSs incorporate a variety of biological, chemical and physical techniques which

work concurrently to remove variety range of contaminants including nutrients,
micro-constituents inclusive of endocrine disrupting chemicals and pathogens from
wastewater.

16.3.8  Coke Oven (CO) By-Product Wastewater Treatment

In the CO effluent, the predominant pollutant is ammonia which would worsen the
water pollution scenario if discharged untreated, so its recovery is of very much
importance. Trickling filter and activated sludge process are the two most common
techniques for the treatment of CO effluents. This treatment process is used by the
steel-producing industries in India.

16.3.9  Urine Separating Process

Urine is part of domestic wastewater which comprises 90% and 50% of the nitrogen
and phosphorus, respectively. Urine separating toilets have been developed and
technologies designed for treating this for the production of fertilizer products with
minimal requirement from outside sources.
Figure 16.1 illustrates the overview of various above advanced wastewater treat-
ment processes.
16  Wastewater and Industrial Effluent Treatment by Using Nanotechnology 305

Fig. 16.1  Overview of advanced wastewater treatment processes

16.4  Nanotechnology

The genealogy of the term ‘nano’ is Greek, meaning of which is ‘dwarf’. In scien-
tific terms, a nanometre is defined as one billionth of a matter (10−9) and can also be
represented by the length of 10 hydrogen atoms lined up in a queue. The process of
nanotechnology started occurring in nature, billions of years ago, when molecules
began organizing themselves into complex forms and structures that launched life
on Earth. By gradual evolution, mutation and adaptations, plants acquired the power
to convert carbon dioxide to oxygen with the help of sunlight by the process which
is known as ‘photosynthesis’. This photosynthesis process still takes place within
tiny structures in plants and is known as ‘chloroplasts’. Chloroplast comprises sev-
eral nanoscale ‘thylakoid discs’, which consists of a green pigment called ‘chloro-
phyll’. Another similar example of natural nanotechnology can be ‘chemical
catalysts’, through the process ‘catalysis’, or in bioscience it is known as ‘enzymes’.
The biomolecules that help in accelerating the rate of a chemical reaction are called
enzymes.
The concept that seeded the idea of nanotechnology was first brought into the
discourse by a well-known physicist named Richard Feynman in the year 1959, in
his talk ‘There’s Plenty of Room at the Bottom’. But Norio Taniguchi, a Tokyo
Science University Professor, first coined the term ‘nanotechnology’ in the
year 1974.
306 S. Maity et al.

16.4.1  What Is Nanotechnology?

The terminology ‘nanotechnology’ portrays a stretch of technologies which can be

complied on a nanometre scale with an extensive application as an advanced tech-
nology. Nanotechnology helps in the innovation of new devices, materials and tech-
nologies using distinct atoms and molecules. Nanotechnology involves around
those materials and particles having dimension about a range of 1–100 nm. These
materials and particles are called nanomaterials and nanoparticles.
Nanomaterials are characterized by their exquisite physical, chemical and/or
biological characteristics which are distinct from their equivalent on the macro
level. The most important feature of nanomaterials is its large surface to volume
ratio; it is this feature which makes it suitable for its widespread usage. The
nanomaterials have completely distinct optical, electrical and magnetic proper-
ties, rapid chemical processes, etc. All these characteristics of nanomaterials
make this technology attractive and also revolutionizing different fields of
applications.

16.4.2  Nanotechnology in Wastewater Treatment

The unique properties of various nanomaterials enable to innovate novel technolo-

gies in terms of wastewater treatment. Nanotechnology is applied in sensing, moni-
toring and removal of wide range of pollutants. Organic pollutants like benzene,
chloroform, polycyclic aromatic hydrocarbons (PAHs), etc. and heavy metal pollu-
tion like mercury, lead, cadmium, cobalt, copper, chromium, arsenic, etc. pose a
serious threat to the environment due to its toxicity to living organisms including
humans. Nanomaterials are expected to enhance the kinetics and efficiency of vari-
ous chemical and physiochemical processes owing to its large surface area, catalytic
activities and high reactivity, hence reducing chemical and energy consumption
which is of uttermost importance in wastewater treatment. Various nanotechnology
methods such as adsorption, nanofiltration, photocatalysis and membrane processes
involve the use of TiO2, ZnO, carbon nanotubes, ceramic membranes, metal (oxides)
and magnetic nanoparticles are used to resolve or reduce pollutant toxicity prob-
lems in wastewater.
Nanomaterials used for water treatment and/or purification can be defined in four
classes (Chorawala and Mehta 2015):
• Dendrimers
• Metal-containing nanoparticles
• Zeolites
• Carbonaceous nanomaterials
16  Wastewater and Industrial Effluent Treatment by Using Nanotechnology 307

16.4.2.1  Adsorption

The adherence of atoms, ions or molecules from a dissolved solid, liquid or gas to a
surface is called adsorption. Efficiency of conventional adsorbent in wastewater
treatment is usually limited due to its surface area or the active sites and the adsorp-
tion kinetics. Where on the other hand in wastewater treatment process the sorption
capacity of the nanosorbents is very high and specific? Nanoparticles exhibit two
important characteristics that make them an excellent adsorbent. That is the large
surface area of nanoparticles and surface multifunctionality, i.e. the ability to chem-
ically react and bind with different contiguous atoms and molecules with ease.
These properties make a nanoparticle more effective adsorbent for various contami-
nants in wastewater. The most important nanosorbent for wastewater treatment is
carbon nanotubes (CNTs) which is used to treat heavy metals like lead, copper, zinc
and cadmium and also organic compounds like polycyclic aromatic hydrocarbons
(PAHs) (Chen et al. 2007; Li et al. 2003; Lu et al. 2006). Metal-based nanosorbent
mainly metal oxides like titanium dioxide, alumina and iron oxide are used for the
treatment of heavy metals like lead, mercury, chromium, arsenic, etc. (Sharma et al.
2009). Polymeric nanosorbents such as dendrimers are also used to treat heavy met-
als in wastewater (Diallo et al. 2005).

16.4.2.2  Nanofiltration

Membrane filtration plays a significant role in providing high level of water purifi-
cation since it removes various types of contaminants present in wastewater.
Nanofiltration (with reverse osmosis [RO]) is a high-pressure membrane treatment
process for wastewater. But with respect to RO, nanofiltration process requires
much lower drive pressure so energy consumption is also low. This process is highly
efficient in the removal of organic and inorganic contaminants, bacteria and
viruses (Zekic et al. 2018). Types of membranes used in nanofiltration technique
can be classified in three categories (Pendergast and Hoek 2011):
• Nanostructured ceramic
• Biologically inspired membranes
• Organic-inorganic membranes
Some benefits of using nanofiltration for wastewater treatment are (Tambe
Patil 2015):
• Lower operating costs
• Lower energy costs
• Reduction of total dissolved solids (TDS)
• Reduction of heavy metals like arsenic, etc.
• Reduction of volatile organic compounds (VOCs) and pesticides
• Reduction of nitrates and sulphates
• Hard water softening
308 S. Maity et al.

16.4.2.3  Nanofiber

Electrospinning is an economical and efficient process to produce ultra-fine fibres

from a wide range of materials like ceramics, polymers or even metals; the resultant
nanofibers possess exceptional properties from minute pore size, large surface area
to high porosity which makes it ideal for its usage in wastewater treatment. For
example, for removal of heavy metal ion, electrospun polyacrylonitrile nanofiber
mats are used (Li and Xia 2004). In industrial wastewater treatment process, an
advanced method is used where nanofiber technology in combination with biologi-
cal process helps in the removal of toxic xenobiotics efficiently. The most important
advantage of using this technology is that the biofilm formed from the bacteria
forms both on the carrier surface and closer to its epicentre (within the carrier) so
that the bacteria can be protected against the harmful effects from the adjacent envi-
ronment (Prachi et al. 2013).

16.4.2.4  Photocatalysis

Photocatalytic oxidation in wastewater treatment is an advanced oxidation process

which is used for the removal of trace elements and also microbial pathogens. It is
a convenient pretreatment to enhance the biodegradability of non-biodegradable
and hazardous contaminants in wastewater (Murakami et al. 2009). Organic com-
pounds which are recalcitrant are also treated by photocatalysis (Han et al. 2009).
The major drawback for wide application of this process is its slow kinetics since
the photocatalytic activity is limited. In wastewater treatment, photocatalyst which
is most widely used is titanium dioxide (TiO2) due to its chemical stability, low
toxicity, raw material abundancy and low cost. Other photocatalysts include fuller-
ene and aminofullerene, but they are expensive and availability is not like TiO2.

16.4.2.5  Nanocatalysts

In wastewater treatment processes, nanocatalysts are widely used as the catalytic

activities are increased by them due to its unique properties like having a large sur-
face area with compatible shape attributes. Nanocatalysts increase reactivity and
degeneration of the contaminators. Catalytic nanoparticles which are widely used
are zero valence metal, semiconductor materials and bimetallic elements, and these
are used for the degeneration of contaminators like polychlorinated biphenyls
(PCBs), halogenated aliphatic, organochlorine pesticides, azo dyes, nitro aromatics
and halogenated herbicides (Bhattacharya et al. 2013). Development of highly effi-
cient nanocatalyst particles has been done for degrading microbial contaminants in
wastewater like silver (Ag) nanocatalyst, n-doped TiO2 and ZrO2 nanocatalyst (Xiu
et al. 2011, 2012; Liau et al. 1997; Li et al. 2008).
16  Wastewater and Industrial Effluent Treatment by Using Nanotechnology 309

16.4.2.6  Sensing and Monitoring

In wastewater treatment, the prime challenge is monitoring water quality parame-

ters due to concentration being low of certain contaminators and deficit of rapid
detection of pathogens. Sensors usually has three major constituents: recognition
element, a signal transducer and a detector.
Detection of pathogens is of utmost importance as it is related directly to public
health. Coliform test which is a conventional indicator system is slow and fails to
sense or monitor the existence of some major or emerging pathogens, which include
bacteria (Helicobacter and Legionella), viruses (hepatitis A and E) and protozoan
(Cryptosporidium and Giardia). Nanomaterials that are most commonly used for
detection of pathogens are quantum dots (QDs), carbon nanotubes (CNTs), mag-
netic nanoparticles, dye-doped nanomaterials and noble metals (Vikesland and
Wigginton 2010; Theron et al. 2010; Yan et al. 2007).
For both detection and concentration check for trace metals or organic contami-
nants, carbon nanotubes (CNTs) are being used since their adsorption capacity is
high as well as the kinetics is quite fast (Duran et al. 2009; Cai et al. 2003). For
detecting pesticides at ppb levels nano–Au is used (Lisha and Pradeep 2009) and
transformed nano–Au detects Hg2+ and CH3Hg+ (Lin and Tseng 2010).
Table 16.1 represents a brief analysis of application of nanotechnology in treat-
ment of wastewater.

16.5  Pros and Cons of Nanotechnology

As we know there are few things in this world that do not have two-faced implica-
tions. Nanotechnology also has both pros and cons (Sharma and Sharma 2012).
Now coming to the pros:
• Efficient  – Use of raw materials will become more efficient with the use of
nanoscale reagents or catalysts which increases the rate of reaction and other
chemical reaction efficiencies.
• Monitoring and protection of the environment – Designing biosensors utilizing
nanomaterials helps to detect environmental pollutions. And designing suitable
technologies using nanotechnology for targeted pollutant(s) above (or at the bor-
derline of) the permissible limits can be eliminated.
• Biological applications – Using advanced nanotechnology, ultrasmall probes can
be developed on planetary surfaces which would help agricultural practices and
to control air, water and soil contamination.
• Biomedical applications  – Advanced nanotechnology can be used to develop
diagnostic tools and for treatment in medical field.
• High precision in reducing the amount of waste.
• Remediating environmental damages.
310 S. Maity et al.

Table 16.1  Application of nanotechnology in treatment of wastewater

Sl. Type of
No. application Nanomaterials used Pollutants References
1 Adsorption Carbon nanotubes Organic compounds Chen et al. (2007)
(CNTs) such as PAHs
(polycyclic aromatic
hydrocarbons)
Heavy metals such as Li et al. (2003), Lu
lead, copper, zinc and et al. (2006)
cadmium
Metal-based nanosorbent Heavy metals such as Sharma et al. (2009)
such as titanium dioxide, arsenic, mercury, lead,
alumina and iron oxide copper, nickel,
cadmium and
chromium
Polymeric nanosorbent Heavy metals such as Diallo et al. (2005)
such as dendrimers copper
2 Nanofiltration Nanostructured ceramic Heavy metals, nitrates Kaufman et al.
Nano-zeolites and sulphates, (2010), Lens et al.
Biological inspired pesticides and VOC (2013), Pendergast
membranes such as (organic chemical) and Hoek (2011)
aquaporin-z from E. coli
3 Nanofiber Polymers, ceramics or Organic compounds Cloete et al. (2010),
even metals Heavy metals Li and Xia (2004)
4 Photocatalysis Titanium dioxide (TiO2) Organic compounds Han et al. (2009),
Pretreatment for Murakami et al.
hazardous, non-­ (2009)
biodegradable and
recalcitrant organic
compounds
5 Nanocatalysts Nano–Ag Microbial Xiu et al. (2011,
Nano–TiO2 contamination 2012), Liau et al.
Nano–ZnO (1997), Li et al.
(2008), Vecitis et al.
Carbon nanotubes (CNTs)
(2010)
Fullerol and amino
fullerene
Semiconductor Organic compounds Bhattacharya et al.
nanoparticles such as PCBs (2013)
Zero-valence
nanoparticles
Bimetallic nanoparticles
(continued)
16  Wastewater and Industrial Effluent Treatment by Using Nanotechnology 311

Table 16.1 (continued)
Sl. Type of
No. application Nanomaterials used Pollutants References
6 Sensing and Magnetic nanoparticles, Detection of pathogens Vikesland and
monitoring noble metals, quantum Wigginton (2010),
dots (QDs), nanoparticles Theron et al. (2010),
doped with dye and Yan et al. (2007)
CNTs
Carbon nanotubes Trace metals or Duran et al. (2009),
(CNTs) organic pollutant Cai et al. (2003)
detection and
concentration
Nano–Au Pesticide detection Lisha and Pradeep
(2009)
Detection of Hg2+ and Lin and Tseng
CH3Hg+ (2010)
Quantum dot (QD)- Detection of Yang et al. (2010)
modified TiO2 nanotubes polycyclic aromatic
hydrocarbons (PAHs)

Potential risks involved:

• Evaluation involving complete risk assessment of human health safety at all
stages of nanotechnology is still not clear.
• Life cycle risk assessment of other environmental implications at all stages is
also not clear.
• Synthesizing nanoparticles requires high energy which causes high energy
demand.
• Recovery and recycling rates of nanoparticles are very low.
• Lack of experienced engineers and trained workers is of major concern.

16.6  Future Aspects

Nanotechnology is a promising and fresh technology which is being considered for

wastewater treatment to provide eco-friendly, economical and convenient treatment
methods. Nanoparticles of wide varieties have proved its effectiveness and effi-
ciency in detection and removal of various water contaminants.
Future research aspects should target how to incorporate nanotechnology with
the existing wastewater treatment technologies. Since its not practically possible to
cease all the existing ongoing wastewater treatment facilities in the ongoing period.
So, designing and developing nanoparticles which could be made compatible with
minimum changes to the existing technology and infrastructure are of much
importance.
312 S. Maity et al.

The limitation of the use of nanotechnology in wastewater treatment is its eco-

nomic cost-effectiveness in terms of infrastructure and operating costs and that it
might be difficult to retrieve the nanoparticles from the treated solutions, which
results in the loss of nanoparticles. The toxicity of the nanoparticles and its environ-
mental impacts are still being investigated to study its impacts on human healthiness
and the environment. So development of ecomical nanoparticles eith enhanced effi-
ciency and prevail over the limitations of using nanotechnology in wastewater treat-
ment is one of the most important future prospect of this technology.
It can be envisioned that this advanced technology, with careful management to
avoid any undesirable consequences, can be a huge contribution and establish itself
as the best wastewater treatment technology.

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Chapter 17
Biomolecular and Cellular Manipulation
and Detection (Nanofluidics and Micro-
and Nanotechnologies in Integrative
Biology)

Shagun Gupta, Vijeshwar Verma, and Vipan Kakkar

17.1  General Introduction

Owing to their size compatibility, it has become possible to interface nanomaterials

with biological samples, thus foreshadowing the inevitable era of nanotechnology
and microfluidics resulting in an emerging interdisciplinary field known as bionano-
electronics (Center for Synthetic Biology). Bionanoelectronics also appends improve-
ments in molecular-scale electronics, a branch of nanotechnology that utilizes single
molecule, or nanoscale collection of single molecules, as electronic components.
Molecular electronics, also termed as single molecule electronics, had made it
feasible to fabricate hardware by synthesizing the devices and circuits in layers that
have the capability of self-assembling, similar to the evolution of structures in living
organisms. Devices having different functions are being manufactured using vari-
ous techniques depending on chemical attractions and can be used for variety of
applications rather than the expensive and complex processes previously used to
etch electronic circuits (Rakshit et al. 2004; Venere 2005). Molecules might be able
to complement or supplement silicon, and in today’s world, instead of traditional
electronic components, various devices such as computers, sensors, and so on can
use molecules, such as DNA, RNA, and proteins. This has spawned new concept –
“biochips,” described in subsequent sections – which have the potential to utilize
proteins in sensors for detecting pollutants and contaminants in sand, water, and air
and for the analysis of blood, urine, and other biological samples (Venere 2005;
Rakshit et al. 2004; Sørensen 2006; Hersam and Reifenberger 2004).

S. Gupta · V. Kakkar (*)

School of Electronics & Communication Engineering, Shri Mata Vaishno Devi University,
Katra, India
e-mail: [email protected]
V. Verma
School of Biotechnology, Shri Mata Vaishno Devi University, Katra, India

© Springer Nature Switzerland AG 2020 315

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_17
316 S. Gupta et al.

17.2  Buckyballs and Nanotubes

One of the major challenges in developing molecular electronics is the better under-
standing of how electricity is transferred between silicon contacts and molecules in
a circuit (Rakshit et al. 2004; Venere 2005). On August 12, 2005, issue of Physical
Review Letters, scientists at Purdue University (West Lafayette, IN) reported that
they had designed a nanotech simulation tool that explains the flow of current
between individual molecules and silicon atoms so that researchers will be able to
fabricate “molecular electronic” devices for advanced sensors and future computers
(Venere 2005). According to them, this will help the researchers to precisely ana-
lyze the changes in electrical conductivity by employing this new simulation tool.
These changes in electrical conductivity depend on how molecules are linked to sili-
con, information that is highly critical for designing the devices properly. In order
to show the flow of current, they have used the tool called buckminsterfullerenes, or
“buckyballs,” named after architect R. Buckminster Fuller. A buckyball molecule,
shown in Fig. 17.2, consists of 60 carbon atoms and is a soccer-ball-shaped mole-
cule with a width of about 1 nm, which is approximately 10 atoms wide. They have
predicted the flow of electricity for the three ways in which buckyballs and silicon
can be connected. Figure 17.1 shows the geometrical structures with the experimen-
tal and theoretical results of all the three scenarios. In the first scenario, there is no
chemical bond, and the buckyball is simply sitting on top of the silicon as shown in
Fig. 17.1a. In the next scenario (Fig. 17.1b), heating or annealing of silicon has been
done in order to connect the molecule to the silicon. And in the third scenario, a
natural defect subsisting in silicon has been considered in which the buckyball is
resting inside a tiny pit, as shown in Fig. 17.1c. This model precisely plotted the
conduction and voltage changes in the three types of connections, and it was seen
that the predictions agreed with actual data obtained by the experiments performed
by different researchers in laboratories for measuring the current flow alterations
(Liang and Ghosh 2005).
Buckyballs are also being explored for improving the (magnetic resonance
imaging) MRI’s ability for the detection of brain tumors. They can also be employed
for destroying these tumor cells by delivering the payloads of radiation. Experiments
on rats have been performed and have shown the MRI detection sensitivity has been
increased by at least 40-fold with the buckyballs being packed with MRI contrast
metal gadolinium. A modified version of buckyballs utilizing a fluorescent metal
atom called terbium has also been created by the scientists for guiding the surgeons
in removing the tumors with high precision and for those cancer cells that have
been missed by surgeons; another metal named lutetium can be added that can
provide a lethal dose of radiation to these cells. For the successful testing in humans,
this research still requires few more years (Amiji 2008). The “buckyball” concept
is now almost over a decade old and has created much excitement among the
researchers because of its potential in different applications, but as a commercial
product, it is still in its infancy. Another geometry similar to buckyballs but tubular
in shape came into existence in 1991 by a Japanese physicist “Sumio Iijima” and
has more practical implementations than buckyballs (ETHW 2017). Such tubular
17  Biomolecular and Cellular Manipulation and Detection (Nanofluidics and Micro… 317

(a) (a)
V/I (dI/dV)

V/I (dI/dV)
(b) (b)
V/I (dI/dV)

V/I (dI/dV)
(c) (c)
V/I (dI/dV)

V/I (dI/dV)

EXPERIMENTAL THEORETICAL
RESULTS GEOMETRY RESULTS

Fig. 17.1  Comparison of experimental conductance–voltage characteristics (G-V) with the

­theoretical results of G-V available in the literature for the different cases of bonding geometries
(Liang and Ghosh 2005)

structures, known as nanotubes, consist of carbon atoms or molecules in the form

of tubes or even tubes-within-tubes. Due to the hollow-shaped geometries of both
the balls and tubes, as shown in Fig. 17.2, they can be used for drug-delivery appli-
cation, as carriers for drugs or other chemicals. These structures made of carbon
atoms have also found applications in the field of electronics for demonstrating the
various electronics components such as transistors, tiny wires, etc. (ETHW 2015).
Nanotubes have been added to the batteries in order to increase their surface area,
and light-emitting nanotubes are being used in the field of telecommunication.
Further, nanotubes are also being used for interacting with nerve cells by sending
signals to them.

17.2.1  Application of Nanotubes in Integrative Biology

17.2.1.1  S
 ending Signals to Nerve Cells via Nanotubes/Neuron-Nanotube
Electric Interface

Nanotubes, as defined above, are tiny hollow filaments of carbon with the size of
about one- ten thousandth of the diameter of a human hair. Nanotubes have gained
much fame due to their versatile properties and have considered as one among the
318 S. Gupta et al.

Fig. 17.2  Geometrical structures of (a) buckyball molecule, (b) a carbon nanotube with close
ends, and (c) a carbon nanotube with open ends. (Earlboysen 2011a, b. Copyright ©2011, John
Wiley and Sons)

most versatile materials ever discovered. They can be cylindrical in shape with open
ends or can be a close-ended geometry as shown in Fig.  17.2b, c, respectively.
Carbon nanotubes (CNTs) have high strength and density features when compared
to steel, are better conductors than copper, can be used as a replacement of silicon
in semiconductor chip industry, and can serve as a surface for the growth of cells, if
deposited on transparent plastic in the form of thin films. Due to these remarkable
characteristics, nanotubes have found applications in almost every field ranging
from designing the elevator cables to lift the payloads into Earth orbit to the minia-
turized computers or chips that are even smaller than human cells. In May 2006, the
researchers at Rice University and University of Texas Medical Branch at Galveston
(UTMB) highlighted the electrical interface capability of nanotube films between
various biomedical instruments or prosthetic devices and living tissues, in a paper
published in Journal of Nanoscience and Nanotechnology (Liopo et al. 2006). They
have reported that the electrical communication between these two entities has been
17  Biomolecular and Cellular Manipulation and Detection (Nanofluidics and Micro… 319

made possible through a transparent conductive layer designed by them by

­stimulating the cells. Neurons that had been cultured from experimental rats and
neuroblastoma cells mainly utilized in test-tube experiments are the two different
cell types employed by the researchers’ group in their experiments. Both the types
of cells have been placed on single-walled carbon nanotubes’ (SWNTs) mats seeded
on flexible transparent plastic sheets and having the thickness equivalent to ten lay-
ers. An important neural protein has been absorbed by the nanotubes forming a
roughly textured carpet for the readily growth of nerves on them. Through these
SWNTs, electrical pulses were transmitted and individual cells’ responses were
recorded by a miniaturized electrode located next to these cells using a microscope.
The researchers have also studied the effect of various types of SWNTs on the
development and growth of neuroblastoma cells. They have compared the cells that
were cultured on unaltered native CNTs and using traditional tissue culture plastic
to the cells that were placed on functionalized SWNTs’ mats. Functionalization of
SWNTs indicates adhering of the surfaces of CNTs with additional molecules in
order to improve the CNTs’ electrical properties for proper growth of cells. It was
seen that native CNTs resulted in better attachment of neuron and supports the
growth well. Next step in the research is to make the attachment of neurons better
so that they can communicate in an improved manner leading to superior biocom-
patibility of these surfaces. This can be done by finding an updated way of function-
alizing the nanotubes (Liopo et al. 2006; Bourzac 2006).
If CNTs are able to record the continuing electrical activity in cells with high
sensitivity, then a device for performing the things like prosthetic control can be
designed using them to both deliver and sense stimuli to the cells (Jain 2013). Thus,
nanotubes are a good hope for stimulating or replacing the damaged or missing
nerve cells in the spinal cord, brain, and eye. Cochlear implant in the people with
severe hearing disability is one of the practically implemented applications of neu-
ral prosthetics. In this, the electrodes are utilized that can respond to the sound and
can transmit the electrical signals directly to the disabled person’s brain. Retinal
prosthetic concept has also gained much popularity which will help restore the
vision of blind people (Bourzac 2006).
In 2016, Usmani et al. in their study have shown that CNTs have the potential as
a nervous system prosthesis and can support nerve fiber growth (Usmani et  al.
2016). Thus, they can provide a functional reconnection and help in bridging the
segregated neural explants. Biocompatible material has been used for in vivo appli-
cations, and its implantation in the small rodents’ brain has not caused large scars
and, thus, did not result in a noticeable immune response unlike the traditional elec-
trodes that caused scarring and inflammation (Amiji 2008).

17.2.1.2  Cell Membrane Interaction with Nanotube Transistor

Advancements in nanotechnology and microfluidics have made it feasible to inte-

grate nanoscale-fabricated structures with various biological molecules and pro-
cesses resulting in better sensing and electronic control over biological systems.
320 S. Gupta et al.

Various interdisciplinary state-of-the-art technologies like lab-on-chip for early

detection of diseases, organ-on-chip, artificial sensory systems, etc. are the out-
comes of such integrations and are critically dependent on the nature of interfaces
between diversified fields. In March 2005, researchers from University of California,
Los Angeles, USA, and Nanomix, Inc., USA, reported the demonstration of an
intact biological system interaction with a nanoelectronic device for the first time
claiming that this achievement could ultimately be helpful in an artificial eye cre-
ation (Artukovic et al. 2005). They tried to overcome the issue of complex hierarchy
in biosystems, as organisms are made up of multiple cells and cell membranes com-
prise tiny objects such as individual proteins located at different distances, by main-
taining the interaction of individual nanotubes with individual proteins and
interaction of nanotube networks with multiple cell membranes. They had utilized a
field-effect transistor (FET) made up of nanotube network with the cell membrane
of a bacterium named Halobacterium salinarum (Liz Kalaugher 2005).
Bacteriorhodopsin, a protein having a light-sensitive membrane, was present in the
cell membrane, and metal electrodes’ connected dense network of CNTs was at the
heart of the transistor. Chemical vapor deposition (CVD) technique had been
employed for growing the CNT network FET onto a substrate, and the cell mem-
brane was deposited on this substrate for connecting the components. A silicon chip
was then placed on top of a 5-nm-thick cell membrane layer, and rhodopsin dipoles’
orientation in the membrane layer was altered by applying an electrical potential to
the upper chip. The electrical properties of FET were tested with the different orien-
tations of neighboring dipoles, and it was seen that bacteriorhodopsin’s electric
dipole remained intact and FET operation was retained. Transfer characteristics of
FET had shown that bacteriorhodopsin’s dipole lies about two-thirds of the way
from the exterior of the cell to the inside of the membrane. In order to calculate the
effect of this dipole on nanotubes, a simple electrostatic model as shown in Fig. 17.3a
was used by the researchers. In this model, rhodopsin molecules form a constant
dipole density line above a nanotube and with density equivalent to “π”; a charge
density denoted by “λ = −rπ/d2” has been induced by the line of dipoles as men-
tioned in Fig. 17.3b. Thus, with the knowledge of both the dipole-moment of bacte-
riorhodopsin and the induced charge, one can calculate the distance of dipoles from
the nanotubes. Conclusively, the researchers have successfully demonstrated that it
is possible to directly connect the living cells with the nanoelectronic devices and
such nanodevices can be used as an investigative tool in various applications
(Bradley et al. 2005).
Further, the response of such electronic device can be utilized to understand vari-
ous crucial aspects of the biological system like the distribution of charge within the
proteins and so on. The scientists have justified their vision of an artificial eye in
which the photon-to-electron conversion is required and which can be achieved by
using a light-absorbing molecular layer coupled to neurons attached to an electronic
device. These nanoelectronic devices also have the potential to directly connect and
manipulate living cells leading to the possibility of detection and modification of
different bioprocesses at the cellular level. Thus, nanobioelectronics can achieve the
breakthroughs in the field of “cellectronics” (Liz Kalaugher 2005).
17  Biomolecular and Cellular Manipulation and Detection (Nanofluidics and Micro… 321

Fig. 17.3 (a) Electrostatic model illustrating the cell membrane geometry with respect to nano-
tubes. Trimers are arranged on a hexagonal lattice, and the purple dots resembling rhodopsin
assemble into these trimers. (b) Model with the dimension specifications as used in the calcula-
tions (Bradley et al. 2005)

To enhance the achievements in nanobioelectronics, scientists have also engulfed

themselves in nanomaterial research. Developments in nanotechnology have
resulted in the discoveries of various nanomaterials having the capabilities to be
used in biological environments and are termed as nanoporous biointerfaces. One
such biointerface that has gained popularity in biomedical applications is nanopo-
rous anodic aluminum oxide (AAO) owing to its exclusive features such as increased
surface area, highly biocompatible nature, etc. Due to these unique properties, AAO
membranes can act as cell interfaces and have found applications in immunoisola-
tion devices, coculture substrates, implant modifications, etc. (Brüggemann 2013).
In order to manipulate and to study the behavior of cells without crushing them
in the process, a cell-transistor interface has been developed by Max Planck Institute
(Munich, Germany) researchers in June 2007 with the notion that the development
of such an interface will usher in a new era of bioelectronics (John Wiley & Sons
2007). To demonstrate this cell-transistor interface, firstly an array of transistors
have been employed by the researchers of institute so as to grow the living cells atop
and thereby enabling a silicon chip to directly monitor the activity of cells and to
detect the efficacy of new drugs on these grown living cells. The results can be read
and interpreted from the chip instantly, thus will help in expediting the drug
development.
The technique of growing the living cells on a transistor array is better than the
traditional methods in which the cells need to be destroyed in order to analyze their
322 S. Gupta et al.

inner workings. For example, a patch-clamp electrode is required to facilitate the

interpretation of movement results of ion stream into and out of the cell while ana-
lyzing the consequences of different drugs on a cell’s serotonin levels. This tech-
nique of using patch-clamp electrode will gradually kill and destroy the cell, and
thus the sample can be used only up to a few hours. Contrastingly, the method
employed by Max Planck researchers maintains the usefulness of sample and cell-­
transistor interface as long as nutrients are provided to the cell. In this technique,
firstly the transistor gate is located which has been placed on each living cell directly
below the serotonin receptors, and when the serotonin is passed through the recep-
tor’s ion channel, the voltage potential at the gate of the transistor is varied (John
Wiley & Sons 2007; Johnson 2007). Then, a computer-controlled monitoring cir-
cuitry has been used to record the activity of change in voltage potential which
ultimately modulates the transistor’s source-drain current. The researchers finally
proved the concept and have evaluated that this interface is able to explain the dos-
age/effect relationship of various drugs on serotonin and the use of computer con-
trol circuitry will automatically lead to the automation of such bioelectronics
devices consisting of batteries for drug discovery tests. The next step in their
research is to design the general and more-universal test setups and techniques for
various applications requiring the harnessing of living cells like detection of differ-
ent toxins (John Wiley & Sons 2007).
According to scientists, this research, involving studying the electrical interfac-
ing between living cells and semiconductors, will provide a platform for different
applications and will be used as a basis for the development and acceleration in the
fields of medical prosthetics, neurocomputation, biosensors, and brain research
(Johnson 2007).

17.2.1.3  Artificial Retina

Current research scenario has entered into an era where retinal implants now
seem to be a practical concept owing to the developments in nanotechnology and
nanomaterials. Due to the thin structure, flexible characteristics of SWNTs and
greater efficiency and versatility of other nanoengineered materials, they are
compatible with eye mechanics such as eye muscle contractions (Amiji 2008). In
order to treat macular degeneration, the most common cause of vision loss in
elderly people especially in the age group above 65  years, the researchers at
University of Texas Medical Branch suggested the replacement of light-sensing
nerves with the combination of CNTs and other nanoparticles that have the capa-
bility of sensing the light, converting it into an electrical signal and then transmit-
ting the message to the nerves so as to establish a communication between the
brain and the eye. In the patients suffering from macular degeneration, these
nerves remain intact and the light-­sensing cells in the center of the retina tear
apart. Nanoparticles used in artificial retina can even help and provide color
­resolution (Bourzac 2006; Jain 2013; Amiji 2008).
17  Biomolecular and Cellular Manipulation and Detection (Nanofluidics and Micro… 323

Apart from nanotubes and buckyballs, advancements in nanotechnology have led to

the emergence of certain new fields like nanorobotics, and some nanostructures such as
nanobombs, nanoactuators, nanosensors, nanowires, etc. have evolved in recent years
which have been explained in subsequent sections with their functionalities. Various
disciplines ranging from nanofabrication processes required for manufacturing nano-
actuators, nanosensors, and nanoscale robots to physical modeling at nanoscales have
been brought together by the emanating field of nanorobotics (Berger 2009).

17.3  Nanobots

Nanorobotics is an emerging technology focusing on designing the machines or

robots with the components’ size in nanometers (10–9 m) (Ghosh and Fischer 2009).
Such devices are popularly termed as nanorobots (nanobots), nanites, nanoids,
nanomites, or nanomachines and are in the research and development phase
(Ignatyev 2010; Yarin 2010). The possibility of integration of photolithography,
nanoelectronics, and new biomaterials have opened up the new avenue for manufac-
turing nanorobots for general medical applications, such as drug delivery, diagnosis,
surgical instrumentation, and so on (Cerofolini et al. 2010; Fisher 2008; Yarin 2010;
Scudellari 2018). The field of medicine can be improved to a greater extent due to
the advantage of nanotechnology to transport the numerous amounts of nanobots in
a single injection. With the advent of artificial intelligence, it is possible to program
these nanobots to adapt the environment and perform the functions accordingly
prior injecting them into the body, thus will boost the proper monitoring and treat-
ment of a disease (Saadeh and Vyas 2014; AZoNano 2017). Nanobots have been
used in the Blue Brain Project of IBM which aims at developing the world’s first
virtual brain that will enable human beings to scan themselves into the computers
and will eventually help to preserve the knowledge, skill, and intelligence of a per-
son forever (Markram 2006). The nanobots will monitor the activities and structure
of the central nervous system and will help in uploading the natural human brain
into computers by traveling throughout the circulatory system including the spine
and brain. Thus, the nanobots can act as an interface between the natural brain and
computer and, thereby, will be useful for patients with Alzheimer’s disease and for
persons with hearing disability, allowing them to hear via direct nerve stimulation
(Markram 2006; Markram 2012).
Nanorobotics have found applications in the field of hematology which involves
the various functions ranging from the development of artificial methods for oxygen
transportation inside the body after an extensive attack to the formation of clots with
the better clotting capabilities in life-threatening hemorrhage situations. Hypothetical
nanobots termed as “respirocytes” can act as artificial red blood cells when injected
and perform their functions in emergency cases. Another type of nanobots knows as
“clottocytes” have the capability of mimicking the natural platelets and work as
artificial platelets for halting the bleeding (AZoNano 2017; Saha 2009).
324 S. Gupta et al.

In the field of cancer theranostics, nanobots designed with embedded chemical

sensors and having enhanced detection abilities can contribute in overall manage-
ment of patients as the chances of survival increases and mortality rate decreases if
the cancer is detected in early stages. In addition to accelerating the prognosis of
cancer, nanobots with chemotactic sensors have also the potential of providing the
therapy and targeted treatment according to the different stages and phases of can-
cer through specific programming (AZoNano 2017; Saxena et al. 2015).
Nanobots can also be used to prevent the biohazards and to improve the response
to epidemics. In resource-constrained situations with limited public infrastructure
and where laboratory analysis is not feasible, it is possible to transmit and analyze
real-time information by using nanobots designed with protein-based biosensors
which is much needed in especially war-torn areas and in regions devastated by
epidemic disease (Cavalcanti et al. 2008; AZoNano 2017).

17.4  Nanoactuators

Nanobiotechnology has enabled us to control the substances not only at the molecu-
lar level, but now with the enhancement in research and applied science, we can
manipulate these substances even at the atomic level, having the dimensions in
nanoscales. Cells in our bodies, microorganisms, and all the biological molecules
including enzymes, nucleic acid (DNA, RNA), receptors, proteins, etc. are all nano-
sized; thus the joint use of nanotechnology and biotechnology has various potential
applications ranging from early detection of several lethal diseases to providing
accurate treatment so as to cure the root cause of these diseases (Shoseyov and Levy
2008). Nanoactuators, one of the significant nanotoolboxes, are inevitable outcomes
of nanobiotechnology. A nanoactuator or a molecular dynamo has been developed
and patented by the researchers of University of Portsmouth, UK, in October 2006
to function as an interface between the modern computer era and the living organ-
isms. The size of this actuator working as a DNA-based electronic switch is compa-
rable to almost one-thousandth of a strand of human hair, and so is invisible to
human naked eye (NanowerkNews 2006). This molecular nanoactuator comprises
of a biological motor powered by adenosine triphosphate (ATP, a naturally occur-
ring energy source found in living cells), a microchip’s miniscule channel in which
a DNA strand is anchored and a magnetic bead. In order to generate the electricity,
these elements work together to create a dynamo effect and ultimately, a device is
developed that can emit the electric signals to communicate with the computer. This
DNA switch can be used as a biosensor for the detection of airborne pathogens and
is also useful for detection of toxins. With further modifications, this nanoactuator
technology-based molecular switch can act as an interface between human muscles
and external devices and thus will be useful for designing artificial limbs controlled
by computers for disabled persons. It has the capability of actually acting as a com-
municator or mediator between the silicon (electronic) world and biological world
(NanowerkNews 2006; Phys.org 2006).
17  Biomolecular and Cellular Manipulation and Detection (Nanofluidics and Micro… 325

17.5  Nanobombs

Nanotechnology has also been applied to improve drug delivery by overcoming the
major issues associated with delivery of drugs for the treatment of various diseases
including cancer. In the recent years, nanomedicine (an application of nanobiotech-
nology) has evolved much by focusing on the development of different types of
nanoparticles for drug delivery (Hood 2004; Freitas 2005). Cancer nanomedicine is
aiming to cover a wide range of applications from imaging and diagnosing to treat-
ing cancers with targeted therapies. Cantilevers, nanopores, nanotubes, quantum
dots, nanoshells, dendrimers, nanobombs, and nanowires are some of the tools of
nanotechnology having applications in the treatment of different cancers (Pathak
and Katiyar 2007; Misra et al. 2010; Azad 2015; Sahoo et al. 2017). Among these,
the nanobombs hold great promise as a therapeutic agent for killing cancer cells. An
advantage over other carbon nanotube treatments being considered by scientists is
that with nanobombs, the nanoparticles injected into the body are also destroyed
along with the cancer cells (ScienceDaily 2005; OSUCCC-James 2015). In 2015,
researchers at Ohio State University Wexner Medical Center, USA, have reported
the development of nanobombs that can burst after swelling when exposed to near-­
infrared (NIR) laser light. These bomb-like nanoparticles might help in overcoming
a biological barrier that has blocked the development of agents such as microRNAs
required for the outright killing of cancer cells or for stalling their growth. These
agents perform these operations by varying the activity, i.e., the expression, of genes
in cancer cells (Wang et al. 2016; Zhang et al. 2015).
A novel treatment protocol employing CO2 bubbling-based “nanobomb” system
(shown in Fig. 17.4) has been developed recently for targetedly suppressing Panc-1
pancreatic tumor via low-intensity ultrasound-activated inertial cavitation. This
exogenous therapeutic low-intensity ultrasound (US) irradiation causes the eleva-
tion in temperature, and the endogenous acidic environment around/within tumor
results in low pH value. In response to variation in temperature and pH, this dual-­
responsive system produces and adsorbs the CO2 bubbles due to the presence of
L-arginine (LA) and hollow mesoporous silica nanoparticle (HMSN) carriers.
Depending upon the increase in temperature and reduction in pH value, CO2 bub-
bles will be released quickly by a dual-responsive CO2 release system. Then, before
dissolution, these bubbles will explode timely as a result of triggering action per-
formed by the therapeutic ultrasound waves. Destruction of blood vessels within
panc-1 tumor and instant necrosis of panc-1 cells have been induced by the related
bio-effects, such as mechanical effects, cavitation, shock waves, and so on, as a
result of the explosion of CO2 bubbles. Consequently, the growth of panc-1 solid
tumor will be inhibited and also the normal organs will not be affected much,
thereby, minimizing the side effects to these organs. This novel treatment approach
is a localized physiotherapy, which is expected to greatly reduce damages to normal
organs during cancer therapy unlike the conventional techniques used for treatments
like chemotherapy (Zhang et al. 2015; Wang et al. 2016).
326 S. Gupta et al.

Fig. 17.4 CO2 nanobomb system (US+HMSN-LA-CO2) explosion technical route diagram for
inhibiting the panc-1 tumor growth. (a) Preparation procedure illustration of HMSN-LA-CO2
(dual-responsive CO2 nanobomb), (b) schematic explanation of therapeutic procedure of HMSN-­
LA-­CO2, (c) illustration of CO2 nanobomb system’s therapeutic mechanism, and (d) reaction for-
mulae used for the chemical adsorption and desorption of CO2 by HMSN-LA (Zhang et al. 2015)

17.6  Nanowires

Nanowires (NWs) are the nanostructures in the form of wires having the dimensions
in the range of 10−9 m. Quantum mechanical effects are considerably important at
nanoscales; thus these nanostructures at such a scale are also known as “quantum
wires” (ScienceDaily). The remarkable properties of these nanowires have enabled
them to be used in various applications (UnderstandingNano). One such nanowire
is molecular nanowire which is designed by repeating the organic or inorganic
molecular units. In 2007, researchers at Yale Institute for Nanoscience and Quantum
Engineering, USA, published a novel approach for synthesizing the nanowires
(YaleUniversity 2007). The integration of these nanostructures directly with the
MEMS (microelectronic systems) has been made possible for the first time by this
approach. The technique used by the researchers involved the plugging into the
biochemical system of cells electronically. A tried-and-true process of wet-etch
lithography on silicon-on-insulator wafers available commercially has been used in
order to overcome the various hurdles associated with the synthesis of NWs. The
nanowires synthesized with this novel technique are structurally stable and have the
17  Biomolecular and Cellular Manipulation and Detection (Nanofluidics and Micro… 327

Fig. 17.5 Schematic
illustration of nanowire
sensors in a solution
(YaleUniversity 2007)

capability of detecting the antibodies or other biomolecules with high sensitivity at

affordable costs, thus possessing the potential of revolutionizing the medical diag-
nostic and therapeutic fields. These NW sensors (Fig. 17.5) with label-free reagents
can also sense the live cellular immune response on real-time basis unlike tradi-
tional assays which usually takes hours to detect the response of cells of immune
system (YaleUniversity 2007). This advancement in nanotechnology has speeded
up the diagnostic field as a fully automatic sensor platform for the detection of cel-
lular and molecular arrays can be thought of due to the possibility of seamless inte-
gration of this approach with CMOS technology (Stern et al. 2007).
Enhancements in the development of nanomaterials have made it feasible to
directly interconnect the living cells with the external world, thus allowing the
probing and manipulation of various biological processes occurring across the cell
membranes, inside the whole cells, or between the neighboring cells. These nano-
structures can act as interfaces between the outer world and inside body mechanism
apart from functioning either at the vicinity of a biomolecule’s surface or inside a
cell. In 2007, a report was published in Journal of the American Chemical Society
in which the authors have highlighted the signal-carrying ability of silicon nanow-
ires (Si NWs) to the living cells (Kim et al. 2007). They have demonstrated that as
the cells grow, Si NWs having dimensions in the range of 1–100 nm can directly
penetrate into them without causing any damage. The interface capability of Si
NWs for carrying out the transmission of signals will help in connecting the pros-
thetics to the living tissues electronically and also for developing the biosensors
(Kim et al. 2007).
Rapid progression in various fields like nanotechnology, molecular biology,
microfluidics, biosensors, VLSI, etc. has empowered the integration of all such
processes on a single platform for POC (point-of-care) detection and management
of various diseases so as to pacify their consequences and to prevent the situations
of epidemics and pandemics. Lab-on-chip is one of the state-of-the-art technologies
that have been developed owing to the possibility of easy integration of all the
above mentioned interdisciplinary fields (Gupta et  al. 2016). Further, current
328 S. Gupta et al.

research scenario has entered into an era where collaboration of these diversified
fields has made it feasible to mimic a whole organ on a chip. In the subsequent sec-
tions, the features and applications of lab-on-chip and organ-on-chip have been
highlighted.

17.7  Lab-on-Chip

Lab-on-chip technology implies those techniques that perform various laboratory

operations on a miniaturized scale such as chemical synthesis and analysis on a
single chip leading to a handheld and portable device. In other words, a LoC is a
device which is capable of scaling single or multiple laboratory functions down to
chip format. The size of this chip ranges from millimeters to a few square centime-
ters (Volpatti and Yetisen 2014).
LoC technology has several advantages compared with conventional techniques
such as minimal sample requirement, rapid analysis time, ease of use, minimized
exposure to hazardous materials, and reduced waste generation (Soutter 2019).
LoCs are capable of analyzing metabolites, molecules, proteins, nucleic acids, cells,
and viruses. It can perform fluidic processes, sensing, analysis, and separation of
biochemical samples. LoC is basically the integration of fluidics, electronics, optics,
and biosensors (Giannitsis and Min 2010). Due to the advent of advanced technolo-
gies such as MEMS, NEMS, the integration of large number of interdisciplinary
modules, as shown in Fig. 17.6, on a single chip (Gene-Quantification) is possible
making the LoC designing much easier (Kakkar 2018, Majlis 2013).
LoCs have found applications in various fields including pharmacy, chemistry,
and biomedical area (Gupta et al. 2016), such as immunoassay LoCs used for bac-
teria detection, flow cytometer LoC (for HIV), DNA chips, gene chips, LoC for
cellular analysis, real-time PCR detection chips, etc. (Chin et al. 2012; Grenier et al.
2011). Today, the research focus is shifting from cells and molecules to organs and
tissues on a chip as explained in the next section.

17.8  Organs-on-Chip

The spectacular growth in the entrenched fields of microfluidics and labs-on-chip

has led to the possibility of fabricating organ-on-chip devices. This development of
organs and tissues on a chip will help researchers to fill the void between the o­ ngoing
in vivo experimentation and the available standard in vitro tests. Organs-on-­chips, a
type of microengineered in vitro tissue models, have the potential of achieving bet-
ter throughput through parallelization by combining realistic physiological cell cul-
ture microenvironment with artificial engineering approaches (Van Den Berg 2013).
One such organ-on-chip termed as blood-brain barrier (BBB) on chip has been
described in an article published in 2013 IEEE 26th International Conference on
17  Biomolecular and Cellular Manipulation and Detection (Nanofluidics and Micro… 329

BIOSENSORS/
ELECTRONICS
BIOTECHNOLOGY

LAB-ON-CHIP
(LoC)
MICROFLUIDICS
(SPUTUM, VLSI
BLOOD, URINE
etc.)

SIMULATION
TOOLS (MEMS,
NEMS etc.)

Fig. 17.6  Interdisciplinary fields of LoC (Gupta et al. 2016; Gupta and Kakkar 2018)

MEMS (Van Den Berg 2013). Human bodies have unique feature of preserving the
homeostasis of the brain and preventing toxic elements from entering into the brain.
This feature is termed as blood-brain barrier (BBB) which doesn’t function properly
in patients suffering from neurodegenerative disorders. The authors in this article
have presented a miniaturized BBB model by immortalizing the endothelial cell line
(hCMEC/D3) of human brain on a microfluidic chip consisting of integrated elec-
trodes used for analyzing the tightness of barrier by calculating the TEER (transen-
dothelial electrical resistance) (Van Den Berg 2013; Griep et al. 2013). Then, on a
single nominal device, both the biochemical and mechanical modulation of barrier
function is done by utilizing tumor necrosis factor alpha (TNF-α) for stimulation
and by exposing it to fluid shear stress respectively. This BBB microfluidic platform
will help in evaluating the passage of drugs in order to treat various neurodegenera-
tive disorders (Griep et al. 2013).
In December 2017, scientists at Lawrence Livermore National Laboratory
(LLNL) have claimed the development of a brain-on-chip device in order to predict
and test the effects of various chemical and biological agents on the brain. This
device has the potential of monitoring various brain disorders and also analyzing the
treatment provided by different pharmaceutical drugs without any human or animal
intervention (ScienceDaily 2017).
Thus, Nano-neuroelectronic systems designed by integrating multidisciplinary
will enable brain researchers to enter an exciting era that promises to bring new
insights into neuronal communication.
330 S. Gupta et al.

17.9  Conclusion

Implementation of new nanotechnological techniques in an economical way and

magnification of their impact have revolutionized the biological world. Many break-
through achievements have already been made, and some are still in the develop-
ment phase as described in this chapter. A state-of-the-art LoC technology has
proven to be a useful technique in various areas including theranostics and is serv-
ing as a promising tool to accomplish several objectives ranging from the designing
of point-of-care platforms to the fabrication of organs-on-chip. Thus, we can say
that the ongoing research involves exploration of several technologies, and new
diagnostic tools have been put forth for utility in clinics and laboratories, but as yet
meager is actually accessible in real practice to aid the society.

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Chapter 18
Bio-Based Nano-Lubricants
for Sustainable Manufacturing

Rahul Anand, Mir Irfan Ul Haq, and Ankush Raina

18.1  Introduction

In today’s contemporary manufacturing industry, there is rising demand of high

productivity with low cost along with improved quality. In order to achieve the pres-
ent production rate demand and challenge of cost competitiveness across the global
markets, material removal rate should be enhanced. Increased material removal rate
demands higher values of cutting parameters, i.e. speed, depth of cut and feed rate,
which carry a great risk of tool wear and failure due to enormous heat generation
and friction at cutting zone between chip and tool (Bruni et al. 2006). Plastic defor-
mation also tends to deteriorate the surface integrity which is an important property
in evaluation of productivity of machining processes (Davim et  al. 2008). Chip
flowing over the tool surface tends to carry the major portion of heat, and some por-
tion is conducted by tool itself; thus reducing the temperature at cutting zone will
largely enhance tool life and surface integrity and reduce tool deterioration
(Dudzinski et al. 2004). Thus cutting fluids in modern industry act as an accessory
in reducing the shear zone temperature by reducing chip tool contact length and
improving the thermal conductivity at interface which greatly optimizes the cutting
parameters and improved tool life (Vieira et al. 2001). Primary function of cutting
fluid used in conventional machining is to simultaneously cool and lubricate the
cutting zone thereby decreasing the coefficient of friction which in turn reduces the
cutting forces required for conventional machining operations like turning, drilling,
milling and grinding (Adler et al. 2006).
However issues related to excessive and conventional use of mineral oil-based
cutting fluids have been debated by the researchers lately which involves disposal of
toxic mineral oils in soil and water, and improper handling of mineral oil-based

R. Anand · M. I. U. Haq (*) · A. Raina

School of Mechanical Engineering, Shri Mata Vaishno Devi University,
Katra, Jammu & Kashmir, India

© Springer Nature Switzerland AG 2020 333

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_18
334 R. Anand et al.

c­ utting by machine operators may cause various health hazards and results in deg-
radation of health of the operator (Soković and Mijanović 2001). Shashidhara and
Jayaram (2010) estimated 80% of total health problems are caused due to mineral
oil-based cutting fluids. Purchasing cost of cutting fluids includes 7–17% of total
machining cost (Klocke and Eisenblätter 1997). European Union almost consumes
annually 320  Mt of cutting fluids during machining processes out of which two
thirds of used fluid has to be disposed (Lawal et al. 2013). Shokrani et al. (2012)
estimated non-biodegradable mineral oil-based cutting fluid increases disposal cost
fourfold the purchasing cost which also includes physical and chemical treatment
cost required before disposing them.
Due to increased disposal, treatment cost and health and environmental prob-
lems, researchers are now investing their interest discovering biodegradable vegeta-
ble and esoteric oil (Tschätsch and Reichelt 2009). These vegetable and ester oils
have biodegradability of 90–95% and have environmental compatibility in terms of
biodegradability, toxicity, safe disposal and additives (Kodali and Nivens 2001; Pop
et al. 2008). These vegetable oils provide a vast range of rheological properties in
terms of flash point, viscosity index and low volatility. Debnath et al. (2014) listed
out detailed developments in biodegradable vegetable-based cutting fluids and their
influence on cutting parameters along with reduction in ecological and economical
complications which were found in mineral oils. Simultaneously researchers are
more focused on achieving more clean production by improving the methods cut-
ting fluid applications at cutting zone (Fratila 2009). Dry machining can never be
one solution to the problem as it affects tool life badly (Diniz and Micaroni 2002).
So more convenient ways of near-dry machining (MQL) are now being adapted to
minimize the use of cutting fluids. Sharma et al. (2009) talk about more such lubri-
cation techniques (cryogenic cooling, MQL, flood and high-pressure cooling) dur-
ing conventional machining processes which lead to clean and sustainable
manufacturing. Lawal et  al. (2013) in his research compared vegetable oil-based
MQL lubrication technique and conventional flood lubrication and concluded that
MQL with vegetable oil-based lubrication has better results than other conventional
techniques in terms of process parameters and cost.
With technological advancements in manufacturing industry, nano-cutting fluids
are now being imposed which profitably meet the challenge of heat dissipation dur-
ing machining by providing stability and improved thermal conductivity to base oil
at wide range of temperatures. These nano additives can be classified into metallic,
non-metallic and nanofibres with diameter range up to 100 nm which are dispersed
in base cutting oil (Chol and Estman 1995). Experimental research (Sharma et al.
2015b, 2016; Su et al. 2016) reveals these nanoparticles dispersed in base oil easily
penetrate into cutting zones, and due to their heat extraction and friction reduction
properties, they reduce too wear and cutting forces. MWCNT (multiwall carbon
nanotubes) (Sharma et al. 2019), Al2O3 (aluminium oxide) (Arumugam et al. 2018),
ZnO (zinc oxide) (Battez et  al. 2008) and MoS2 (molybdenum disulphide)
(Rajendhran et al. 2018) are some of the nanoparticles which have improved ther-
mal and tribological properties. Due to enhanced machining performance, addition
of nanoparticles has minimized the use of cutting fluids, saving the environment and
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 335

Eco Friendly
Machining

Vegetable oils for sustainable

Cutting fluids manufacturing

Addition of Enhanced thermal

conductivity, viscocity,
Nanoparticles in heat transfer, surface finish,
Iubricants tool life, chip morphology

MQL
Safe and healthy environment
Lubrication system Effective penetration
Cost and quantity reduction

Machining processes Reduced cutting temperature,

Turning, Milling, Drilling, cutting forces, tool wear,
Grinding surface roughness

Recent Hybrid nanoparticles

Research Bio-based cutting oil
Trends

Fig. 18.1  Flow chart representation of the machining processes involved

decreasing the cost of production. This paper widely discuss about vegetable oils
and heat extraction and friction reduction mechanisms of nanofluids with MQL
technique in conventional machining operations turning, drilling, milling and grind-
ing (Fig. 18.1).

18.1.1  Types of Cutting Fluids

El Baradie (1996) in his research classified cutting fluids along with their composi-
tion and also addressed issues like green machining, recycling of cutting fluids and
their disposal.

18.1.1.1  Neat Cutting Oils

It mainly includes pure mineral oils or mineral oils with some load-carrying addi-
tives such as:
(a) Blends of mineral oil and fatty oil
(b) Blends of mineral oil and sulphurized fatty oil
(c) Blends of mineral oil and chlorofatty oil
(d) Blends of mineral oil and sulpho-chlorinated fatty oil
(e) Extreme pressure additives
336 R. Anand et al.

18.1.1.2  Water-Soluble Fluids

Water-soluble fluids are predominantly mineral oils blended with emulsifiers, and
when this blend is added to water, an oil-in-water emulsion is produced which facil-
itates the high-speed cutting process because of its better cooling capabilities ().
Water-soluble fluids are further classified as.

18.1.1.3  Emulsifiable Oils

These are soluble oils made by blending the oil with emulsifying agents and other
materials which form the dispersion phase in water for long period of time by break-
ing the oil into minute particles. These are further classified as:
(a) General purpose soluble oil (it includes nanoparticles-enriched cutting.)
(b) Clear type soluble oils
(c) Fatty soluble oils
(d) EP soluble oils

18.1.1.4  Chemical (Synthetic Fluids)

These chemical coolants and lubricants include inorganic chemical agents dissolved
in water with no mineral oil. It includes soaps and wetting agents for reduction in
surface tension, nitrides for corrosion resistance, chlorine and sulphur for lubrica-
tion, glycols as blending agents and humectants and germicides to control bacte-
rial growth.

18.1.1.5  Semisynthetic Fluids

This type includes combination of chemical fluids and emulsifiable oils in water
which forms stabilized emulsion with small droplet size that can facilitate heavy-­
duty machining.

18.1.2  M
 ethods of Application of Cutting Fluids
in Conventional Machining

During machining of metals, conversion of energy to heat takes place in the regions
of plastic deformation due to work involved in shearing the workpiece (da Silva and
Wallbank 1999). High temperatures are thus produced on the cutting edges and chip
tool interfaces which control the tool wear rate, tool life, MRR and surface finish of
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 337

the material. Large part of this heat is conducted away by the chip, and the rest is
conducted by the tool which acts as a sink. Researches have shown that on reducing
the cutting, temperature will increase tool life and reduce the tool wear (Khan and
Ahmed 2008). Cutting fluids are thus applied to carry away the heat from the cutting
tool and workpiece interface thereby reducing the temperature which is critical for
tool wear. 7–17% of the total cost of machining is acquired by the cutting fluid alone
(Klocke and Eisenblätter 1997). Several techniques have been developed to increase
the efficiency of cutting fluid and enhance the machining process by environment-­
friendly means.
Along with the improvement in the conventional cooling techniques and reduc-
tion in temperature rise, researchers have focused on environmental problems like
disposability, toxicity, misting, staining and self-cleanliness involved using cut-
ting fluids.

18.1.2.1  Cryogenic Cooling

In cryogenic cooling liquid nitrogen (LN) is applied at cutting tool, workpiece or at

the cutting zone in order to reduce the cutting temperature and enhance low-­
temperature machining (Evans and Bryan 1991). The nitrogen absorbs heat and
evaporates to atmosphere thereby cooling the cutting edges of the tool and by form-
ing a fluid gas layer between the chip and tool interface. Cryogenic cooling is an
environmentally friendly and efficient way of maintaining a safe working tempera-
ture well below the critical or softening temperature of tool (Dhar et al. 2002). Thus
reduction in temperature results in reduced flank and crater wear thereby improving
the product quality and productivity. Cryogenic cooling is more predominant at
lower cutting speed due to more effective penetration of cryogen between chip and
tool interface (Khan and Ahmed 2008). Its cooling capability decreases with
increase in cutting speed due to obstruction in penetration of cryogen in hot chip
tool interface. Turning with carbide inserts with liquid nitrogen cryogenic cooling,
it was observed that tool life improves which attributes to reduction in notching,
abrasion, adhesion and diffusion type of wear.

18.1.2.2  Solid Lubricant/Coolant

Use of conventional cutting fluids cause environmental pollution, ecological

imbalance and serious biological hazards to workers along with increased cutting
cost (Sreejith and Ngoi 2000; Tan et  al. 2002). Now all these factors instigate
researchers to avoid use of cutting fluids with some other cooling methods. Solid
lubrication is one of the techniques which strive to minimize the use of cutting
fluid (Shaji and Radhakrishnan 2003). Molybdenum disulphide (MoS2) and
graphite are most commonly used solid lubricants due to their lamellar structure;
these lamellas incline between loaded surfaces and glide over each other in order
338 R. Anand et al.

to reduce friction and contact. Boron nitride, calcium fluoride and tungsten disul-
phide are other materials which can be used. During turning of AISI 52100 steel
at high speed of 125  m/s, it was observed that due to layered lattice structure,
cutting forces were minimized, and due to good adhesion property of molybde-
num disulphide, lower value of surface roughness (13–15% reduction) than
graphite (7–10% reduction) was observed (Dilbag and Rao 2008; Lathkar and
Bas 2000).

18.1.2.3  High-Pressure Cooling Technique

High-pressure coolant delivery technique allows the coolant to penetrate in tool-­

chip and tool-workpiece interface thereby enhancing the cooling effect and lower-
ing the tool wear rate by effectively lubricating the contact regions (Diniz and
Micaroni 2007; Wertheim et al. 1992). Pressurized coolant thus forms a hydraulic
layer of wedge shape between tool-workpiece interface which facilitates high-speed
machining (Mazurkiewicz et  al. 1989). Researchers have found that pressurized
coolant not only increase the effectiveness of cooling but also reduce the chip tool
contact time by taking the chip off the rake surface thereby significantly improving
the tool life (Ezugwu and Bonney 2005). Turning titanium under high-pressure con-
ditions reduces chip tool interface temperature and cutting forces and improves sur-
face roughness as chip tool contact time is reduced (De Lacalle et al. 2000). Cutting
forces significantly reduce cutting forces while machining Inconel 718 alloy due to
improved lubrication at tool-workpiece interface (Ezugwu et al. 2005).

18.1.2.4  Air/Vapour/Gas Cooling

For protection of ecology and environment, the use of green cutting fluids has
become a major concern in machining. Water vapour and gas emerge as best alter-
natives for cooling and lubrication than conventional synthetic cutting fluids. Liquid
Nitrogen and Nitrogen gas at high pressure serve best operating conditions for
machining. Application of nitrogen, oxygen and CO2 provides lower cutting forces
than dry and wet cooling operations with reduced surface roughness (Altan et al.
2002; Çakıra et al. 2004; Godlevski et al. 1998). Mist application of air-oil at 0 °C
provides simultaneous effect of cooling and lubrication which reduces wear by 13%
as compared to air-jet cooling (Ko et al. 1999). During machining of the AISI 1045
steel (in presence of nitrogen gas, water vapour, mixture of gas and water vapour),
water vapour alleviate friction by filling up the cavities in the cutting zone by capil-
lary action which thus improves tool life twice than dry machining (Liu et al. 2007).
During turning of En32b plain carbon steel, the nitrogen gas provided the best cut-
ting conditions with reduced crater (55%) and flank wear (30%) than dry machining
by reducing the chip tool contact length (Stanford et al. 2009).
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 339

18.1.2.5  Minimum Quantity Lubrication

MQL (minimum quantity lubrication) also referred as near-dry machining or micro-

machining is an environmental-friendly alternative to flood and dry machining.
Lubricant is mixed with air and is injected on the cutting surfaces through different
techniques (Varadarajan et  al. 2002). MQL is the best lubrication technique that
leads to clean and sustainable production along with better heat convection, tool life
and surface finish and improved chip morphology (Philip et  al. 2001; Wertheim
et al. 1992). Lubricant is either mixed inside or outside the nozzle with compressed
air to form an aerosol which is applied to the cutting interface with the help of the
nozzle with industrial range of 10–100  ml/h (Kamata and Obikawa 2007).
Biodegradable vegetable oils as cutting fluids are preferred because of their superior
lubrication performance at high pressure. MQL helps in reducing wear that are sen-
sitive to temperature (abrasion wear and diffusion wear) thereby maintaining the
hardness and reducing the notch growth in tool. In investigations it was observed
that chip tool contact length and cutting forces reduced with MQL technique than
conventional dry and wet turning. MQL of air-oil mixture when sprayed at
0.276 Mpa through 0.762 mm via nozzle at low cutting speed reduces tangential
cutting force by 26.6% than in dry machining and 32.2% of that in flood cooling (Li
and Liang 2007).

18.1.2.6  Nano-Enriched Cutting Fluids

Researchers have investigated that addition of nanoparticles enhance the machining

and tribological properties of the cutting fluids. Nanoparticles with properties like
rolling, sliding and filming action ensure better lubrication thereby reducing power
consumption and cutting forces. Observations also tell that addition of nanoparti-
cles not only penetrates inside shearing zone but also increases heat transfer capa-
bility of the cutting fluid as nanoparticles have much higher thermal conductivity
than liquid alone as shown in the table. Nanoparticles with MQL lubrication tech-
nique are now being investigated as new research trend in the field of lubrication.

18.1.3  M
 QL (Minimum Quantity Lubrication) Application
Technique

MQL technique involves spraying mixture of lubricant with air at a high pressure at
machining zone with help of nozzle (Duchosal et al. 2013). MQL system consists of
nozzle jet to spray the air-oil mixture, pressure gauges and oil reservoir. Due to the
venture effect, a vacuum is created inside the mixing chamber which sucks the
340 R. Anand et al.

lubricating oil from the oil sump (Khan et al. 2009). The compressed air passing
through the chamber atomizes the lubricant stream into fine aerosol micron-sized
particles which is sprayed in cutting zones as mist by the nozzle. It effectively acts
as a coolant and penetrates deep into the tool-workpiece interface.
There are two main methods of cutting fluid application to the machining
zones in MQL.

18.1.3.1  Internal Application

In this application the oil and compressed air are applied to the cutting zone inter-
face through tool itself. It’s also called as through-tool application. Further it is also
divided into two types.
(i) Single channel: In this system of MQL technique, compressed air and oil are
mixed in mixing chamber before being supplied through cutting tool to machin-
ing zone.
(ii) Dual channel: Compressed air with cutting fluid in this delivery system are dif-
ferently supplied and are mixed just before the machining zone.

18.1.3.2  External Application

In this application the oil and compressed gas are applied to the cutting zone through
external nozzle arrangement. Furthermore there are two more methods of external
application.
(i) Ejector nozzle: The oil and compressed air are supplied differently, and atomi-
zation takes place just outside the nozzle.
(ii) Conventional nozzle: Micro-sized fine aerosol mist is made in external atomizer
and is then sprayed through the conventional nozzle.
Zeilmann and Weingaertner (2006) investigated the effect of external and internal
delivery applications on drilling temperature by drilling titanium alloy (Ti-6AL-4V).
It was observed that temperature rise in internal delivery system was 50% less than
external delivery system due to improper penetration of externally supplied aerosol
mixture. Tsao (2007) on milling aluminium alloy (A6061P-T651) investigated that
using sulphurous boric acid cutting fluid in MQL reduces average flank wear by
12.5% compared to dry milling. Along with flank wear, surface finish and tool life
also improved using MQL tan wet and dry machining using different types of car-
bide tools (Kamata and Obikawa 2007). Kishawy et al. (2005) investigated cutting
forces and wear and surface roughness conditions in both MQL flood and dry lubri-
cation. MQL showed preferable results over dry machining due to its economic and
environmental advantages.
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 341

18.2  Vegetable Oil-Based Lubricants

18.2.1  P
 hysicochemical Properties of Vegetable Oil-Based
Lubricants

Bio-based lubricants which are usually vegetable oils and other natural sources pos-
sess less toxicity and eco-friendly biodegradability. Vegetable oils which can be
edible and nonedible and which differ in geographical and tropical regions of the
world can be used as bio-lubricants. Main emphasis nowadays is laid on nonedible
vegetable oils which are considered as unused crops (Atabani et al. 2013). Principal
component of these vegetable oils is triacylglycerols which constitute 98% compo-
sition followed by diglycerols and fatty acids (Rudnick 2005). This triglyceride
structure is responsible for structural stability and high viscosity at high machining
temperatures.

18.2.1.1  Viscosity

Viscosity plays an important role in reducing wear and metal-to-metal contact

(Salimon et  al. 2010). High viscosity measures more resistance to flow, and less
viscous lubricant has less resistance to flow (Mobarak et  al. 2014). Long carbon
chain length, compact branched and saturated structure enhance the viscosity of the
oil (Knothe and Steidley 2005; Rudnick 2005). There are various modification tech-
niques through which viscosity of the vegetable oils can be improved to sustain
viscous properties at higher machining temperatures. Presence of one double bond
will increase the viscosity of oil, whereas presence of two or more double bonds
will decrease the viscosity (Rodrigues et  al. 2006). Epoxidized soybean oil pos-
sesses high viscosity at extreme cutting temperatures than other vegetable oils (Ting
and Chen 2011).

18.2.1.2  Viscosity Index

It is the measure of variation in viscosity with temperature. The higher the viscosity
index of oil, the lower is the variation with increase temperature. Oil having high
viscosity index will maintain the thickness of the film at higher temperatures which
reduces wear and enhances cutting conditions (Masjuki et al. 1999). Generally veg-
etable oils possess high viscosity index than mineral oils. Canola, palm oil-based
lubricants, showed higher viscosity index than mineral-based cutting oils due to
their enhanced intermolecular interactions and polyunsaturated structure (Sripada
et al. 2013).
342 R. Anand et al.

18.2.1.3  Flash Point

Flash point is an important property of a lubricant which refers to the lowest tem-
perature at which a particular lubricant will turn to form vapours. Higher flash point
thus minimizes the risk of leakage and thus provides safe machining operation at
various range of temperatures (Gnanasekaran and Chavidi 2018).

18.2.1.4  Pour Point

Pour point is another important characteristic of lubricating oil which is defined as

lowest temperature at which lubricant will become semi-solid and loses its ability to
flow. Thus lubricants with low flash point are more suitable for machining at low
temperatures (Benchaita and Lockwood 1993). If lubricant doesn’t possess low
pour point property, the lubricant will cease to flow at low temperature and will
increase friction and wear during machining. For most of the vegetable oil pour
point is lower than −10 °C which results in poor flow of oil at low temperatures due
to bending and continuous stacking of triglyceride structure and formation of
macro-­crystals (Asadauskas and Erhan 1999; Quinchia et  al. 2012; Rhee et  al.
1995). These crystal structures and strong intermolecular bonding sometimes cease
the ability of oil to flow at low temperatures which attributes to loss in kinetic energy
due to self-­stacking (Erhan et al. 2006). Oils that have more unsaturated fatty chains
will have lower pour points; rapeseed oil (−21 °C) has lower pour point than olive
oil (−10 °C) due to increased unsaturated fatty chains which restricts the formation
of packed crystals during cooling (Gryglewicz et al. 2003).

18.2.1.5  Oxidation Stability

Oxidation stability of a lubricant refers to the capability of the vegetable oil to

resist reaction with oxygen, the rate of which is also influenced by pressure, tem-
perature and presence of impurities (Mobarak et al. 2014). A lubricant should pos-
sess high oxidative stability as low oxidation stability may lead to ­polymerization
which increases viscosity and degrades the functional properties of lubricant on
machining (Asadauskas et  al. 1996; Lal and Carrick 1994; Suda et  al. 2002).
Critical factor that influences the oxidation stability is the presence of polyunsatu-
rated compounds in the molecular chains which can easily react with oxygen from
oxides, peroxides and acids (Wu et al. 2000). Thus the higher is the unsaturation,
the more is the chance of oxidation (Fox and Stachowiak 2007). Removal of β-CH
group allows the formation of carboxylic acid which deteriorates the quality of
lubricating oil (Zulkifli et al. 2014).
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 343

Table 18.1  Physicochemical properties of different vegetable oils

Viscosity Density × Flash Pour
40 °C 103 point point Viscosity
Vegetable oil (mm2/s) kg/m3 (°C) (°C) index
Sunflower oil (Rac and Vencl 2009) 47.6 0.917 245 −20 218
Rapeseed oil (Arumugam and Sriram 35.0 0.930 320 −10 220
2013)
Palm oil (Barnwal and Sharma 2005) 39.6 0.918 267 – –
Soybean oil (Honary 1996) 29.0 0.913 328 −10 246
Jatropha oil (Mofijur et al. 2012) 35.4 0.918 186 –
Karanja oil (Bobade and Khyade 2012) 40.2 0.924 225 −3 –
Coconut oil (Nakpong and 28.1 0.920 – – –
Wootthikanokkhan 2010)
Safflower oil (Singh and Singh 2010) 31.3 0.914 260 −06.7 –
Calophyllum inophyllum oil (Atabani 71.9 0.896 221 4.3
et al. 2013; Habibullah et al. 2015)

Plant oil-glycerine ester consists of different fatty acids with critical points and
β-CH group (Wagner et al. 2001) (Table 18.1).

18.3  Role of Nanoparticles in Cutting Fluids

In recent approaches in order to increase the lubricity of base oil in MQL, scientists
have used nanoparticles along with base oil which significantly improve thermal
and heat transfer capabilities, reduce frictional coefficient and increase load-bearing
capabilities of the mechanical systems. Adhesion and stress concentration were
reduced to a large extent with the help of nano-cutting fluid thereby reducing
mechanical failure and wear (Chang and Friedrich 2010). Sharma et  al. studied
improved thermophysical properties and reduced cutting forces, surface roughness
and tool wear relative to base fluid used alone which improved machine perfor-
mance (Sharma et al. 2015a). Kumar et al. (2012) recorded that increase in concen-
tration of nanoparticles increases thermal conductivity which reduces the cutting
zone temperature by easy extraction of heat from cutting zone. A variety of mecha-
344 R. Anand et al.

nisms that are involved in the enhancement of lubrication properties of the cutting
fluid have been explored.

18.3.1  Mechanism of Nanolubrication

18.3.1.1  Ball Bearing/Rolling/Sliding Effect

Rapoport et al. (2002) investigated layered materials like graphite; MoS2 when used
as nano additives in cutting fluids eliminate the metal-to-metal contact between
asperities due to their slippery nature that leads to fast displacement from contact
area. Such effect facilitates the shearing nature of the cutting fluids. Wu et al. (2007)
studied the transition from sliding to rolling friction and deposition of nanoparticles
(CuO) in the worn surfaces which decreases the shear stress and improves the tribo-
logical property of cutting fluids.

18.3.1.2  Polishing Mechanism

It is a surface enhancement phenomenon in which nanoparticles penetrate into rub-

bing surfaces and polish the surface which decrease the contact wear of mating
surfaces. Tao et  al. (1996) studied the polishing effect of diamond nanoparticles
dispersed in paraffin oil which increased the hardness of the rubbing surface than
the test material. Lee et al. (2009b) studied the surface enhancement property of the
nano oil by comparing the friction coefficient of disc type specimen dipped in min-
eral oil and nano oil.

18.3.1.3  Mending Mechanism

The nanoparticles accumulate over the contact surface and compensate for the lost
mass on the contact surface thereby reducing the wear scars resulting in smooth
surface (Lee et  al. 2009a). Liu et  al. (2004) investigated the mending effect and
mechanism of copper nanoparticles on pin-on-desk setup. SEM and STM observa-
tions exhibit the presence of copper in the worn-out areas thereby reflecting the
contribution of mending effect.

18.3.1.4  Formation of Tribofilm

This process produces a protective film over the mating surfaces. Nanoparticles on
reacting with the surface layer of the material produce some tiny secondary particles
which help in smoothening of nano bumps on the mating surfaces (Gupta and
Harsha 2018). Hu et  al. (2002) demonstrated the tribofilm formation by adding
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 345

magnesium borate (10 nm) in SN 500 oil which reduced the coefficient of friction
and surface wear by forming the protective wear film over the mating surfaces.

18.3.2  Preparation of Nanofluids

18.3.2.1  Two-Step Method

Most common method for the preparation of nanofluids is two-step method in which
powder form with specific size of nanotubes and nanoparticles are produced as first
step. During second step mixing of these nanoparticles is carried out in the base
fluid directly with the help of magnetic stirrer, ultrasonic devices or homogenizer
(Drzazga Michałand Dzido et  al. 2012; Duangthongsuk and Wongwises 2009;
Hwang et al. 2007; Khairul et al. 2014; Manimaran et al. 2014). Two-step method
works well with oxide nanoparticles and metallic nanoparticles as well (Manna
2012). Al2O3/water and TiO2/water nanofluids were prepared using two-step method
of nanofluid preparation (Chon et  al. 2005; Haghighi et  al. 2013; Li et  al. 2008;
Murshed et al. 2005; Wang et al. 2009). Li et al. (2008) using two-step method pre-
pared Cu/water fluid to check the influence of pH value and surfactant addition on
thermal conductivity. By two-step method, preparation of nanofluids on mass scale
is possible which has already increased the rate production in industries; however
problem of transportation and storage cannot be avoided in this process (Yu et al.
2012). Formation of agglomerates due to high surface energy of nanoparticles is
also a major disadvantage of two-step method which is further improved by one-­
step method in preparation of nanofluids (Mohammed et al. 2011). However two-­
step method can be used to form nanofluid solution with any base fluid (Wang and
Mujumdar 2007).

18.3.2.2  One-Step Method

One-step method combines both production and deposition of nanoparticles as

nanofluids. In this method of preparation, problem of storage and transportation is
ward off, and agglomeration of nanoparticles is minimized which enhances the sta-
bility of nanoparticles (Li et  al. 2009). In one-step process, nanofluid is directly
prepared by physical vapour deposition (PVD) technique or by condensation tech-
nique known as VEROS (vacuum evaporation onto a running oil substrate) (Akoh
et al. 1978). Eastman et al. (1996) directly dispersed the vapours of condensed metal
to nanoparticles in the base fluid thereby modifying the VEROS technique of one-­
step method. Direct evaporation and condensation of one-step method developed by
Choi et  al. (2002) provides enhanced stability and largely controls the size of
nanoparticles. Lo et al. (2005) introduced a submerged arc nanoparticle synthesis
system (SANSS) using two different dielectric liquids which enhances stability and
minimizes agglomeration effectively. Nanoparticles produced are of polygonal,
346 R. Anand et al.

square, circular and needle-like shape. Later on Chang and Kao (Chang and Kao
2007) modified this technique and improved the nanoparticle synthesis both quanti-
tatively and qualitatively. Disadvantage of this method is residual reactants that are
left after incomplete reaction later arise as impurity in nanofluid solution, and other
disadvantage is its compatibility with low vapour pressure base fluids only (Wang
and Mujumdar 2007).

18.3.3  Importance of Nanofluid Stability

Stability of nanoparticles means nanoparticles do not tend to agglomerate with pas-

sage of time at a significant rate (Yu et al. 2012). Stability is hence susceptibility of
nanoparticles to agglomerate due to high surface energy which not only blocks
microchannels but also influence thermophysical properties like thermal conductiv-
ity, density and viscosity with time (Ghadimi et al. 2011). Rate of agglomeration
depends on the frequency of collision and probability of cohesion during collision
due to Brownian motion. Stability of nanoparticles is the basic requirement for its
wide application and utilization. Stability of nanofluids depends on preparation
method, type of base fluids, sonication time and added surfactants. Stability is
achieved when electrostatic repulsive forces between the nanoparticles are higher
than attractive forces (Missana and Adell 2000; Popa et al. 2010). Agglomeration is
generally reduced by steric and electrostatic mechanisms. In steric stabilization
mechanism, additives like surfactants are added which form a protective layer over
the nanoparticle and cease its ability to agglomerate or collide with other nanopar-
ticle (Zhu et al. 2007). In electrostatic stabilization adsorption of ions create an ionic
layer over the nanoparticle surface which enhances the repulsive forces between
nanoparticles thereby increasing the stability of nanofluid (Mukherjee and Paria
2013) (Fig. 18.2).

18.4  Nanoparticle-Enriched Cutting Using MQL

18.4.1  MQL-Assisted Drilling with Nanoparticles

Minimum quantity of lubrication has largely reduced cost of machining and has
enhanced machining parameters on large scale. Attempts to reduce the use of cut-
ting fluid in machining are turning out to be a good alternative than flood and dry
machining. MQL drilling is found out more promising than dry and wet conditions
for low aspect ratio, and with further modifications in supply and cutting fluid, high
aspect ratios can be achieved by Mathew and Vijayaraghavan (2017). Nam et al.
(2011) studied the characteristics of nanofluid micro-drilling using MQL on alu-
minium 6061. Varying the concentration of nanodiamonds and type of base fluid, it
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 347

Fig. 18.2  Fishbone diagram representation of various parameters involved in MQL-assisted

machining

was observed that nanodiamond-enriched MQL improves the quality of holes and
lubrication which attributes to rolling, ball bearing and cooling characteristics of
nanoparticles. Furthermore 1% of nanodiamond was more effective in reduction of
torque and thrust forces than 2% of nanodiamond. Huang et al. (2016) analysed the
micro-drilling operation with different drilling conditions. It was concluded that
applying nanodiamonds in vegetable oil with MQL reduces the machining zone
temperature due to improved heat transfer rate by nanoparticles. Application of
nanoparticles also reduces the burr around the holes improving the quality of holes.
Addition of nanoparticles reduces forces and torque required for drilling thereby
improving the tool life of drill. Nam et  al. (2015) conducted 25 experiments by
multi-optimization techniques (RSM and GA) and deduced that minimum thrust,
and torque forces at high spindle speed were obtained at 2 vol% of nanodiamonds
in conventional oil. Considering same parameters (drill diameter, spindle speed,
feed direction and concentration), Chai et al. (2016) dispersed MWCNT in hydro-
genated oil using surfactants. TEM and FTR results analysis shows increase in ther-
mal conductivity with some abrupt changes at different temperatures. 9.8% increase
in thermal conductivity by adding 100 ppm nanoparticles at 50 °C was the highest
observed value. Chatha et al. (2016) investigated influence of Al2O3 mixed nano-
fluid (1.5 vol%) on drilling 6063 aluminium with HSS tool. Addition of nanoparti-
cles showed better machining results in terms of surface roughness, cutting speed
and thrust forces as compared to dry, flood and pure MQL conditions due to their
enhanced lubricating and cooling characteristics. Furthermore increase in number
of holes drilled and reduction in chip contact length were observed with nanofluid
MQL machining than dry and pure MQL machining. Garg et al. (2016) performed
computational modelling using different techniques (ANFIS and GP), and relation
348 R. Anand et al.

between feed rate, drill diameter and MRR was established. For lower values of
torque and thrust forces, drill diameter was critical parameter.
Mosleh et  al. (2017) experimentally compared performance of nanodiamond
(ND) and molybdenum disulphide (MoS2) in alcohol-based lubricant under extreme
pressure test. Results showed that addition of MoS2 increases load-carrying capac-
ity by 16% and increases service life of tool by 25%; on the other hand, dispersion
of nanodiamond in base oil reduced the service life and has unfavourable response
on tribological and lubrication properties of nanofluid. There is increase in tool life
with addition of MoS2 by 25%, while ND mixed nanofluid deteriorates both lubrica-
tion and tribological properties. Addition of TiO2 nanoparticles increases heat trans-
fer and lowers the drilling temperature at interface as compared to dry and base
fluids (Salimi-Yasar et  al. 2017). Nam and Lee (2018) investigated influence of
nanodiamonds in vegetable oil on machinability of titanium alloy (Ti-6Al-4V).
Results showed that nanodiamonds (35 nm) at low feed rate (10 mm) penetrate deep
into drilling zones and provide ball-bearing effect which reduces the thrust force
and torque required. Chip adhesion with drill surface and burr formation signifi-
cantly reduced (Table. 18.2).

18.4.2  MQL-Assisted Grinding with Nanoparticles

Shen et al. (2008b) studied the influence of Al2O3-enriched nanofluid in grinding

cast iron with MQL. Different modes of lubrication, dry, flooded, pure water, syn-
thetic oil (5 vol%) with MQL, water-based MQL with Al2O3 and ND nanofluid of
1.5 vol%, were experimentally used in this study. It was observed that grinding ratio
increases with larger fractions of Al2O3 (4  vol%) due to formation of tribofilm
between grinding wheel and workpiece. MQL with Cimtech 500 outperformed
other modes of lubrication in reducing surface roughness. 2.5% Al2O3 provided bet-
ter surface finish than any other concentration in base fluid. Furthermore
nanodiamond-­rich nanofluid provided better results than Al2O3-rich nanofluid. On
increasing flow rate in MQL, cooling rates at grinding interface can be enhanced.
Using same setup as Shen et al. (2008a, b), investigated effect of MoS2 nanopar-
ticles in grinding using paraffin oil, soybean oil and CANMIST as base oil with
MQL lubrication technique. It was recorded that MoS2 with CANMIST oil reduces
grinding force by 27% thereby improving G-ratio by 46%, superior of all other
base fluids.
Alberts et  al. (2009) investigated experimentally the effect of nanofluid with
varying size of graphite nanoparticles (xGnP) on machining D2 steel with MQL
mode of lubrication. It was observed that large-size nanoparticles (15 μm) effec-
tively reduce grinding forces, surface roughness and grinding energy than small-­
size nanoparticles (1 μm).
Kalita et  al. (2010) studied the grinding performance of soybean mixed with
MoS2 nanofluid. 25% reduction in coefficient of friction was recorded with nano-
mixed MQL as compared to flood lubrication and 10% reduction as compared to
Table 18.2  Literature review of MQL-assisted drilling with nanoparticles
Parameters Mode of
Nanoparticle Cutting Depth of nanofluid
Author Base fluid (size) Workpiece speed Cut Feed rate supply Process findings
Nam et al. Paraffin and ND (30 nm) Aluminium 60,000 RPM 0.4 mm 50 mm/ MQL No. of holes drilled increased with use
(2011) vegetable oil 6061 min of nanofluid due to enhanced cooling
and lubrication rate
In order to reduce drilling torques and
thrust forces, 1% of ND was effective
than 2% of ND
Huang Vegetable oil ND (<100 nm) Aluminium 48,000 RPM 0.52 mm 8 μm/rev MQL Addition of (2 wt%) of nanofluid
et al. alloy 7075-T6 reduces the drilling torque and
(2016) improves hole quality by reducing the
burrs
Nam et al. Paraffin and ND (30 nm) Aluminium 60,000 RPM – 15 mm/ MQL
(2015) vegetable oil 45,000 RPM min
30,000 RPM
Chai et al. Hydrogenated MWCNT Steel 1800 RPM 20 mm 0.02 m/ – A 10% increase in thermal conductivity
(2016) oil (10–12 nm) min was observed with a very less addition
of nanoparticles in the base fluid
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing

Chatha Soybean oil Al2O3 (20 nm) Aluminium 30, 53.7 m/ 20 mm 60 mm/ MQL HSS drills drilled nearly 200 holes with
et al. 6063 min min less burr formation in MQL and
(2016) flooded lubrication in response to 27 in
dry drilling
Nanoparticles along with vegetable oil
enhance the lubrication properties and
reduce friction and wear thereby
forming as protective coating on the
surface
(continued)
349
Table 18.2 (continued)
350

Parameters Mode of
Nanoparticle Cutting Depth of nanofluid
Author Base fluid (size) Workpiece speed Cut Feed rate supply Process findings
Mosleh Boelube oil MoS2 4340 steel 9.144 m/min – 0.63 mm/ – 2–4% by weight concentration of MoS2
et al. 70,104 (70–100 nm) min increased the load-carrying capacity up
(2017) ND (3–7 nm) to 16% of base fluid
0.5–1% by weight concentration of ND
enhanced the tribological and lubricity
of base fluid thereby increasing tool
life by 25%
Garg et al. Vegetable oil ND Aluminium 60,000 RPM 15 mm/ MQL Drill diameter and feed rate were
(2016) (nanodiamond) 45,000 RPM min optimized as critical parameters for
30,000 RPM 12.5 mm/ higher MRR
min
10 mm/
min
Salimi-­ Soluble oil TiO2 (20 nm) Steel 1800 RPM 20 mm 0.02 m/ – Addition of TiO2 enhances the thermal
Yasar min and lubricating properties with
et al. increased heat transfer rate than base
(2017) fluid alone
Nam and Vegetable oil ND (35, 80) Ti-6Al-4V 60,000 RPM 0.4 mm 10 mm/ MQL Small size (35 nm), high weight
Lee min concentration 0.4% and low feed rate
(2018) 10 mm/min enhanced machinability
Burr formation and chip adhesion were
minimized due to bearing characteristic
of nanoparticles at drilling zone
R. Anand et al.
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 351

pure MQL using soybean. Furthermore SEM and EDS analysis confirmed presence
of Mo-S-P multilayer and tribolayer that reduces frictional wear between machining
surfaces and enhances G-ratio without reducing material removal rate.
Kalita et al. (2012a) using EN24 and cast iron as working material studied the
influence of MoS2-rich paraffin oil and soybean oil under different lubricating con-
ditions. 50% increase in G-ratio along with reduction of frictional coefficient (min
0.22) and 53% reduction in energy consumption was observed with both soybean
and paraffin oil-based MQL lubrication. Changing the abrasive size on grinding
wheel on same setup as 508–356 μm (Kalita et al. 2012b) recorded 48–52% reduc-
tion in force ratio along with reduction of peak temperature of cutting zone by 8.5%
on addition of 2 wt% of nanoparticles. X-ray and SEM microanalysis showed the
presence of plate-like lamella of Mo-S-P layers (molybdenum sulphur phosphorus
tribofilm) thereby providing enhance lubricating properties by shearing and rolling
mechanisms.
Prabhu et  al. (2015) using fuzzy logic neutral technique analysed the surface
roughness and microcracks on machining D3 tool steel. Using ANOVA analysis it
was observed that cutting speed was the most important factor (65.1% with CNT
and 58.38% with/without CNT) that influence the surface roughness of steel work-
piece. Addition of MWCNT improved the surface roughness and microcracks.
ANN model developed produces surface roughness close to actual value with mini-
mum error of 0.88–9.3% and hence can be used to record surface finish values
before machining.
Vasu and Kumar (2011) experimentally studied the influence of adding Al2O3
nanoparticles with emulsifier as base fluid on machining steel EN-31 workpiece.
20–30% reduction in machining temperature was observed at wheel workpiece
interface. FEM model used records that 1% addition of Al2O3 reduces surface
roughness and energy partition.
Prabhu and Vinayagam (2012) using Taguchi analysis investigated the influence
of CNT nanoparticles in grinding AISI D3 tool steel. Depth of cut, spindle speed
and feed rate were considered as design factors, and eight experiments were per-
formed using L8 orthogonal array. Minimum surface roughness (0.4478 μm) was
recorded using CNT nanofluid, and crack width recorded with CNT also reduced
from 2.22 to 1.93  mm. Using same setup as Vasu and Kumar (2011), Lee et  al.
(2012) considering antitoxic and super tribological properties of nanodiamond and
Al2O3 mixed them with 150 and 20 nm each at 4% and 3% vol each in paraffin oil.
Results of machining were compared with dry and pure oil-based MQL lubrication
conditions. MQL with nanofluid was more effective in reducing cutting forces than
dry and pure MQL. High concentration along with small diameter of nanoparticle
reduces cutting forces significantly. Furthermore large size of nanoparticle effec-
tively reduces surface roughness.
Mao et  al. (2012) experimentally studied the performance of Al2O3 nanofluid
with MQL technique on machining AISI 52100 hardened steel with aluminium
oxide abrasive grinding wheel. Reduction in cutting zone temperature (40%),
decrease in grinding forces and improved surface morphology was recorded with
Al2O3 nanofluid MQL than pure water MQL grinding. Furthermore ball bearing and
352 R. Anand et al.

rolling mechanisms of nanoparticles effectively enhance lubricating and cooling

conditions at cutting zone.
Mao et al. (2013b) also investigated influence of air pressure and nozzle angle
during machining with Al2O3 nanofluids. Spraying parameter (0.2, 0.4, 0.6, 0.8 MPa)
pressure with nozzle direction and spraying distance 20, 40 and 60 mm were used
experimentally. It was observed that optimized parameters can be obtained with
nozzle set at 15° with horizontal than tangential or directly towards wheel.
Prabhu and Vinayagam (2013) investigated effect of grinding glass with SWCNT
using water as base fluid in MQL system of lubrication. Electrolytic process tech-
nique (ELID) was used with metal-bonded diamond grinding wheel for machining.
Reduction in surface roughness and microcracks from 0.3758 to 0.1791  μm and
2.88 to 1.58 was calculated with atomic force microscopy.
Mao et al. (2013a) concluded that higher concentration (1, 3, 5 vol%) of Al2O3
nanoparticles reduces grinding forces (2.32, 2.19, 2.12 N/mm). It was further inves-
tigated that oil-based MoS2 require lower grinding force than water-based nanofluid
in MQL-based nanofluid machining.
Li et al. (2013) studied surface heat generation on the surface of three workpiece
(45 steel, 2Cr13, zirconia ceramics) through numerical simulation. Grinding opera-
tion was performed under three lubricating conditions: dry, flood cooling and oil-­
based pure MQL and MQL with CNT nanoparticles. It was observed that CNT
nanofluid with MQL effectively reduces the surface temperature than any other
mode of lubrication thereby enhancing the surface quality and minimizing the burns
on the surface of grinding wheel. Addition of surfactant (SDBS) reduced the chance
of agglomeration and enhanced cooling and lubrication properties of the nanofluid.
Jia et al. (2014) experimentally investigated influence of machining with nano-
fluid of MoS2, PCD (polycrystalline diamond) and ZrO2 nanoparticles using MQL
technique. Results were compared with dry, water-based flood cooling, pure MQL
using soybean oil and nanoparticle with mixed MQL. It was observed that tangen-
tial forces decreased by 45.88% in pure MQL grinding, 62.34% in nanofluid-based
MQL and 69.33% in flood grinding. Furthermore it was observed that MoS2 forms
a physical layer of molybdenum trioxide on the surface which reduces the load-­
carrying capacity at the grinding zone.
Wang et al. (2014) studied the relationship between crack formation and surface
morphology of the workpiece (quenched 45 steel) using MoS2 nanofluid-based
MQL technique through mathematical model. Bump height reduces with increase
in speed and with increase in number of cracks, whereas when a number of cracks
reduce with increase in peripheral speed, the bump height increases with increasing
crack length. Experimental values were smaller than simulated values which attri-
butes to cooling and lubrication effects of nanoparticles.
ManojKumar and Ghosh (2015) investigated performance of MWCNT mixed
nanofluid in machining of AISI 52100 steel using small amount of cutting fluid
lubrication (SQL). Results of dry, oil-based flood lubrication, oil-based SQL and
nanofluid mixed SQL were compared. It was observed that enhanced thermal con-
ductivity which improved chip morphology and minimum coefficient of friction
(0.07) was recorded with 1  vol% of MWCNT.  G-ratio improved with MWCNT
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 353

nanofluid, and results of surface roughness were comparable with flood lubrication
using SQL.
Mao et al. (2014a) performed grinding of AISI 52100 steel with nanofluid using
MQL technique. Canola oil as cutting fluid, dry, deionized water, Al2O3 with MQL
and MoS2 with MQL were used for experiments. It was observed that MQL with
nanofluid due to their rolling and sliding properties at grinding zone reduce the
frictional coefficient and grinding forces thereby improving the surface finish of the
workpiece than any other mode of lubrication.
Zhang et  al. (2015c) compared performance of different lubricating oils (soy-
bean oil, rapeseed oil, palm oil) in grinding 45 steel workpiece using MoS2 (2 wt%)
nanofluid-based MQL. Addition of MoS2 in soybean oil enhanced viscosity which
further improved lubrication properties of base fluid reducing grinding forces and
grinding energy. Adding CNT, MoS2 and ZrO2 nanoparticles at different concentra-
tions, each (1, 2, 3 wt%) (Zhang et al. 2015b) concluded that 2 vol% of CNT showed
best cooling effect due to its higher conductivity than any other concentration of
nanoparticles. Using same experimental conditions (Zhang et al. 2015a), compared
grinding energy of MoS2, CNT and ZrO2 in colza oil as base fluid. MoS2 with jet
MQL recorded 32.7% J/mm3 less specific grinding energy than that of CNT
and ZrO2.
Zhang et  al. (2016) experimentally investigated the influence of nanofluids
(MoS2, CNT, MoS2-CNT) with different concentrations (2, 4, 6, 8, 10, 12 vol%).
Increasing the surface roughness resulted in increase in surface roughness value
from 2% to 12%. Furthermore lowest G-ratio was observed with MoS2-CNT which
attributes to physical collaboration of both nanoparticles in lubrication mechanism.
Setti et al. (2015) analysed the influence of Al2O3 and CuO nanofluids on machin-
ing titanium alloy with MQL technique. Considerable reduction in coefficient of
friction and cutting temperature was observed with water-based Al2O3 nanofluid
than with CuO-based cutting fluid. Chip morphology also revealed about cooling
and antiwear and self-cleaning lotus effect of nanoparticles.
Sinha et  al. (2017) experimentally analysed the performance of nanofluids
(Ag, ZnO) while machining Inconel 718 using considerably small amount of
cutting fluid using SQL. Significant reduction in grinding forces, wear and small
frictional coefficient was recorded with use of ZnO nanoparticle with improved
surface finish on machined workpiece. This attributes to better lubricity and spread-
ing ability of ZnO nanoparticles.
Wang et al. (2017b) compared the performance of Al2O3 at different concentra-
tions (0.5–4 vol%) using MQL technique in grinding nickel-based alloy. Minimum
contact angle (45°) for maximum lubricity and spreadability was observed at
2  vol%. Best tribological properties of nanofluid were obtained with 2  vol% of
Al2O3; increase in concentration reduces the surface quality of workpiece. 24.3%
reduction in force ratio and 34.1% reduction in grinding energy than pure MQL has
been observed. Wang et  al. (2017a) further added different nanoparticles (MoS2,
SiO2, ND, CNT, Al2O3, ZrO2) in palm oil as base fluid. Al2O3 provided best antifric-
tion property by reducing frictional coefficient by 20% and w-ratio by 65%.
Improved lubrication properties on addition of nanoparticles attribute to formation
354 R. Anand et al.

of tribofilm and polishing effect at wear zones and sliding surfaces. Li et al. (2017)
using same setup and conditions as Wang et al. (2017a) experimentally analysed
physical properties of different nanoparticles in grinding nickel alloy. Increase in
concentration by volume of nanoparticles (up to 2  vol%) increases thermal heat
transfer and viscosity of nanofluid. CNT with 2  vol% concentration records the
lowest temperature (108°), and SiO2 records lowest grinding force ratio. Furthermore
lower contact angle will improve lubrication effect (Table 18.3).

18.4.3  MQL-Assisted Turning with Nanoparticles

Krishna et al. (2010) experimentally studied the influence of mixing nanosolid sus-
pensions of nanoboric acid in coconut oil and SAE-40 oil in machining AISI 1040.
Turning operation was conducted on lathe with carbide inserts. It was recorded that
flow rate of 10 ml/min and 0.5% concentration of nanoboric acid with coconut oil
shows better performance in terms of heat transfer, tool wear and surface finish than
nanoboric acid suspension in SAE-40 oil. With increase in concentration (up to
0.5  wt%) of nanoparticles, thermal conductivity increases, and due to reduced
friction, there is a reduction in cutting temperature as well.
Yan et  al. (2011) on mixing different concentrations of nanosolids MoS2, Cu,
CuO (1, 3, 5, 10, 20 wt%) and graphite fibre (0.2, 0.5, 1, 3, 5 wt%) in calcium-based
greases in turning of RB-SiC ceramic, established that due to formation of thin tri-
bolayer direct contact between tool and workpiece were significantly reduced.
10 wt% of copper nanoparticles in grease produces best surface finish and minimum
tool wear which attributes to higher microplasticity of cu nanoparticles than others.
Khandekar et  al. (2012) experimentally studied the effect of adding Al2O3
nanoparticles in turning AISI 4340 steel under dry, flood and nano-enriched servo-
cut base fluid. Addition of 1% of Al2O3 enhances wettability of cutting fluid which
enhances heat transfer property of cutting fluid. Enhanced heat dissipation and cool-
ing characteristics of nano-enriched cutting fluid reduce cutting forces and tool
wear during machining.
Amrita et  al. (2013) experimentally investigated the influence of adding
nanographite at different concentrations (0.1, 0.3, 0.5 wt%) in turning AISI 1040.
Cutting fluid was supplied under different conditions of dry, flood and mist (5, 10,
15 ml/min) at different air pressures. With increase in pressure, droplet size of aero-
sol decreases which enhance lubrication and cooling property of cutting fluid.
15 ml/min and 0.5 wt% of Al2O3 decrease tool wear by 94.04% and 75.24% than dry
and flood lubrication, respectively, for carbide tool. 71.92% reduction in tool wear
was observed in case of HSS steel tool as compared to flood lubrication. Furthermore
76.25% and 56.98% reduction in cutting forces in case of carbide tool and 84.02%
and 77.76% reduction in HSS steel was observed as compared to dry and flood
machining.
Srikiran et al. (2014) investigated the influence of nanographite mixed cutting
fluid in machining AISI 1040 steel using carbide insert. Cutting forces increase by
Table 18.3  Literature review of MQL-assisted grinding with nanoparticles
Parameters Mode of
Workpiece Cutting Depth nanofluid
Author Base fluid Nanoparticle material speed of cut Feed rate supply Process findings
Shen et al. Deionized Al2O3, ND (40, Dura-Bar 30 m/s 10 μm 2400 mm/ MQL 2.5% of Al2O3 provided better surface
(2008b) water, 100, 200 nm) 100-70-02 min finish than 1% or 4% concentration
Cimtech 500 ductile iron across and along grinding direction
Higher G-ratio was obtained by adding
nanoparticles without any considerable
change in grinding temperature
Shen et al. Paraffin oil MoS2 Dura-Bar 30 m/s 10 μm MQL 27% reduction in grinding forces was
(2008a) Soybean oil (<100 nm) 100-70-02 observed for CANMIST OIL, 21 for
CANMIST oil ductile iron paraffin oil and 9% for soybean oil
Higher G-ratio for higher
concentrations for MoS2 was observed
Alberts et al. IPA xGnP D2 tool steel 25 m/s 50 mm 0.75 m/ MQL Larger size (15 μm) nanoparticles of
(2009) TRIM SC200 (5–10 nm) (62 HRC) min graphite dispersed in IPA solution
records reduction in specific energy,
surface roughness and cutting forces
Kalita et al. Soybean oil MoS2 Dura-Bar 30,000 2 mm 40 mm/s MQL G-ratio improved without affecting the
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing

(2010) 100-70-02 mm/s MRR

ductile iron MQL accompanied with MoS2 reduced
the coefficient of friction thereby
reducing tangential grinding forces
Prabhu and SAE20W40 MWCNT AISI D2 tool 2000 0.1 mm 1.9 mm/ MQL Surface tribology improved from micro
Vinayagam oil (10–20 nm) steel RPM 0.2 mm min level to nano level by adding 2% of
(2010) 2500 2.5 mm/ multiwall carbon nanotube (MWCNT)
RPM min
Vasu and Kumar TRIM E709 Al2O3 EN-31 steel 1400 25 μm 100 mm/s MQL Using TRIM E709 emulsifier, the
(2011) oil (<100 nm) RPM 50 μm 150 mm/s cutting temperature reduced to 20–30%
75 μm 200 mm/s compared to plain emulsifier
355

(continued)
Table 18.3 (continued)
356

Parameters Mode of
Workpiece Cutting Depth nanofluid
Author Base fluid Nanoparticle material speed of cut Feed rate supply Process findings
Prabhu and SAE20W40 CNT AISI D3 tool 2000 0.1 μm 1.9 mm/ MQL Addition of CNT increases the flash
Vinayagam oil (10–20 nm) steel RPM 0.2 μm min point and fire point of the base fluid by
(2012) 2500 2.5 mm/ 6.3 and 5%
RPM min Surface finish was improved with the
use of nanoparticles, from 0.54045 μm
without to 0.4478 μm with CNT
Lee et al. (2012) Paraffin oil Al2O3 SK-41C tool 80,000 5.0 μm 120 mm/ MQL Size of nano-Al2O3 was recorded as
ND steel RPM min critical parameter in reducing the
surface roughness than ND
Small size and higher concentration of
ND were more effective in reducing the
grinding forces
Mao et al. (2012) Deionized Al2O3 (40 nm) AISI 52100 31.4 m/s 10 μm 0.05 m/s MQL Added nanoparticles of Al2O3 provide
water steel the ball-bearing effect which reduces
the grinding forces, reduces the
interface temperature and provides
better lubricating conditions than water
alone
Kalita et al. Paraffin oil MoS2 Dura-Bar 30 m/s 10 μm 0.06 m/s MQL Lowest frictional coefficient of 0.22
(2012a) Soybean oil (100 nm) 100-70-03 20 μm 0.1 m/s and 53% reduction in the energy
EN24 steel consumption was observed in grinding
alloy with nanofluids
50% increase in G-ratio and increase in
tool life were also observed with nMQL
Kalita et al. Soybean oil MoS2 Dura-Bar 30 m/s 10 μm 0.06 m/s MQL Formation of a tribo-chemical film on
(2012b) (100 nm) 100-70-03 20 μm frictional surfaces reduces the friction,
wheel wear and energy
R. Anand et al.
Mao et al. Deionized Al2O3 (60 nm) AISI 52100 31.4 m/s 10 μm 0.05 m/s MQL Angular position of nozzle and
(2013b) water steel increased air pressure results in
enhanced grinding conditions with
reduced cutting speed and surface
roughness
Shorter spraying distance improves the
grinding performance
Prabhu and Water-soluble SWCNT Glass 1200 m/ 30 μm 20 m/min – ELID technique with CNT
Vinayagam oil min nanoparticles tend to improve surface
(2013) finish from (reduced from) 1.788 to
0.722 μm and microcracks
Mao et al. Deionized Al2O3 (40, 80, AISI 52100 31.4 m/s 10 μm 0.05 m/s MQL Oil-based nanofluids have better
(2013a) water 70 nm) steel surface finish and reduced cutting
forces as compared to water-based
nanofluids
Higher conc. of Al2O3 lowers the
grinding temperature and grinding
forces
Increase in diameter reduces the
grinding forces but adversely affects the
surface finish of workpiece
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing

Mao et al. Deionized Al2O3 (10 nm) – – – – MQL It was concluded that the best
(2014b) water dispersion property of Al2O3 was found
when conc. is (0.5 wt%), pH value is 7
and ultrasonic vibration time is 1 h
Jia et al. (2014) Soybean oil MoS2 Hardened 45 30 m/s 10 μm 4 m/min MQL Anti-attrition effects of MoS2 were
ZrO2 steel observed the best
Polycrystal Both PCD and ZrO2 provided the roller
diamond bearing characteristic at the sliding
(PCD) interface
MoS2 Reduced grinding forces, friction
coefficient and energy were achieved at
357

6% conc. by mass
(continued)
Table 18.3 (continued)
358

Parameters Mode of
Workpiece Cutting Depth nanofluid
Author Base fluid Nanoparticle material speed of cut Feed rate supply Process findings
Wang et al. LB1000 MoS2 (50 nm) Quenched 45 5–60 m/s 10– 0.01– MQL Grinding temperature gets reduced by
(2014) steel 45 μm 0.1 m/s addition of nanoparticles, and there is
elastic recovery of workpiece material
due to effective cooling and lubrication
ManojKumar Deionized MWCNT Hardened 25 m/s 10 μm 6 m/min 0.6 vol% of MWCNT proved better
and Ghosh water AISI 52100 20 μm 10 m/min than soluble oil in reducing grinding
(2015) forces
MWCNT nanofluid has potential to
substitute synthetic oils in grinding
hardened steel
Mao et al. Deionized Al2O3 (10 nm) AISI 52100 31.4 m/s 10 μm 0.05 m/s MQL 1.2 wt% of Al2O3 reduces grinding
(2014a) water MoS2 (70 nm) forces due to reduced coefficient of
Canola oil friction
Grinding temperature also reduces due
to increase in convective heat transfer
Zhang et al. Liquid MoS2 (50 nm) 45 steel 30 m/s 10 μm 3 m/min MQL Optimum lubricating properties were
(2015c) paraffin achieved at 6% of MoS2 in soybean oil
Palm oil Soybean having low viscosity proved
Rapeseed oil suitable for nanoparticles as base oil in
Soybean oil jet MQL
Zhang et al. Soybean oil MoS2 (50 nm) Hardened 45 35 m/s 20 μm 0.05 m/s MQL 2% volume conc. of CNT gave ideal
(2015b) CNT steel experimental results with excellent
ZrO2 cooling effects
MoS2 with soybean as base fluid gave
best lubrication results
R. Anand et al.
Setti et al. (2015) Water Al2O3 Ti-6Al-4V 17 m/s 5 μm 9 m/min MQL Nanofluids enhance micron level grain
CuO fracture and reduce surface
temperature, wear and friction between
wheel and workpiece by forming a
tribofilm
Zhang et al. Colza oil MoS2 (50 nm) Hardened 45 35 m/s 20 μm 0.05 m/s MQL Lubrication performance and surface
(2015a) CNT steel finish enhanced with 2 vol% of MoS2
ZrO2 among all three
Prabhu et al. SAE20W40 MWCNT AISI D3 tool 2000 0.1 mm 1.9 m/s MQL Using ANOVA cutting speed was found
(2015) steel RPM 0.2 mm 2.5 m/s significantly affecting surface
2500 roughness
RPM
Zhang et al. Synthetic oil MoS2 (30 nm) Ni-based alloy 30 m/s 10 μm 3000 mm/ MQL Blend of MoS2-CNT records the lower
(2016) CNT GH4169 440 min grinding ratio and surface roughness
MoS2-CNT C steel over MoS2 and CNT used alone
Li et al. (2013) Vegetable oil CNT (50 nm) 2Cr13 steel 40 m/s 1 μm 3 m/s MQL Better grinding performance can be
45 steel 5 μm achieved by 2 vol% of nanofluid due to
ZrO2 10 μm improved tribological properties of
CNT
Wang et al. Palm oil Al2O3 (50 nm) Nickel-based 30 m/s 10 μm 3000 mm/ MQL The force ratio and specific grinding
(2017b) alloy GH4169 min ratio lower down with use of nanofluids
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing

440C steel in MQL than pure MQL-based fluid

2.0 vol% of Al2O3 provides best
tribological performance
Sinha et al. Deionized Ag Inconel 718 18 m/s 10 μm 6 m/min Nanofluid (Zno) girding minimizes the
(2017) water Zno chance of redeposition of debris and
oxide layer formation on ground
machined surface
Due to better wettability and lubricity
of nanofluids, no wear land was
observed on the surface
359

(continued)
Table 18.3 (continued)
360

Parameters Mode of
Workpiece Cutting Depth nanofluid
Author Base fluid Nanoparticle material speed of cut Feed rate supply Process findings
Wang et al. Palm oil MoS2 Nickel-based 30 m/s 10 μm 3000 mm/ MQL Al2O3 provide best surface morphology
(2017a) CNTs alloy GH4169 min due to formation of thick tribofilm
ND 440C steel which reduces friction and wear
SiO2 Nanofluids MoS2, SiO2 and Al2O3
Alpha-Al2O3 provide better performance capabilities
than base oil alone, and they are also
termed as environmental-friendly
nanofluids
Li et al. (2017) Palm oil MoS2 Nickel-based 30 m/s 10 μm 3000 mm/ MQL SiO2 have lowest grinding force ratio
CNTs alloy GH4169 min with CNT having high conductivity
ND 440C steel
SiO2
Alpha-Al2O3
Pashmforoush Water Cu Inconel 738 20 m/s 10 μm 50 mm/s Surface roughness decreased by
and Bagherinia 20 μm 100 mm/s 59.19% using copper nanofluid, and
(2018) 30 μm 150 mm/s adhesion of workpiece chips on wheel
also reduced by 62.16%
R. Anand et al.
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 361

1.08 times when diameter of the nanographite decreased from (70–90  nm) to
(5–10  nm) which attributes to increase in frictional resistance due to sliding and
sticking phenomenon that increases cutting forces. Smaller size of nanoparticles
results in increased surface roughness due to continuous rubbing, increase in tem-
perature and tool chatter which degrades the surface quality of workpiece.
Chan et al. (2013) experimentally studied that surface properties and waviness of
the workpiece can be enhanced by 19% and 22% with use of nano-droplet-enriched
cutting fluid (NDCF). NDCF reduces the thrust forces by 26% and increases cutting
to thrust force ratio reducing viscosity which can further improve surface roughness.
Saravanakumar et al. (2014) investigated the performance of silver nanoparticles-­
enriched cutting fluid in turning. It was experimentally observed that with addition
of silver nanoparticles, there is reduction in cutting forces by 8.8% and surface
roughness by 7.5% as compared to conventional fluids used for machining.
Formation of a tribofilm with use of silver nanoparticles reduces the coefficient of
friction and tends to increase tool life by bringing down the cutting temperature.
Amrita et al. (2014a) investigated different parameters in machining AISI1040
steel with uncoated carbide tool on addition of nMoS2 (nano molybdenum sul-
phide), NBA (nanoboric acid) and FNG (functionalized nanographite). Addition of
surfactant (SDBS) enhanced the stability of nanoparticles in base fluid. MQL tech-
nique with and without application of nanofluids provided better cutting perfor-
mance than dry machining. nMoS2-enriched cutting fluid significantly reduces
surface roughness, wear and cutting forces compared to other nanofluids. NBA con-
siderably reduces cutting temperature at the machining zone.
Sayuti et al. (2014b) designed his experiments using Taguchi method with differ-
ent process parameters during turning of AISI 4140 hardened steel using SiO2
nanoparticles. Using fuzzy logic and Taguchi analysis minimum surface roughness
and tool wear was achieved by 0.5 wt% of SiO2 at 30° and 60°, respectively. Increase
in concentration degrades surface finish and increases tool wear.
Padmini et al. (2015) mixed nMoS2 and boric acid (H3BO3) in sesame oil and
coconut oil separately. The samples were then analysed under different lubricating
conditions. Using MQL-based lubrication system with nano enrichment of both
MoS2 and boric acid, cutting forces and surface roughness were reduced up to 82%
and 37% as compared to dry machining. nMoS2 effectively reduces interface tem-
perature of 37% and 31% in coconut and sesame oil, respectively.
Padmini et al. (2016) investigated influence of adding nMoS2 in coconut, sesame
and canola oil at different concentrations in turning of AISI 1040 steel. It was
recorded that 0.5 wt% of MoS2 effectively reduces cutting forces, surface roughness
and tool wear by 37%, 39% and 44% as compared to dry machining. Furthermore
nMoS2 forms a fullerene-like nanofilm interface which results in reducing coeffi-
cient of friction.
Amrita et al. (2014b) investigated the influence of adding nanographite 0.3 wt%
in water-soluble oil. AISI 1040 steel was turned using different lubrication tech-
niques: dry, flood, pure fluid with MQL and nano-enriched cutting fluid, and results
were compared experimentally. It was observed that mist application of nanofluid
due to formation of fine aerosols enhances the cutting condition by bringing down
362 R. Anand et al.

interface temperature and reducing the tool wear. 54% reduction in cutting tempera-
ture, 25% in tool wear and 71% in surface roughness were observed as compared to
flood lubrication.
Gupta et  al. (2016) investigated influence of nMQL during turning in CNC
machine using cubic boron nitride inserts. Al2O3, MoS2 and graphite were mixed in
vegetable oil for experimentation. After performing 29 experiments and optimiza-
tion through ANOVA, it was recorded that cutting speed, cooling condition and feed
rate contribute 40.20%, 36.50% and 20.13% and are significant parameters.
Furthermore it was observed that graphite effectively reduce the cutting temperature
as compared to other nanoparticles due to formation of lamellar structure between
machining interfaces.
Su et al. (2016) investigated experimentally the performance of graphite-LB2000
and graphite-PriEco6000 nanofluids under different lubricating conditions.
Experiments were conducted on turning AISI 1045 annealed carbon steel with
uncoated carbide insert under dry, MQL and MQL with graphite-oil mixture. It was
observed that MQL with graphite-enriched LB2000 nanofluid shows better perfor-
mance than graphite-enriched PriEco6000 in terms of reduction in machining tem-
perature and cutting forces.
Ali et al. (2017) studied influence of surfactant (SDBS w) in nano-enriched mix-
ture of Al2O3 and soluble oil at different concentrations (0.1, 0.4, 0.6  wt%).
Increasing the concentration of nanoparticles surface roughness of the workpiece
reduces. Feed rate was calculated as most significant factor using ANOVA analysis.
Raju et al. (2017) investigated the performance of MWCNT (2 vol%) with dis-
tilled water. Machining with MWCNT reduces tool wear by 40% and cutting forces
by 5–8% in comparison with base fluid and dry machining, respectively. Furthermore
presence of nanoparticles reduced the contact angle by 33.33% as compared to con-
ventional fluid which enhances the wear resistance capability of cutting fluid.
Behera et al. (2017) experimentally compared the spreading coefficient of differ-
ent surfactants (CTAB, SDS, Tween-20, PVP) on cutting tool surface. Reduction in
tangential force (29.72%), coefficient of friction (7.25%) and feed force (19.39%)
were observed with Tween-20-NF compared to dry and other surfactant-rich
­nanomachining. Reduction of about 33.35% in chip tool interface was observed
with Tween-20 NF compared to dry environment.
Hegab et al. (2018b) experimentally observed the performance of MWCNT-rich
nanofluid on turning titanium alloy by varying cutting speeds. Using ANOVA anal-
ysis it was recorded that MWCNT-rich nanofluid gave better results in power con-
sumption and flank wear than base fluid alone. Significant improvement on cutting
temperature, cooling and wetting characteristics of base fluid was observed by using
MWCNT. Continuing their work Hegab et al. (2018a) studied the effect of turning
with nano-enriched cutting fluid on chip morphology and tool wear on machining
Inconel 718. MWCNT and Al2O3 have been used to enhance the lubrication proper-
ties of base fluid. Less deformation in chip and enhancement in interface bonding of
tool and chip were observed which attributes to increase in shear angle and superior
cooling characteristics of cutting fluid.
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 363

Sartori et al. (2018) observed the cooling and lubrication characteristics of solid
lubricants (graphite and PTFE) using MQL technique on turning Ti-6Al-4V alloy.
Reduction in crater and nose wear was observed due to improved dynamic viscosity
of solid lubricant-assisted MQL-MQC (Table 18.4).

18.4.4  MQL-Assisted Milling with Nanoparticles

Park et al. (2011) experimentally analysed the effect of nano-enhanced lubrication

in ball milling AISI 1045 steel workpiece using MQL technique. Nanographene
(xGnP) particles were mixed with vegetable oil, and experiment was conducted in
vertical milling machine under dry, flood, water-soluble mineral oil, units cooltube
200 (vegetable oil) and xGnP nanoparticle in vegetable oil with MQL. 0.1 wt% and
1 μm diameter are regarded as optimum concentration and size of nanoparticle for
enhanced cutting performance as compared to 1 wt% and 15 μm. The layered struc-
ture of nanographene reduces coefficient of friction significantly.
Sarhan et  al. (2012) investigated the effect of SiO2 nano-enriched milling of
AA6061-T6 alloy using MQL. It was observed that SiO2 mixed with mineral oil
improved milling performance in terms of specific power, cutting forces and coef-
ficient of friction as compared to base fluid alone which attributes to sliding and
rolling action of nano SiO2. Using same setup (Sayuti et al. 2013a) studied the effect
of concentration, nozzle angle and cutting temperature. Using ANOVA analysis
minimum cutting force was observed with 0.2 wt% SiO2 and 60° nozzle angle, and
minimum cutting temperature was observed with 15° nozzle angle at 2 bar air pres-
sure. Surface roughness can be minimized with high concentration of nanoparticles
and with 30° nozzle angle.
Sayuti et al. (2013b) studied the influence of carbon anion-enriched nanofluid on
machining aerospace aluminium alloy (duralumin Al-2017-T4) using vertical mill-
ing machine. 0%, 0.5%, 1% and 1.5 wt% concentrations of carbon anion were used
during machining, and it was observed that 21.99% and 46.32% reduction in cutting
forces and surface roughness can be obtained by nano-enriched cutting fluid as
compared to conventional oil lubrication. Higher concentration of nanoparticles
reduced cutting forces and improved surface quality. Sayuti et al. (2014a) concluded
that addition of SiO2 improves the surface morphology during milling and reduces
the thermal deformation of workpiece which attributes to the rolling action and
formation of thin tribofilm that improves surface quality and conductivity.
Rahmati et al. (2014) analysed the milling performance on aluminium alloy and
recorded improvement in surface finish by 3.87% with 0.5 wt% MoS2-enriched cut-
ting fluid as compared to conventional oil. With further increase in concentration of
nanoparticles, surface finish deteriorates. FESEM and XRD were used to study sur-
face morphology.
Najiha et  al. (2015) analysed the performance of water-mixed nanoparticles
(TiO2) and compared the results with that of conventional oil-mixed nanoparticles.
It was observed that both techniques produce almost same results for tool wear,
Table 18.4  Literature review of MQL-assisted turning with nanoparticles
364

Parameters
Workpiece Cutting Depth of Mode of
Author Base fluid Nanoparticles material speed cut Feed rate lubrication Process findings
Krishna et al. Coconut oil, Nanoboric acid AISI 1040 60, 80, 0.1 mm 0.14, 0.1, MQL Percentage increase in conc. of
(2010) SAE-40 (50 nm) steel 100 m/min 0.2 mm/rev nanoboric acid increases the
thermal conductivity and decreases
specific heat
0.5% of nanoboric acid reduces
cutting temperature and improves
tool life and surface finish
Yan et al. Calcium-based MoS2 RB-Sic 1000 RPM 2 μm 20 mm/min MQL Best surface quality and less tool
(2011) grease GF wear were obtained at 10 wt% cu
Cu conc. in grease
CuO
Khandekar Servocut S Al2O3 AISI 4340 350 m/min 0.1 mm 0.1 mm/rev MQL Addition of 1% of Al2O3 in base
et al. (2012) fluid enhances the wettability of
base fluid
50% reduction in cutting forces by
using nanofluids as compared to
dry machining
54.4% reduction in surface
roughness when nanofluid is used
Amrita et al. – Nanographite AISI 1040 40.7 m/min 1 mm 0.14 mm/rev MQL Min tool wear, tool chip interface
(2013) (<80 nm) temperature and cutting forces
were observed for 15 ml/min flow
rate and 0.5 wt% of nanoparticles
Amrita et al. Conventional Nanographite AISI1040 40 m/min – 0.14 mm/rev MQL 70%, 25% and 20% reduction in
(2014b) water (nano-SO) (<80 mm) 10 ml/ cutting temperature was observed
min with nanofluid cutting than dry,
flood and mist fluid applications
R. Anand et al.

Surface roughness reduced by

42%, 32% and 28%, respectively
Srikiran SAE-40 oil Nanographite AISI 1040 51 m/min 0.25 mm 0.05 mm/rev MQL Cutting forces, frictional forces and
et al. (2014) (5–10 nm) 78 m/min 0.50 mm 0.08 mm/rev tool interface temperature increase
(15–30 nm) 126 m/min 0.75 mm 0.10 mm/rev due to decrease in size of
(40–60 nm) 192.6 m/ 1.0 mm 0.125 mm/rev nanoparticles from 70–90 nm to
(70–90 nm) min 5–10 nm
Chan et al. JAEGER – 6061-T651 2000 RPM 30 μm 30 mm/min – Reduced roughness and enhanced
(2013) SW-105 oil brass 8000 RPM 20 μm 20 mm/min waviness were observed by using
Pure copper cutting fluid with nano-droplet-­
enriched cutting fluid (NDCF)
Saravana-­ Distilled water Ag – 50.4 m/min 3 mm 0.1 mm/rev MQL Surface roughness decreased by
kumar et al. 64.8 m/min 5 mm 0.2 mm/rev 7.5% with use of nanoparticles
(2014) Rate of heat transfer at chip tool
interface improved with decrease
in cutting forces by 8.8%
Amrita et al. Water-based FNG (80 nm) AISI 1040 65 m/min 0.75 mm 0.14 mm/rev MQL MoS2 (0.3 wt%) recorded better
(2014a) soluble oil NBA (100) surface properties with lower wear
nMoS2 (100) and reduced cutting forces
Sayuti et al. Mineral oil SiO2 (5–15 nm) AISI 4140 0.15 mm/ 0.5 mm 0.15 mm/rev MQL Minimum tool wear was obtained
(2014b) rev with 0.5% conc. of nanoparticles
and 2 bar pressure in mineral oil
with 60° nozzle angle and
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing

improved surface roughness at 30°

angle of nozzle
Padmini Coconut oil Boric acid AISI 1040 60 m/min 0.5 mm 0.14 mm/rev MQL As compared to dry machining,
et al. (2015) (CC), sesame oil MoS2 (<100 nm) (30 HRC) nMoS2 with coconut and sesame oil
(SS) reduces surface roughness by 46%
nMoS2 effectively reduced tool
wear by 28% and 38% in coconut
and sesame oil
(continued)
365
Table 18.4 (continued)
366

Parameters
Workpiece Cutting Depth of Mode of
Author Base fluid Nanoparticles material speed cut Feed rate lubrication Process findings
Padmini Coconut oil (CC) Boric acid AISI 1040 40 m/min 0.5 mm 0.14 mm/rev MQL 5% coconut oil and nMoS2 reduces
et al. (2016) Sesame oil (SS) MoS2 (<100 nm) 60 m/min 0.17 mm/rev cutting forces by 37%, cutting
Canola oil 100 m/min 0.20 mm/rev temperature by 24% and tool wear
(CAN) by 44% than any other nanofluid
Gupta et al. Vegetable oil Al2O3 (<50 nm) Titanium 215 m/min 1 mm 0.10 mm/rev MQL Lower cutting temperature and
(2016) MoS2 (grade 2) 250 m/min 0.15 mm/rev cutting forces were observed using
Graphite graphite-based nanofluids
Su et al. LB2000 Graphite AISI 1045 55 m/min 1 mm 0.10 mm/rev MQL Using nanofluids cutting forces and
(2016) PriEco6000 96 mm/min temperature reduced 11.9% and
21% with respect to dry machining
Ali et al. SolCut Al2O3 (<50 nm) Ti-6Al-4V 75 m/min 1 mm 0.10 mm/rev MQL Taguchi method was applied to find
(2017) 85 m/min 0.15 mm/rev set of combinations of parameters
95 m/min 0.20 mm/rev for producing optimum surface
roughness, tool wear and power
consumption
Raju et al. Distilled water MWCNT EN31 1500 RPM 1 mm 0.1 mm/rev – Tool wear improved by 49% using
(2017) MWCNT nanofluid as compared to
dry machining, and 30% reduction
was observed than conventional
fluid
9–12% reduction in surface
roughness and cutting forces
reduce by 5–8% with use of
MWCNT-­enriched nanofluid over
conventional fluid
R. Anand et al.
Behera et al. Deionized water Al2O3 Inconel 718 60 m/min 0.5 mm 0.2 mm/rev MQL Reduction in chip curling, cutting
(2017) 80 m/min forces and coefficient of friction
was observed as a result of good
spreading behaviour of nanofluids
Hegab et al. – MWCNT INCONEL 40 m/min – 0.2 mm/rev MQL Addition of MWCNT and Al2O3
(2018b) Al2O3 718 50 m/min 0.3 mm/rev reduces cutting forces due to
60 m/min 0.4 mm/rev increase in shear angle and
adequate dissipation of heat
Hegab et al. ECOLUBRIC MWCNT Ti-6Al-4V 120 m/min – 0.1 mm/rev MQL 2 wt% of nanoparticles in base
(2018a) E200 170 m/min 0.15 mm/rev solution provides better cutting
220 m/min 0.2 mm/rev performance at less power
consumption than 4 wt% of
nanofluid
Sartori et al. AstroCut HD PTFE (polytetra-­ Ti-6Al-4V 80 m/min 0.25 mm 0.2 mm/rev MQL Addition of PTFE assisted the
(2018) XBP fluoroethylene) MQC cratering phenomenon, and tool
(5 μm) wear reduced with less abrasion of
Graphite cutting edge
Sharma et al. Alumina Graphene AISI 304 60 m/min 0.6 mm 0.08 mm/rev MQL Addition of graphene in alumina
(2018) steel 90 m/min 0.9 mm 0.12 mm/rev increases its wettability
120 m/min 1.2 mm 0.16 mm/rev 1.25 vol% of alumina and Al-GnP
hybrid nanofluid shows lowest
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing

coefficient of friction and wear

367
368 R. Anand et al.

but edge chipping is reduced in water-based MQL due to higher cooling rate and
higher concentration of aluminium in deposited layer on flank face. Using same
setup (Najiha and Rahman 2016) compared the wear phenomenon for TiO2-enriched
water and conventional oil using MQL technique. Adhesion and abrasion wear were
found to be major tool wear phenomenon in all three cases of lubrication (flood,
MQL with vegetable oil, and MQL with water) which were comparable in all three
modes of lubrication. Furthermore it was observed that due to cooling effect and
high latent heat produced by water-based MQL, edge fracture and edge chipping
were not seen. Varying concentrations of nanoparticles (0.5, 2.5, 4.5 wt%) of TiO2
in same setup (Najiha et al. 2016) recorded minimum tool wear at 2.5 vol% com-
pared to other lubricating conditions. Experimental results were then compared
with those of three-level fuzzy logic system.
Kim et  al. (2016) compared four different lubrication techniques (dry, flood,
MQL with hBN in vegetable oil with and without chilly CO2 gas in end milling of
Ti-6Al-4V alloy). 0.1  wt% of hBN provided enhanced milling performance than
other lubrication techniques. Cooling and lubrication effect of both chilly CO2 gas
and hBN effectively reduce surface roughness, chip adhesion of machined surface
and tool wear.
Muthusamy et al. (2016) analysed the wear analysis on milling of AISI 304 with
TiO2 mixed ethylene glycol nanofluid with different concentrations (0.5, 1.0, 1.5
vol%). Milling AISI 304 steel with tin-coated carbide tool using TiO2 mixed nano-
fluid increase tool life (54.9 min) as compared to water-soluble coolant (32.67 min).
Enhanced tool life was obtained with 1 vol% of TiO2 at all cutting speeds. It was
observed from results shown by EDX and ESM that a layer formation by embed-
ment of nanoparticles from nanofluid acts as a protective layer for cutting tool.
Lv et al. (2018) studied the effect of hybrid nanoparticles graphene dioxide and
silicon dioxide (GO and SiO2) in water-based MQL lubrication technique at varying
concentrations of both. On end milling of AISI 304, it was observed that addition of
0.02:0.05% of GO:SiO2 in water resulted in reduced tool wear, with improved sur-
face finish and tool life. SiO2 and GO nanoparticles penetrate into the pits of the
friction region thereby forming a smooth surface which enhances the rolling effect
of SiO2 and slipping of GO sheets thereby forming a thin protective layer which
distributes stress concentration and separates the sliding pairs minimizing wear
(Table 18.5).

18.5  Future Scope

Previous researchers have focused more on lubricants containing single type

nanoparticles in mineral oils preferably. In the above study, the authors have tried to
experimentally investigate the blending of two different types of nanoparticles hav-
ing two different properties and mechanisms they involve in. The blending of graph-
eme (GnP) with TiO2 (titanium dioxide) in a fixed ratio (1:1) along with a
biodegradable oil improved tribological and thermophysical properties of the oil for
Table 18.5  Literature review of MQL-assisted milling with nanoparticles
Parameters
Cutting Feed rate/
Workpiece speed/wheel Depth workpiece Mode of
Author/year Base fluid Nanoparticles material speed of cut speed lubrication Process findings
Park et al. Vegetable oil xGnP (1 μm) AISI 1045 3500 RPM 1.0 mm 2500 mm/ MQL Addition of xGnP nanoparticles
(2011) 4000 RPM 0.6 mm min increases wettability and reduces
friction
0.1 wt% of xGnP resulted in
improved cutting performance
without agglomeration
Sarhan et al. ECOCUT SiO2 (5–15 nm) Aluminium 500 RPM 5 mm 100 mm/ MQL SiO2 nanoparticles reduce contact
(2012) SSN 322 alloy min friction due to which there is less
mineral oil AA6061-T6 consumption of specific energy and
power
Sayuti et al. ECOCUT SiO2 (5–15 nm) Aluminium 5000 RPM 5 mm 100 mm/ MQL Minimum cutting force can be
(2013a) SSN 322 alloy min observed at 0.2 wt% of SiO2, and
AA6061-T6 minimum cutting temperature was
observed at 15° nozzle orientation
angle
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing

Sayuti et al. Alumicut oil Carbon anions Duralumin 75.408 m/ 1.0 mm 100 mm/ MQL Best surface topography and reduced
(2013b) (5–20 nm) AL-2017-T4 min min cutting forces were observed at
1.5 wt% conc. of carbon anions
Rolling action of nanoparticles
reduces cutting forces and surface
finish by 21.995 and 46.32%
Sayuti et al. ECOCUT SiO2 Aluminium 5000 RPM 5.0 mm 100 mm/ MQL Addition of SiO2 improved the
(2014a) SSN 322 alloy min surface morphology with formation
AA6061-T6 of thin tribofilm thereby reducing
frictional wear and thermal
deformation during machining
369

(continued)
Table 18.5 (continued)
370

Parameters
Cutting Feed rate/
Workpiece speed/wheel Depth workpiece Mode of
Author/year Base fluid Nanoparticles material speed of cut speed lubrication Process findings
Rahmati et al. ECOCUT MoS2 Aluminium 8000 RPM 5 mm 2100 mm/ MQL 0.5 wt% of MoS2 improved the
(2014) HSG 905S (20–60 nm) alloy min surface quality than 1 wt% of MoS2
oil AA6061-T6
Najiha et al. Deionized TiO2 (40 nm) Aluminium 5300 RPM 3 mm 440 mm/ MQL Higher cooling rates with reduced
(2015) water alloy 5500 RPM min chipping of tool were observed with
AA6061-T6 addition of TiO2 in deionized water
Najiha and Deionized TiO2 (40 nm) Aluminium 5300 RPM 3 mm 440 mm/ MQL 2.5 vol% reduces BUE formation
Rahman water alloy 5500 RPM min and reduces chipping of tool material
(2016) AA6061-T6 with improved cooling conditions
Kim et al. Vegetable oil (hBN) Titanium 45,000 RPM 100 μm 5 μm/tooth MQL Chilling effect of CO2 reduces
(2016) hexagonal alloy cutting forces, tool wear and
boron nitride Ti-6Al-4V improved surface finish
(70 nm) Micro-end-milling performance
improved by adding 0.1 wt% of hBN
Muthusamy Ethylene TiO2 AISI 304 1500 RPM 0.1 mm 0.02 mm/ MQL Tool life increased by 40.55% with
et al. (2016) glycol steel 2500 RPM 0.3 mm tooth addition of TiO2 in base fluid
0.04 mm/
tooth
Park et al. Vegetable oil xGnPs Ti-6Al-4V 46.5 m/min 2 mm 0.15 mm/ MQL, Addition of nanoparticles reduces
(2017) 76.4 m/min rev cryogenic tool wear and friction at higher
100 m/min cooling cutting speed even when base fluid
120 m/min vaporize at high surface temperature
Lv et al. Water PEG GO (5–10 nm) AISI-304 100 m/min 1 mm 0.12 mm/ MQL 0.02 wt% of GO and 0.50 wt% of
(2018) solution SiO2 (5–10 nm) tooth SiO2 in base fluid reduce tool wear
and improve surface roughness due
to their ball-bearing effect
R. Anand et al.
18  Bio-Based Nano-Lubricants for Sustainable Manufacturing 371

manufacturing operations. The nanofluid was then experimentally tied for turning
operation on a commercial lathe machine with minimum quantity lubrication tech-
nique to minimize the usage of the prepared nanofluid providing cost benefits.
1. The present work can further be extended to discover environment-friendly veg-
etable oils that have the potential to be used as cutting fluids in common manu-
facturing operations.
2. Suitable additives in the form of nanoparticles with different weight fractions,
shapes and sizes can be used to enhance the thermophysical properties of cutting
oils. This would be helpful in developing nano-lubricants with enhanced tribo-
logical properties for the machining of specific metals and alloys.
3. Moreover, the present work can further be extended to the optimization of
nanoparticle volume fraction, their shape and their size. This would be helpful in
developing nano-lubricants with improved tribological properties for the machin-
ing of specific metals and alloys.
4. Different tool and workpiece combinations can be checked for optimum tool life
and economic analysis.

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Chapter 19
Nanomaterials Used for Delivery
of Bioactives

Akhlesh Kumar Jain and Umesh Gupta

19.1  Introduction

Progression in genetic engineering has led to propagation of gigantic diversity of

bioactives which demands effective means of carriers for intracellular delivery in
order to achieve specific objectives such as selective tumor targeting, genetic vac-
cination, regenerative medicine, and treatment of functional loss. Generally, these
biologics are prone to enzymatic degradation and deactivation. Hence, immense
arrangement of efforts has been made to develop nanometric size vehicles which
could not only deliver the medicaments to the desired site of action but also protect
for unwanted degradation. In this regard, nanoparticles have been shown great
promise as a delivery vehicle for smaller molecules, plus large bioactives, i.e., pro-
teins, peptides, vaccines, or nucleotides by either restricted or tissue-specific deliv-
ery. In addition, formulation scientists are fascinated about nanocarriers as a
delivery vehicles as proportion of quantity of surface atoms or molecules to the
total count of atoms or molecules enhanced drastically hence effective surface area
multiplied exponentially (Hadjipanayis et al. 2010). Further, nanoparticles are in
great number and could access regions of poor access such as injured tissues, tumor
cells, inflamed organs, etc. due to their tiny size (Jong and Borm 2008).
Nanotechnology concentrates on encapsulating drugs in bio-friendly nanocompos-
ites, i.e., polymeric nanoparticles, nanoliposomes, solid lipid nanoparticles, micel-
lar systems, and bioconjugates. A schematic diagram of different varieties of
nanocarriers used for delivery of bioactives is depicted in Fig. 19.1. These carriers
are usually explored to enhance oral bioavailability, to sustain medicament release

A. K. Jain (*)
School of Pharmaceutical Sciences, GGV Central University, Bilaspur, Chhattisgarh, India
U. Gupta
Department of Pharmacy, Central University of Rajasthan, Kishangarh, Rajasthan, India

© Springer Nature Switzerland AG 2020 381

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_19
382 A. K. Jain and U. Gupta

Fig. 19.1  Classification of most commonly used nanocarriers for drug delivery

in desired organ, to ­dissolve the therapeutics for intravascular administration, to

enhance the drug stability against enzyme-mediated degradation, and to achieve
targeted (cellular/organ) delivery of drugs. In addition, the release of encapsulated
cargo from nanocarriers can be controlled in the organ of interest in order to pro-
duce desired therapeutic level for desired period of time to generate maximum
therapeutic benefits. Usually, nanoparticles have shown greater cellular uptake
compared to microparticles (Desai et al. 1996). Several important human disorder-
related diseases have demonstrated significant improvement after treatment of pro-
tein-/peptide-loaded nanocarriers (Yu et al. 2016). Macromolecules have large size,
high hydrophilicity and susceptibility to physical and chemical degradation, struc-
tural fragility, and complexity; hence, these characteristics strongly affect pharma-
cokinetic and pharmacodynamic behavior in  vivo. Moreover, development
processes such as higher temperature, exposure to organic solvents, etc. addition-
ally compromise the stability of these macromolecules. To overcome all these chal-
lenges, extraordinary efforts are made to incorporate therapeutics in hydrogels,
micellar systems, nanocapsules, nanoemulsions, nanoliposomes, and niosomes.
Afterward, surface modification of these carriers by specific ligands was explored
with an aim to deliver protein therapeutics into the organs of interest in active form.
Nanomedicines approved by FDA are enlisted as per variety of carrier/material
used in development of the formulation (Table  19.1). The key objective of
Table 19.1  List of nanomedicines approved by FDA classified by type of carrier/material used in the preparation of the formulation
Commercial name Year
(Company) Ingredient active Carrier Application Advantage approved
Doxil®/Caelyx™ Doxorubicin Liposomes Kaposi’s sarcoma; ovarian Increased site-specific delivery 1995; 2005;
(Janssen) cancer; multiple myeloma (tumor) and decreased 2008
systemic toxicity
Abelcet® (Sigma Tau) Amphotericin B lipid Liposomes Fungal infection Decreased toxicity 1995
complex
DaunoXome (Galen) Daunorubicin Liposomes Kaposi’s sarcoma Increased site-specific delivery 1996
(tumor) and decreased toxicity
DepoCyt© (Sigma Cytarabine Liposomes Lymphomatous meningitis Increased site-specific delivery 1996
Tau) (tumor) and decreased toxicity
AmBisome® (Gilead Amphotericin B Liposomes Fungal and/or protozoal Reduced nephrotoxicity 1997
Sciences) infections
Curosurf /poractant Proteins SP-B and SP-C Liposomes Lung activator for stress Decreased toxicity and 1999
alfa (Chiesi disorder; pulmonary increased delivery for smaller
19  Nanomaterials Used for Delivery of Bioactives

Farmaceutici) surfactant for respiratory volume

distress syndrome
Visudyne (Bausch and Verteporfin Liposomes Ocular histoplasmosis, Increased site-specific delivery, 2000
Lomb) myopia, decreased vision (lesion vessels) photosensitive
release
DepoDur® (Pacira Morphine sulfate Liposomes Prolonged release Loss of pain (postoperative) 2004
Pharmaceuticals)
Marqibo® (Onco TCS) Vincristine Liposomes Acute lymphoblastic Increased site specific delivery 2012
leukemia (tumor) and decrease toxicity
Onivyde® (Merrimack) Irinotecan Liposomes Pancreatic cancer Increased site specific delivery 2015
(tumor) and decrease toxicity
(continued)
383
Table 19.1 (continued)
384

Commercial name Year

(Company) Ingredient active Carrier Application Advantage approved
Adagen (Sigma Tau Pegademase bovine PEGylated adenosine Immunodeficiency disease Improved circulation time in 1990
Pharmaceuticals®) deaminase enzyme body and decreased
immunogenicity
Oncaspar (Enzon Asparaginase PEGylated asparaginase Acute lymphoblastic Improved protein stability due 1994
Pharmaceuticals) leukemia to PEGylation
Copaxone® (Teva) Glatopa Glutamate, alanine, Multiple sclerosis Regulation of clearance and 1996
lysine, and tyrosine polymer with controlled
random polymer molecular weight
Renagel® (Sanofi) Sevelamer hydrochloride Poly(allylamine Chronic renal diseases Increased site-specific delivery 2000
or sevelamer carbonate hydrochloride) and increase in circulation
time in body
PegIntron® (Merck) Interferon-alpha (IFN-α2b) PEGylated IFN-α2b Hepatitis C Improved protein stability due 2001
protein PEGylation
Pegasys® (Genentech) Interferon-alpha (IFN-α2a) PEGylated IFN-α2a Hepatitis B and C Improved protein stability due 2002
protein PEGylation
Eligard® (Tolmar) Leuprolide acetate Polymer (PLGH Prostate cancer Prolonged drug delivery and 2002
(poly(dl-lactide-co- circulation time in body
glycolide)
Neulasta® (Amgen) PEG-filgrastim PEGylated granulocyte Neutropenia induced by Improved protein stability due 2002
colony- stimulating chemotherapy to PEGylation
factor (GCSF) protein
Somavert® (Pfizer) PEG-visomant PEGylated HGH Acromegaly Improved protein stability due 2003
receptor antagonist to PEGylation
Macugen® (Bausch & PEG-aptanib PEGylated anti vascular Macular degeneration; Improved stability due to 2004
Lomb) endothe- lial growth neovas cular age-related PEGylation
factor aptamer (decreased vision)
A. K. Jain and U. Gupta
Commercial name Year
(Company) Ingredient active Carrier Application Advantage approved
®
Mircera (Hoffman-La Methoxy polyethylene Chemically synthesized Anemia associated with Improved stability due to 2007
Roche) glycol-epoetin beta erythropoiesis- renal failure due to diseases PEGylation
stimulating agent
Cimzia® (UCB) Certolizumab pegol PEGylated antibody Crohn’s disease; rheumatoid Increased stability and 2008; 2009;
fragment(Certolizumab) arthritis; psoriatic arthritis circulation time in body 2013; 2013
and ankylosing spondylitis
Krystexxa® (Horizon) Pegloticase PEGylated porcine-like Chronic gout Improved protein stability due 2010
uricase to PEGylation
Plegridy® (Biogen) Interferon beta (IFNβ 1a) PEGylated IFN-β1a Multiple sclerosis Improved protein stability due 2015
protein to PEGylation
ADYNOVATE Factor VIII PEGylated factor VIII Hemophilia Improved protein stability due 2015
(Baxalta) to PEGylation
Rapamune® (Wyeth Sirolimus Nanocrystals Immunosuppressant Increased bioavailability 2000
Pharmaceuticals)
Megace ES (Par Megestrol acetate Nanocrystals Anti-anorexic Reduced posology 2001
Pharmaceuticals)
19  Nanomaterials Used for Delivery of Bioactives

Aviriza (Pfizer) Morphine sulfate Nanocrystals Mental stimulant Prolonged release and 2002/2015
increased bioavailability
Ritalin LA® (Novartis) Methylphenidate HCl Nanocrystals Mental stimulant Increased drug loading and 2002
bioavailability
Zanaflex® (Acorda) Tizanidine HCl Nanocrystals Muscle relaxant Increased bioavailability and 2002
decreased posology
Emend® (Merck) Aprepitant Nanocrystals Antiemetic drug Increased absorption and 2003
bio- availability
Vitoss® (Stryker) Calcium phosphate Nanocrystals Bone substitute Mimics bone structure by cell 2003
adhesion and growth
OsSatura ® (IsoTis Hydroxyapatite Nanocrystals Bone substitute Mimics bone structure by cell 2003
Orthobiologics) adhesion and growth
(continued)
385
Table 19.1 (continued)
386

Commercial name Year

(Company) Ingredient active Carrier Application Advantage approved
Ostim® (Heraseus Hydroxyapatite Nanocrystals Bone substitute Mimics bone structure by cell 2004
Kulzer) adhesion and growth
Tricor® (Lupin Fenofibrate Nanocrystals Hyperlipidemia Increased bioavailability 2004
Atlantis)
Focalin XR® (Novartis) Dexmethylphenidate HCl Nanocrystals Mental stimulant Increased bioavailability 2005
NanOss (Rti Surgical) Hydroxyapatite Nanocrystals Bone substitute Mimics bone structure by cell 2005
adhesion and growth
EquivaBone® (Zimmer Hydroxyapatite Nanocrystals Bone substitute Mimics bone structure 2009
Biomet)
Invega® Sustenna® Paliperidone palmitate Nanocrystals Schizophrenia Decreased release of poor 2009/2014
(Janssen Pharms) schizoaffective disorder water-soluble drugs
Ryanodex® (Eagle Dantrolene sodium Nanocrystals Malignant hypothermia Allows higher administration 2014
Pharmaceuticals) at higher doses
Estrasorb® (Novav) Estradiol Micelles Menopause hormone Sustained release 2003
therapy
Abraxane® (Celgene) Paclitaxel (ABI-007) Albumin-bound Breast cancer; non-small Increase site-specific delivery 2005, 2012,
paclitaxel nanoparticles cell lung cancer and (tumor) and solubility 2013
pancreatic cancer
INFeD (Sanofi Aventis) Iron Iron dextran (low MW) Chronic kidney failure with Increased dose capacity 1957
iron deficiency
DexIron/Dexferrum Iron Iron dextran (high MW) Chronic kidney failure with Increased dose capacity 1957
(Sanofi Aventis) iron deficiency
Feridex/Endorem Superparamagnetic iron SPION coated with Imaging material Superparamagnetic character 1996, 2008
(AMAG oxide nanoparticles dextran
Pharmaceuticals®) (SPION
Ferrlecit® (Sanofi Sodium ferric Sodium ferric gluconate Chronic kidney failure with Increased dose capacity 1999
Aventis) iron deficiency
A. K. Jain and U. Gupta
Commercial name Year
(Company) Ingredient active Carrier Application Advantage approved
Venofer (Luitpold Iron oxide Iron sucrose Chronic kidney failure with Increased dose capacity 2000
Pharmaceuticals) iron deficiency
GastroMARK; umirem Superparamagnetic iron SPION coated with Imaging material Superparamagnetic character 2001/2009
(AMAG oxide nanoparticles silicone
Pharmaceuticals™) (SPION
Feraheme (AMAG Ferumoxytol ultrasmall Ferumoxytol SPION Chronic kidney failure with Prolonged steady release and 2009
pharmaceuticals) superparamagnetic iron with polyglucose iron deficiency decreased number of doses
oxide nanoparticles sorbitol carboxymethyl
(SPION) ether
Nanotherm (MagForce) Iron oxide Aminosilane-coated Brain tumor Thermotherapy for destroy 2010
Iron nanoparticles tumor cells or sensitized for
additional therapies
Reproduced under Creative Commons license (http://creativecommons.org/publicdomain/zero/1.0/)
19  Nanomaterials Used for Delivery of Bioactives
387
388 A. K. Jain and U. Gupta

p­ reparation of nanocarriers is to organize particle size, surface characteristics, as

well as efficient delivery in fully active forms. As a result, critical characterizations
play a vital role in controlling in vitro as well as in vivo behavior of nanoparticles.

19.2  Classification of Nanocarriers

19.2.1  Liposomes

Liposomes are made of phospholipid bilayer enclosing aqueous cavity which could
encapsulate small molecular weight drugs, peptides, proteins, and nucleotides
(Yousefi et al. 2009; Patel et al. 2011). Usually, they have a particle size from 25 nm
to several micrometers as per the number of bilayers present in the liposomes.
Liposomes are proved to be versatile carriers because they offer flexibility in terms
of vesicle size, surface charge, bilayer composition, and encapsulation ability which
also make these carriers useful for delivery of bioactives. Lipid combination made
of distearoyl phosphatidylcholine, dimyristoyl phosphatidylglycerol, and choles-
terol (Anderson et al. 1999); a blend of phosphatidylcholine, castor oil, and polyeth-
ylene glycol attached to distearoyl phosphatidylethanolamine (Song et  al. 1996);
and a blend of distearoyl phosphatidylglycerol, distearoyl phosphatidylcholine, and
cholesterol (Rezler et al. 2007) are usually used for the preparation of liposomes.
Usually aqueous compartment contains hydrophilic agents, whereas lipophilic
drugs are inserted into the lipid bilayer (Patel et  al. 2009). Bioactives which are
prone to degradation are prepared using reverse-phase evaporation process which
bypasses unwanted exposure of/to harmful solvents. Liposomes having nano size
range can also prolong the release of entrapped bioactives, warranting sustained
effect at the site of interest. Pulmonary delivery of insulin is achieved via liposomes
which has shown number of advantages as an alternative to insulin injection such as
sustained blood glucose levels with a higher pharmacological bioavailability com-
pared to dry powder inhalation (Bi et al. 2008). Further, Bak proteins and voltage-­
dependent anionic channel (VDAC) were loaded into the liposomes and produce
apoptosis into mammalian cells through cytochrome C and caspase activation
(Liguori et al. 2008).
Removal of liposomes from blood circulation takes place in a size-dependent
manner through membrane fusion actions and interactions with specific serum pro-
teins (opsonins). Despite the fact that cell surface receptors cannot detect liposome
directly as a foreign particle, they identify liposomes via cellular and serum proteins
that are adhered to liposomal surface (Ishida et al. 2002). Circulation time of lipo-
somes can be enhanced, and also macrophage uptake can be reduced by means of
PEGylation which provides anti-opsonizing properties to the liposomes, once it is
decorated on the exterior surface by forming a hydrophilic layer of polymer, hence
sheltering the charge associated with liposome surface. Usually, RES cells identify
and react with liposomes through opsonins, but hydrophilicity of PEG layer helps in
escaping the liposomes. Kedar et  al. (1994) have significantly enhanced survival
19  Nanomaterials Used for Delivery of Bioactives 389

time of mice with metastatic carcinoma (earlier subjected to cyclophosphamide

chemotherapy) was enhanced by two to six times followed by treatment with
SSL-IL-2 compared to IL-2 even after lower doses and fewer administrations com-
pared to plain interleukin-2 (IL-2). Enhanced cellular translocation of TAT peptide
(transactivator of transcription of human immunodeficiency virus) was reported by
incorporating it into the liposomes (Carsten et al. 2004). Dioleoyl phosphatidyletha-
nolamine (DOPE) and guanidinium-cholesterol cationic lipid liposomes success-
fully entrapped the β-galactosidase enzyme and the anti-cytokeratin8 (K8) antibody
and enhanced cellular delivery of β-galactosidase devoid of any negotiation in its
activity (Chatin et al. 2015). In recent time, the applicability of bilosomes as a via-
ble approach for oral administration of larger peptides and proteins along with asso-
ciated biopharmaceutical challenges has been reviewed by Ahmad et al. (2017).
Niosomes are spontaneously gathered non-ionic surfactants vesicles generally
made of alkyl or dialkyl polyglycerol ether class surfactants are (Malhotra and Jain
1994). Lamellar structures fashioned by mingling cholesterol and non-ionic surfac-
tant and followed by hydration which leads to closed bilayer vesicle upon providing
some energy such as physical agitation. Such bilayer structures are spontaneous
arrangement of surfactant in such a way that allows hydrophilic heads to remain
exposed to the aqueous phase while lipophilic tails acquaint themselves with the
lipid phase. Niosomes are extensively investigated as a cheaper substitute of lipo-
somes however is of synthetic origin. These vesicles as a carrier systems are closely
having similar physical characteristics, in vitro release behavior, as well as in vivo
behavior to the liposomes. These carriers not only have maximum advantages of
liposomes, but also the economy, enhanced stability, and flexibility in storage con-
ditions make them as ideal alternatives to phospholipids vesicles. Cholesterol is
used to facilitate vesicle preparation, which are less leaky. Additionally, stabilizers
could also be added to avoid aggregation of niosomes by repulsive, steric, or elec-
trostatic effect. Theoretically niosome formation necessitates the existence of a spe-
cific type of amphiphile which possesses an aqueous head and a liphophilic tail and
aqueous solvent. The lipophilic unit may consist of one or two alkyl or perfluoroal-
kyl moieties or, in certain cases, a single steroidal group usually from C12 to C18.
Unit chain alkyl as lipophilic tail is more toxic compared to respective dialkylether
chain although the ester-based surfactants are chemically somewhat unstable com-
pared to ether-type surfactants. C16EO5 (polyoxyethylene cetyl ether) or C18EO5
(polyoxyethylene stearyl ether) surfactants are mainly utilized for synthesis of poly-
hedral vesicles. Various aspects manipulating the formation of niosomes are as fol-
lows: nature of surfactants, membrane composition, nature of encapsulated drug,
and hydration temperature which is responsible for shape and size of the niosomes.
The perfect condition for hydration is favored to be above the gel-to-liquid phase
transition temperature of the system. The following are applications of niosomes:
delivery of anti-cancer drugs, i.e., doxorubicin, paclitaxel, methotrexate; delivery of
peptide drugs, i.e., insulin, oligonucleotide; ophthalmic drug delivery; and also
transdermal drug delivery. Niosomes demonstrated greater stability to both tem-
perature and oxidation in contrast to the major components of liposomes, i.e.,
­phospholipids, hence are easy to handle without any serious precautions to be taken
390 A. K. Jain and U. Gupta

in storage (Fang et al. 2001). The vasoactive intestinal peptide (VIP) is therapeuti-
cally utilized for the management of Alzheimer’s disease however unable to cross
the blood–brain barrier (BBB) similar to other endogenous peptides; hence, its par-
enteral delivery is restricted. The entrapment of VIP in glucose decorated niosomes
significantly enhances brain transport of peptide compared to control niosomes (up
to 86%, in 5 min) (Biswal et al. 2008). Niosomes containing ethanol showed elastic
behavior, hence increasing the intracellular translocation and greater stability of the
Tat-GFP fusion protein against chemical degradation (Manosroi et  al. 2011).
Niosomes were used as a transporter of insulin and demonstrated noteworthy plasma
glucose-lowering effect which continued for prolonged period of time (Khaksa
et al. 2000). Further niosomes are also used as adjuvant for oral vaccination which
demonstrated significant enhancement of antibody levels after encapsulation of
ovalbumin into niosomes and shown better immune response compared to Freund’s
complete adjuvant (FCA), in the BALB/c mice (Rentel et al. 1999).

19.3  Particulate Carriers

19.3.1  Polymeric Nanoparticles

Nanoparticles are known as particulate suspensions or dried particles with a size in

the range of 10–1000 nm. As per the method used for their preparation, nanoparti-
cles, nanospheres, or nanocapsules could be produced. Contrasting to nanospheres
in which drugs are dispersed in polymer matrix, nanocapsules are vesicular sys-
tems in which the drug exits as a core in an aqueous or oily cavity which is covered
by coating of polymer; hence, they are “reservoir” system. Nanoparticles not nec-
essarily exhibit size-dependent characteristics which alter greatly in fine particles
or bulk materials. The drug/bioactive may be solubilized, dispersed, encapsulated,
or adhered to a nanoparticle matrix. A supplementary trustworthy technique to
increase the stability of bioactives is encapsulation into a nanoparticle, which pro-
tects it from the non-friendly atmosphere inside the biological system and improves
the delivery at the site of action (Niven et al. 1994). Encapsulated bioactives were
released from the nanoparticles by different mechanisms, i.e., diffusion, erosion,
swelling, or polymer degradation. Nanoparticles provide an appropriate way of
transporting low molecular weight therapeutics, plus larger bioactives, i.e., pro-
teins, peptides, or genes through localized or targeted delivery to the desired organ.
Nanotechnology concentrates on encapsulating therapeutics in biocompatible
nanocomposites, i.e., nanoparticles, nanocapsules, micellar systems, and nanocon-
jugates. These carriers could be utilized to offer targeted drug delivery (cellular/
tissue) in order to enhance oral bioavailability, to prolong drug/gene response at the
desired site, to dissolve drugs for IV administration, and to stabilize therapeutic
agents against enzymatic degradation. Additionally, the release of an entrapped
material from nanoparticles to attain wanted therapeutic response in target site for
19  Nanomaterials Used for Delivery of Bioactives 391

necessary extent should be managed. Nanoparticles have comparatively higher

intracellular uptake than ­microparticles. Polymeric nanoparticles hold remarkable
assurance for the efficient cure of disorders as they have marvelous physicochemi-
cal characteristics, i.e., size, surface charge, hydrophilicity, and lipophilicity, hence
considered as prospective carriers for bioactives, i.e., vaccines, peptides, anticancer
drugs, genes, etc. Eventually, nanoparticles offer numerous advantages compared
to free drug, such as protection from unwanted reactions with biological moieties
and breakdown, improving the absorption into a desired organ (tumors), and esca-
lating the pharmacokinetics of the therapeutics. Additionally, rate of medicament
release from nanoparticles can be amended effortlessly to match up desired thera-
peutic levels into target organ for desired period of time. Once designed properly,
nanoparticles can serve as a model delivery vehicle by preferentially picked up by
cancer cells or tumor mass and also avoids early degradation of medicament during
its transport. Further, intracellular delivery of the associated agents could be accom-
plished by engulfment through endocytosis/phagocytosis of nanoparticles.
Moreover, characteristics of a polymer could be easily altered; nanoparticles com-
prise of a versatile carrier system that can be modified to synthesize the nanoparti-
cles which are capable to cross through the biological obstacles and transport the
load into the cells and/or intracellular space. As per the rate and extent of prolonged
and controlled release of the incorporated protein, various natural and/or artificial
polymers have been explored for the formulation of nanoparticles, i.e., chitosan,
dextran, starch, albumin, gelatin, 2-methoxyethyl vinyl ether, copolymer of maleic
anhydride and cyanoacrylates, poly(lactic acid) (PLA), poly(lactic acid-co-glycolic
acid) (PLGA), PEG-PLA block copolymers, and poly(n-hexadecyl cyanoacrylate)
(Soppimath et al. 2001; Solaro and Chiellini 2006; Rytting et al. 2008; Solaro 2008;
Duan et al. 2009). A list of polymers which are frequently used for development of
nanoparticles as protein carriers is shown in Table 19.2. Out of different techniques
reported for the development of polymeric nanoparticles, majority of them reports

Table 19.2  Most widely used polymers for development of nanoparticles as drug carriers
(Vauthier and Bouchemal 2009; Vyas and Khar 2002)
Natural Colloid
Synthetic homopolymers Copolymers polymers stabilizers
Poly(lactic acid) Polylactide-poly(ethylene glycol) Chitosan Dextran
Poly(lactide-co-glycolide) Poly(lactide-co-glycolide)- Alginate Pluronic F68
poly(ethylene glycol)
Poly(ε-caprolactone) Poly(ε-caprolactone)-poly(ethylene Gelatin Poly(vinyl
glycol) alcohol)
Poly(isobutylcyanoacrylate) Poly(hexadecylcyanoacrylate-co-­ Albumin Tween® 20 or
poly(ethylene glycol) cyanoacrylate) Tween® 80
Poly(isohexylcyanoacrylate) Agarose
Poly(n-butylcyanoacrylate) Pullulan
Polyacrylates and
polymethacrylates
Polystyrene
392 A. K. Jain and U. Gupta

two key steps: the first step is emulsion formation, and the second is solvent evapo-
ration or gelation/precipitation of polymer or polymerization. A schematic demon-
stration of commonly used techniques for development of polymeric nanoparticles
is shown in Fig. 19.2. Great attention has been given to biodegradable polymers
which are self-­eliminating, hence overcoming the concern of surgical removal of
carrier system. Permeation of insulin and tetanus toxoid were increased through
oral and nasal mucosa by encapsulating it into PEG and chitosan-coated PLA/
PLGA nanoparticles, respectively (Vila et  al. 2002). Nanoparticles composed of
biodegradable polymers poly(ε-caprolactone) (PCL) and blend of PLA and PLGA
not only protected insulin from proteolytic degradation into the GI tract but also
fruitfully decrease plasma sugar concentration after oral administration to diabetic
rats (Damge et al. 2007). Higher toxoid levels were observed in the blood stream
and lymph nodes with PEGylated nanoparticles containing tetanus toxoid after

Polymer solution Adding of Polymer Sonicate to get particle

solution in a poor solvent size in nano range
with continuous stirring

Entrapped
proteins Adsorbed Conjugated proteins

Fig. 19.2 (a) Schematic representation of the commonly used method for the preparation of
­polymeric nanoparticles. (b) Schematic of the entrapment of protein in nanocarrier composites
 19  Nanomaterials Used for Delivery of Bioactives 393

120

100

80
Plasmsa glucose
(% of initial )

60

40

20

0
0 0.5 0.75 1 1.5 2 2.5 3 4 6 8
Time (hrs)
SC Nasal Control

Fig. 19.3  Hypoglycemic effect of EE NPs in the presence of Na glycocholate after nasal admin-
istration and plain SC insulin to STZ-induced diabetic rats (mean ± SE, n = 5). ∗Hypoglycemic
action of SC insulin is higher (P < 0.05) at 2 h compared to nasal NPs. ∗∗Hypoglycemic action of
nasal insulin is significantly higher compared to SC and control. EE NPs = epichlorohydrin cross-­
linked starch NPs made via emulsion method. (With kind permission from Elsevier Jain et  al.
(2008))

nasal and oral administration to rats (Vila et  al. 2005). Previously, our research
group has established the usefulness of starch nanoparticles for nasal delivery of
insulin (Jain et al. 2008) which showed superior hypoglcemic response compared
to nasal insulin solution (Fig. 19.3). One of the approaches which is widely used for
protein delivery by conjugation with various nanocarriers is receptor-mediated
endocytosis (vide infra). In this regard, our research group previously tested the
in vivo efficacy of vitamin B12 (VB12) coupled dextran nanoparticles after oral
administration of VB12 coupled dextran NPs containing insulin (Fig.  19.4). We
have also demonstrated the prevalence of VB12-mediated RME uptake of NPs by
co-administering the large excess of VB12 to saturate the receptors 1 h prior to dos-
ing of VB12-conjugated nanocarriers (Chalasani et  al. 2007). Carboxymethyl-β-
cyclodextrin-decorated chitosan (CMCD-g-CS) nanoparticles showed higher
in vitro release profile of BSA in simulated intestinal fluid compared to gastric fluid
(Song et al. 2017). Conjugation of cell-penetrating peptide (CPP) to the surface of
the 15 nm chitosan nanoparticles (prepared by nanoemulsion method) was carried
out and tested in Caco-2 cell line for translocation of insulin across the cell mono-
layer and found to be effective with 15–19% increase in insulin levels (Barbari
et  al. 2017). An exhaustive inventory of nanomedicines which are granted FDA
approval and are classified as per type of carrier/material utilized in production of
the nano formulation is shown in Table 19.1.
394 A. K. Jain and U. Gupta

Fig. 19.4  VB12-mediated uptake study of dextran NPs of medium crosslinking density conju-
gated with O’Hexyl derivative of vitamin B12 (NPs-M35’OH) in terms of plasma glucose reduc-
tion after oral administration to STZ diabetic rats (n = 3, mean ± S.E.) (Δ) VB12 + 20 IU/kg. (▲)
10 IU/kg. (●) 20 IU/kg.∗ (■) Plain insulin control. ∗ n = 6. (With kind permission from Elsevier
Chalasani et al. (2007))

19.3.2  Solid Lipid Nanoparticles (SLNs)

SLNs are composed of solid lipids which are stabilized by means of surfactants in
an aqueous suspension. They hold close resemblance to nanoemulsion; the only dif-
ference is that liquid lipid is substituted with a solid lipid. This replacement of oils
with solid lipids controls drug release in an outstanding style, since solid lipid low-
ers mobility of drug significantly, as compared to oil phase (Martins et al. 2007).
SLNs have gained attention in the last few years as carrier system for m­ acromolecules
(Marcato and Duran 2008). SLNs are coupled with few advantages and at the same
time circumvent some drawbacks of many different carriers such as nanoparticles,
liposome, ethosomes, and lipid emulsion.
The advantages offered by SLNs include:
(i) They have drug targeting and controlled drug release ability.
(ii) Protection of labile drugs against photochemical, chemical, and oxidative
degradation.
(iii) Limited toxicity compared to polymeric nanoparticles, as SLNs are made of
physiological and biocompatible lipids.
(iv) Equally suitable for both hydrophilic and lipophilic drugs.
(v) Bypass exposure of macromolecules to non-friendly hydrophobic solvents.
(vi) SLNs are useful for delivery of macromolecules through various routes such as
oral, pulmonary, intravenous, ophthalmic, and dermal (Garcia-Fuentes et  al.
2003; Hou et al. 2003; Liu et al. 2008; Joshi and Muller 2009).
19  Nanomaterials Used for Delivery of Bioactives 395

Delivery of macromolecules particularly proteins, peptides, and genes might

face problems pertaining to their entrapment, as most of them have hydrophobic
moieties that show adsorbing behavior onto surfaces (e.g., plastic and glass). This
tendency could explain the ways to discrete losses in the amount of bioactives which
reaches to the site of action (Duncan et al. 1995).
Mainly researchers described three models for incorporation of drugs or bioac-
tives into the SLNs (Muller et al. 2000; Mehnert and Mader 2001), namely, (i) the
drug-enriched shell model, (ii) the homogeneous matrix model, and (iii) the drug-­
enriched core model. These three models have different formulation composition
such as chemical composition of the lipid, bioactive, and surfactants, along with the
production method. Contrasting to most of the microsphere and nanoparticle which
are made of polymers, SLN preparation techniques avoid potentially toxic organic
solvents which may deteriorate bioactives. In addition, under prominent conditions,
SLNs can be produced to entrap a huge variety of drugs and emerge to accomplish
the desires of optimum nanocarriers (Muller et al. 1995; Wissing et al. 2004). The
synthesis of SLN depends on solidification of dispersed phase. As a result, due to
hydrophilic nature of bioactives, they have shown poor entrapment into the lipo-
philic material of SLN that tends to distribute into the aqueous phase during the
course, which is promoted by the utilization of emulsifier (surfactants) and stabiliz-
ers. Solid lipid nanoparticles are usually prepared by solid lipid nanoparticles by hot
homogenization technique (Fig.  19.5). Also, SLN can demonstrate partial

Fig. 19.5  Schematic depiction of various steps involved in the preparation of solid lipid nanopar-
ticles by hot homogenization technique
396 A. K. Jain and U. Gupta

e­ ntrapment owing to drug leakage during storage. In the last few decades, research-
ers have continuously publicized encouraging results regarding encapsulation of
bioactives in SLNs. Numerous peptides such as somatostatin, lysozyme, LHRH,
insulin, malaria antigens, calcitonin, and HBsAg have been encapsulated into the
SLNs and studied for their stability, in vitro drug release kinetics, and in vivo per-
formance (Table 19.3).
Various strategies have been explored to load macromolecules in ligand-­
decorated SLNs to enhance oral bioavailability and showed protein activity via both
caveolae- and clathrin-mediated endocytosis (Fan et al. 2014). However, mucus was
an obstacle to the translocation of SLNs. The absolute bioavailability of peptides
was improved by 2.45 to 1.98 times compared to unmodified SLNs, suggesting their
effectiveness in oral bioavailability enhancement of proteins. In another report, the
gonadorelin (a model peptide) was incorporated into the SLN developed by solvent
diffusion technique and evaluated for various parameters. (Hu et al. 2004). Lysozyme
(a model peptide) was solubilized into the melted lipid phase, and it remained intact
during the course of the process without diminishing its activity and found solubility-­
dependent entrapment efficiency of the peptide in the hydrophobic phase (Almeida
et  al. 1997). In another study, physiochemical stability, intracellular uptake by
Caco-2 cells, and in vitro cytotoxicity of beta-carotene (BC) SLNs were evaluated
and found minimum cytotoxicity of SLNs particularly after dilution (≥10 times) (Yi
et al. 2014). Goppert and Muller (2005) studied adsorption pattern of human plasma
protein on the outermost layer of SLNs after IV injection and found SLN as a poten-
tial targeted drug delivery formulation.

19.4  Inorganic Nanocarriers

Current evolution in nanotechnology has led to the utilization of different inorganic

nanoparticles such as mesoporous silica nanoparticle, carbon nanotube, calcium
phosphate, and gold nanoparticle for drug delivery (Malmsten and Zauscher 2013).
Gradually inorganic nanoparticles are adding weight; among them are carbon nano-
tubes, gold nanoparticles, and nanospheres, hence widely studied as drug carrier, as
their nanometer size enables them to move easily inside the body. The macromole-
cules could be either placed inside of the nanotube or bound to the particle surface.
The major advantages of inorganic nanocarriers are hydrophilic nature, low toxicity
profile, biocompatibility, their resistance to microbial growth, and higher stability.

19.4.1  Silica Nanoparticles

Silicates and surfactant co-assembled to produce mesoporous silica, a class of

surfactant-­templated inorganic compound. Biocompatible nature of mesoporous
silica nanoparticles (MSNs) is ideal for biological uses, hence used for delivery of
19  Nanomaterials Used for Delivery of Bioactives 397

Table 19.3 Peptide and protein molecules successfully incorporated into the solid lipid
nanoparticles
Protein/peptide entrapped Method of development
S. into solid lipid of solid lipid Entrapment
no. nanoparticles nanoparticles efficiency References
1. BSA Adsorption onto SLN n.a. Gualbert et al.
(2003)
2. Calcitonin Solvent evaporation >90% Garcia-Fuentes
(w/o/w) et al. (2005a, b)
3. CyA HPH hot dispersion 96.6–97.8% Olbrich et al.
HPH hot dispersion 88.4% (2000)
HPH hot dispersion n.a. Zhang et al.
HPH hot dispersion 96.1% (2000)
Warm microemulsion 13% protein Radtke and
(o/w) content Muller (2001a,
b)
Muller et al.
(2006)
Ugazio et al.
(2002)
4. Gonadorelin Solvent displacement 50.4–69.4% Hu et al. (2004)
5. HAS Adsorption onto SLN 12.4–32.4% Cavalli et al.
(stealth) (1999)
7–13.5%
6. Insulin Solvent displacement 26.8% Zhang et al.
Solvent evaporation n.a. (2006)
(w/o/w) 67.9% Garcia-Fuentes
Solvent evaporation 75% et al. (2003)
(w/o/w) Zhang et al.
Supercritical CO2 (PGSS) (2006)
Caliceti et al.
(2006)
7. [D-Trp-6] LHRH Warm microemulsion 90% Morel et al.
(w/o/w) (1994)
8. Lysozyme HPH cold dispersion 43.2–59.2% Almeida et al.
(1997)
9. Ovalbumin Adsorption onto SLN 70–97% Videira et al.
Melt dispersion (o/w) >80% (2002)
Videira et al.
(1998)
10. Thymopentin Warm microemulsion 5.2% or 1.7% Morel et al.
(o/w with ionic pair or (1996)
w/o/w)
11. Yak interferon-α Double emulsion solvent 83.7% Li et al. (2010)
evaporation (w/o/w)
BSA bovine serum albumin, CyA cyclosporine A, HPH high-pressure homogenization, LHRH
luteinizing hormone-releasing hormone, n.a. not available, PGSS particles from gas-saturated
solution technique
398 A. K. Jain and U. Gupta

therapeutics (Radin et al. 2002; Lai et al. 2003); however, they are not bioresorb-
able. Pore size and pore structure could be altered by ease by selection of surfactant
and co-assembly conditions. Higher porous surface along with huge effective sur-
face area of Mesoporus silica nanoparticles (MSN), hence MSN are being exploited
as potential nanocarriers for bioactive molecules. Dimension, shape, and surface
functionalization of MSN control the release rate of encapsulated bioactives. FITC-
cytochrome C was effectively delivered into the HeLa cells after encapsulation into
the MSN through a diffusion-mediated process. Also, it was demonstrated by con-
focal images that FITC-cytochrome C effectively runs away from the endosomal
degradation pathways (Tan et al. 2004; Lu et al. 2007). These cellular uptake and
endosomal breakout processes of MSNs are energy dependent, whereas surface
modification of MSNs by amine and guanidinium makes them able to infiltrate into
the cells by a clathrin- and covalent-free pathway (Xing et al. 2005; Slowing et al.
2006). Prasetyanto et al. (2016) published a straightforward approach to encapsu-
late a highly cytotoxic protein by encapsulating into the organosilica matrices
which disintegrate while contact to a chemical response and demonstrated success-
ful cellular delivery into the C6 glioma cells. Alternatively, ligands and antibodies
govern the cellular translocation of MSNs by receptor-mediated endocytosis.
Moreover, MSNs have been coated with release retarding agents such as chitosan-
PEG copolymers, to modulate the release rate of entrapped material (Tan et  al.
2004; Lu et al. 2007). Encapsulation efficiency of OVA (ovalbumin) was multiplied
by 2.5-fold after surface modification of NPs with positively charged amine because
of electrostatic interaction. Amino group modified the zeta potential of the particle
from negativity toward positivity (Mahony et  al. 2013). Amino-modified silica
nanospheres along with photoluminescent CaF2:Tm,Yb nanocrystals have shown
higher protein loading and prolonged release of the encapsulated cargo and showed
usefulness in cell uptake of bioactives (Li et al. 2017). Besides its use as a delivery
vehicle, MSNs were investigated as an immune booster which elicit immune
response even at smaller OVA levels. These NPs are synthesized under controlled
conditions allowing the modification of pore shape and surface groups (Vallet-Regi
et  al. 2007), which could be later on conjugated with various mAb structures.
Larger pores offer chances for higher loading of mAbs. Surface-functionalized
MSN has been encapsulated with a mAb against tumor cell surface protein and
administered to mice with melanoma (Lei et al. 2010). The administration of parti-
cle-encapsulated mAb demonstrated enhanced suppression of tumor enlargement
when compared to pure mAb injection. Findings suggest that encapsulation of
mAb into MSN did not change the therapeutics effect or immunological potential,
however and by assisting prolonged release of antibody results in enhancement of
the half-life of the mAb at the tumor tissue. Mice with malignant mesotheliomas
treated with intraperitoneal injection of doxorubicin (DOX) encapsulated into the
MSNs which were attached to mesothelin-­specific antibody (Macura et al. 2013).
The surface-decorated MSN were shown higher effectiveness compared to plain
DOX at lower dose level hence able to s­ ignificantly diminish the undesired effects
19  Nanomaterials Used for Delivery of Bioactives 399

of DOX. MSN were also attached to antibody directed against epidermal growth

factor in order to treat lung cancer cells, with cytotoxic drug pyrrolidone-2, and
demonstrated a 38% reduction in tumor growth with low systemic toxicity
(Sundarraj et al. 2014). Also, silica nanospheres composed of vacant core pooled
with pH-sensitive chitosan transported encapsulated protein into breast cancer cells
through targeting antibody ErbB2 and found higher levels in tumors because of
lower local pH at tumors (pH  4.0 Vs physiological pH) upon administration to
mouse model (Deng et al. 2011)

19.4.2  Gold Nanoparticles

Gold nanoparticles proved their applicability in biomedical field since they are bio-­
inert, are biocompatible, have low toxicity, have flexibility of surface modifications,
and have cellular imaging ability. Delivery of β-galactosidase into the cells using
gold nanoparticles of 2.5 nm in size are explored as useful transporter for and found
that β-galactosidase was effectively reached inside the cell membrane of HeLa cells
(Ghosh et al. 2010). The mechanism through which gold NPs internalized depend
on the surface characteristics, i.e., surface charge and/or size, mainly taken up by
endocytosis, whereas antibody-decorated GNPs followed the receptor-mediated
endocytic pathway (Tkachenko et  al. 2003; Connor et  al. 2005). Also, gold NPs
were covalently conjugated with protein antigens without any chemical interactions
and acted as adjuvant in order to produce a vaccine for cancer immunotherapy. Five
nm gold nanoparticles were utilized for protein delivery by treating Balb/c mouse
with OVA and AUNPs and were found to be highly effective in producing anti-OVA
IgG antibodies (Tang et  al. 2013). Gold nanocarriers, including nanorods, multi-
functional nanocarriers made of a gold nanoshell, and conventional nanospheres,
were conjugated with remedial mAbs and proven to be extremely selective to the
target cells without losing any antibody functionality (Shao et al. 2011; Bisker et al.
2012; Cho et al. 2014; Lee et al. 2014; Shen et al. 2014).

19.4.3  Calcium Phosphate Nanoparticles

Calcium phosphate nanoparticles (CaP) having a diameter of 40–50  nm were

developed, and their surface was altered by PEG; hence, these modified nanopar-
ticles had zeta potential very close to zero and are used for protein delivery.
Coating of pH-­ responsive material which solubilizes intestinal pH protected
encapsulated insulin against the gastric degradation. In vitro release of insulin was
negligible in acidic atmosphere whereas insulin was released for a time span of 8 h
in intestinal pH (Ramachandran et  al. 2008). Zinc is reported to be used for
400 A. K. Jain and U. Gupta

r­ etarding insulin release (long-acting insulins); thus, calcium phosphates, zinc cal-
cium, and zinc phosphates look attractive contenders for developing c­ eramic-based
insulin carriers. Oral delivery is not only the most favored way of administration
of drugs but also provides advantage of patient compliance. Preferably, the absorp-
tion of nanoparticles takes place via Peyer’s patches region which arrived at the
lymphatic system hence bypasses the first-pass metabolism during which insulin
degraded significantly. BioSante Pharmaceuticals, a US-based company, success-
fully synthesized calcium phosphate nanoparticles and entered into the first stage
of toxicity studies.

19.5  Concluding Remarks

Delivery of macromolecules is required to be more creative approach than smaller

molecular weight therapeutics and demand safer administration, deserve enormous
assurance for the treatment of complex diseases. In vivo delivery of macromole-
cules is emerging importance day by day particularly after latest advancement in
recombinant technology which leads to commercial supply of huge variety of thera-
peutically effective macromolecules. The survival of these agents in the biological
environment is of vital importance due to possible denaturation or enzymatic degra-
dation in the absence of an ideal carrier. The selected carrier must provide the com-
plete protection and should be able to translocate the cargo as per desired needs.
Hence, it is critically important to design a suitable carrier of appropriate size, com-
position, and surface behavior as well as biocompatible. Out of the huge range of
the carriers studied, nanocarriers emerged as an outstanding choice during the last
decades for their successful therapeutic effects through oral, pulmonary, buccal,
nasal, as well as parenteral routes.
Because of the biocompatible nature of lipids utilized in synthesis of nanoli-
posomes and solid lipid nanoparticles, these carriers are proved to be more safe
than other types of nanocarriers. Moreover, lipid-based carriers serve as strong
immunological adjuvants, capable of eliciting cellular and humoral response
against a range of infectious agents related to human disease. However, generally
they show considerable instability because of inadequate shelf-life and shorter
half time. Indeed, because of high stability of polymeric nanoparticles over other
nanocarriers, they emerged as promising carriers of bioactives to meet specific
requirements. In addition, surface decoration of these nanoparticles with specific
ligands RES uptake can be drastically decreased which is a key constraint with
these carriers. On the other hand, synthesis of polymeric nanocarriers generally
involves use of organic solvents which could have deleterious effect on macro-
molecules. Therefore, these drawbacks could be beaten by the picking up protein
friendly method for particle synthesis by employment of self-assembling
­water-soluble polymers.
19  Nanomaterials Used for Delivery of Bioactives 401

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Chapter 20
Efficacy of Nano-phytochemicals Over
Pure Phytochemicals Against Various
Cancers: Current Trends and Future
Prospects

Asif Jafri, Saima Amjad, Shabana Bano, Sudhir Kumar, M. Serajuddin,

and Md Arshad

20.1  P
 hytochemicals and Nano-phytochemicals as Potent
Anticancer Agents

Cancer remains a universal destructive disease and the second most common cause
of death in humans. Approximately 7.6 million mortalities per year are attributed to
cancer. Developing nations are facing more cancer incidence and now represent
about 60% of the deaths (Siegel et al. 2017). The World Health Organization has
predicted that about 15 million new incidences of cancer will emerge globally in
2020. Anticancer activity is the consequence of natural or synthetic compounds to
reverse, repress, or check the development of cancer. As the present radiotherapy
and chemotherapy treatments do not distinguish normal cells from cancer cells and
thus can cause severe side effects, researchers and the pharmaceutical industry are
concerned to develop a smart drug that can cure this destructive disease without
affecting normal healthy cells (Jafri et al. 2018). Fortunately, India is a vast resource
of medicinal plants and natural products. Epidemiological observation suggests that
Indian herbs, spices, and their isolated phytochemicals possess significant antican-
cer potential and that their consumption is associated with reduction of the progres-
sion of some cancers. The anticancer properties of several phytochemicals isolated
from different medicinal plants have been reported. Table 20.1 depicts the antican-
cer properties of some potent phytochemicals and their anticancer mechanisms.

Asif Jafri and Saima Amjad contributed equally with all other contributors.

A. Jafri · M. Arshad (*)

Molecular Endocrinology Lab, Department of Zoology, University of Lucknow,
Lucknow, India
S. Amjad · S. Bano · S. Kumar · M. Serajuddin
Department of Zoology, University of Lucknow, Lucknow, India

© Springer Nature Switzerland AG 2020 407

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0_20
408 A. Jafri et al.

Table 20.1  Potent phytochemicals and their anticancer mode of action against some cancers
Nature of
Sample Name of phytochemical and Mode of action in the
no. phytochemicals the plant source induction of apoptosis References
1. Apigenin A flavonoid present Encourages apoptosis, Shukla and
in the flowers of inhibits oxidative stress by Gupta
chamomile plants but scavenging free radicals, (2010)
also found in plenty promotes anti-angiogenesis
in parsley, celery,
celeriac, and
chamomile tea
2. Berberin An alkaloid present Apoptosis induction, blocks Tan et al.
in Hydrastis cell-cycle progression, (2011)
canadensis inhibits signal transduction
Common name: pathway, impairs cell
Goldenseal or adhesion and invasion
orangeroot
3. Combretastatin Phenolic compound Inhibits angiogenesis, Tozer et al.
A4 found in Combretum encourages cell-cycle arrest (2002)
caffrum via inhibition of tubulin
Common name: polymerization
Cape bushwillow
4. Cucurbitacin B A terpenoid present Apoptosis induction, Kaushik
in Trichosanthes inhibits cell-cycle et al. (2015)
cucumerina progression, impairs signal
Common name: transduction pathways,
Chichinda, snake prevents angiogenesis
gourd or Padwal
5. Curcumin Curcuma longa Enhances the expression of Ahmad et al.
Common name: tumor suppressor genes and (2016)
Turmeric or Haldi downregulation of
oncogenes, promotes
anti-angiogenesis, inhibits
signal transduction pathway,
damages cell adhesion and
invasion properties
6. Epigallocatechin-­ Camellia sinensis Initiates apoptosis, reduces Singh et al.
3-­gallate (EGCG) Common name: oxidative stress by (2011)
Green tea scavenging free radicals,
inhibits angiogenesis,
enhances the expression of
the tumor suppressor gene,
inhibits signal transduction
pathways
7. Ellagic acid A predominant Triggers apoptosis, reduces Zhang et al.
phenol abundant in oxidative stress and (2014)
numerous fruits and scavenges free radicals,
vegetables inhibits angiogenesis,
damages cell adhesion and
invasion properties
(continued)
20  Efficacy of Nano-phytochemicals Over Pure Phytochemicals Against Various… 409

Table 20.1 (continued)
Nature of
Sample Name of phytochemical and Mode of action in the
no. phytochemicals the plant source induction of apoptosis References
8. Emodin A glycoside present Encourages apoptosis, Wei et al.
in Rhamnus frangula hinders tyrosine kinase (2013)
Common name: enzyme action, reduces
Alder buckthorn oxidative stress by
scavenging free radicals,
augments anti-angiogenesis,
inhibits signal transduction
pathway, upregulates the
expression of tumor
suppressor genes
9. Ferulic acid or A phenolic phyto-­ Induces apoptosis, reduces Srinivasan
hydroxycinnamic compound present in oxidative stress by et al. (2007)
acid the cell walls of scavenging free radicals
plants
10. Gambogic acid A glycoside present Induces apoptosis, promotes Kashyap
in Garcinia hanburyi anti-angiogenesis, inhibits et al. (2016)
(resins) telomerase enzyme action,
Common name: inhibits signal transduction
Gamboge pathway
11. Genistein Found in Genista Encourages apoptosis, Li et al.
tinctoria inhibits angiogenesis, (2012)
Common name: inhibits cell-cycle
Dyer’s greenweed or progression, induces the
Dyer’s broom expression of tumor
suppressor gene
12. Hesperitin Found abundantly in Induces apoptosis, promotes Roohbakhsh
citrus fruits anti-angiogenesis, et al. (2015)
encourages the expression
of tumor suppressor gene
13. Honokiol A lignin present in Induces apoptosis, promotes Fried and
Magnolia grandiflora anti-angiogenesis, and Arbiser
Common name: inhibits tumor growth; (2009)
Southern magnolia, impairs signal transduction
lily tree, laurel pathways
magnolia
14. Isoliquiritigenin A terpenoid present Enhances apoptosis, impairs Orlikova
in Glycyrrhiza signal transduction et al. (2011)
uralensis pathways, inhibits cell-cycle
Common name: progression, obstructs
Liquorice root, angiogenesis, damages cell
liquorice, sweetroot, adhesion and invasion
Gan Cao properties
15. Kaempferol A flavonoid present Encourages apoptosis, Kim and
in various plants and inhibits angiogenesis Choi (2013)
plant-derived foods
(continued)
410 A. Jafri et al.

Table 20.1 (continued)
Nature of
Sample Name of phytochemical and Mode of action in the
no. phytochemicals the plant source induction of apoptosis References
16. Luteolin Found in Salvia Induces apoptosis, inhibits Lin et al.
tomentosa and also oxidative stress by (2008)
found in some scavenging free radicals,
dietary sources prevents the expression of
including carrots, the oncogene, impairs signal
green pepper, transduction pathway,
chamomile tea, encourages the expression
broccoli, parsley, of a tumor-suppressing
olive oil gene, promotes cell-cycle
arrest, prevent angiogenesis
17. Morin Morus alba Promotes apoptosis, Park et al.
Common name: encourages (2015)
White mulberry anti-angiogenesis
18. Naringenin A predominant Promotes apoptosis, inhibits Ahamad
flavanone, abundant angiogenesis, encourages et al. (2014)
in grapefruit and also tumor suppressor gene
found in a variety of expression, impairs signal
fruits and herbs transduction pathway
19. Nobiletin A flavonoid isolated Encourages apoptosis, Rawson
from citrus peels inhibits angiogenesis, et al. (2014)
induces the expression of
tumor suppressor gene,
scavenging free radicals,
and reduces oxidative stress
20. Piperine A predominant Induction of apoptosis, Jafri et al.
alkaloid of Piper upregulates tumor (2019)
nigrum suppressor genes, activation
Common name: of caspase-3, damages
Black pepper signal transduction
pathways
21. Quercetin A major flavonoid Encourages apoptosis, Khan et al.
present in several reduce oxidative stress by (2016)
fruits and vegetables: scavenging free radicals,
apples, berries, red inhibits angiogenesis,
onions, green tea, impairs signal transduction
etc. pathway
22. Resveratrol A phenol found in Encourages apoptosis, Varoni et al.
cranberry (Vaccinium reduces oxidative stress by (2016)
macrocarpon), scavenging free radicals,
grapes (Vitis promotes cell-cycle arrest,
vinifera), and peanut inhibits expression of
(Arachis hypogaea) oncogene
(continued)
20  Efficacy of Nano-phytochemicals Over Pure Phytochemicals Against Various… 411

Table 20.1 (continued)
Nature of
Sample Name of phytochemical and Mode of action in the
no. phytochemicals the plant source induction of apoptosis References
23. Silibinin Silybum marianum Induces apoptosis, promotes Ting et al.
Common names: anti-angiogenesis, reduces (2013)
Carduus marianus, oxidative stress by
milk thistle, blessed scavenging free radicals,
milk thistle, Scotch hinders cell-cycle
thistle progression, enhances tumor
suppressor gene expression,
impairs cell adhesion and
invasion properties
24. Tetrandrine An alkaloid present Apoptosis induction, Chen (2002)
in Stephania anti-inflammatory and
tetrandra anti-carcinogenic
Common name: Fang effectiveness, anti-­
Ji angiogenic agent
25. Thymoquinone A predominant Promotes apoptosis, reduces Woo et al.
quinone found oxidative stress by (2012)
abundantly in Nigella scavenging free radicals,
sativa arrests cell cycle, impairs
Common name: cell adhesion and invasion,
Caraway, black encourages enzyme
cumin, or Kalonji induction and thus enhances
detoxification, hinders
angiogenesis
26. Vincristine A potent alkaloid Encourages apoptosis in Moudi et al.
existing in cancerous cells, inhibition (2013)
Catharanthus roseus of cell-cycle progression via
Common name: inhibiting polymerization of
Sadabahar or tubulin
periwinkle
27. Vinblastine An alkaloid existing Encourages apoptosis in Moudi et al.
in Catharanthus cancerous cells, inhibition (2013)
roseus of cell-cycle progression via
Common name: inhibiting polymerization of
Sadabahar or tubulin
periwinkle
28. Zerumbone A predominant Encourages cell-cycle Rahman
terpenoid found arrest, inhibits expression of et al. (2014)
abundantly in the oncogene, reduces
Zingiber zerumbet oxidative stress by
Common name: scavenging free radicals
Awapuhi, bitter
ginger, pinecone
ginger
(continued)
412 A. Jafri et al.

Table 20.1 (continued)
Nature of
Sample Name of phytochemical and Mode of action in the
no. phytochemicals the plant source induction of apoptosis References
29. α-Mangostin A xanthonoid Triggers apoptosis, reduces Jafri et al.
obtained from oxidative stress by (2018)
Garcinia mangostana scavenging free radicals,
Common name: encourages cell-cycle arrest,
Mangosteen enhances caspase-3 activity
30. β-Lapachone A quinone found in Induces apoptosis, impairs Kung et al.
Tabebuia signal transduction pathway, (2014)
avellanedae reduces oxidative stress by
Common name: Pink scavenging free radicals
tabebuia

20.2  T
 he Advantage of Nano-phytochemicals Over Pure
Phytochemicals

Phytochemicals have potential ability to protect against many chronic diseases such
as heart disease, diabetes, neuronal degeneration, and cancer (Subramanian et al.
2016). Phytochemicals possess significant antiproliferative and apoptotic effects
against various cancer cells and are widely used in anticancer research (Fig. 20.1).
These phytochemicals induce apoptotic effects on various cancerous cells through
different apoptotic signaling pathways and check cell-cycle progression, regulating
the antioxidant system and detoxification.
Although the phytochemicals possess marvelous antiproliferative and apoptotic
potential, they also have some limitations to be target-effective drugs because of
their lower solubility in water, poor penetration power for entering targeted cells,
restricted therapeutic potential, hepatic disposition, and prompt absorption by nor-
mal cells (Bhadoriya et al. 2011). Hence, to overcome these issues, scientists have
shifted their interests toward a nano-based targeted drug delivery system of some
promising phytochemicals to enhance their aqueous solubility, target specific
to cancerous cells, improving cellular uptake, bioavailability and reducing the quan-
tities of phytochemicals to achieve a secure therapeutic level of these potent phyto-
chemicals for future targeted drug delivery systems (Fig.  20.2). The
nano-phytochemicals also have various advantages over the pure phytochemicals in
having excellent stability in the blood, a multi-efficient design, and hence improved
anticancer effectiveness compared to the pure phytochemicals.

20.2.1  Role of Nanoform Phytochemicals in Cancer Research

Nanotechnology has improved the bioavailability, solubility, and targeted delivery

of active phytochemicals by using nanoparticles as a carrier and enhancing the bio-
activity of potent phytochemicals (Nishiyama 2007). There are some previous
20  Efficacy of Nano-phytochemicals Over Pure Phytochemicals Against Various… 413

Fig. 20.1  Apoptotic induction by phytochemicals and nano-phytochemicals in cancer cells

Fig. 20.2  Schematic presentation of nanocarrier nano-phytochemicals and their advantages in

cancer research

reports of the active phytochemical-loaded nanoparticles targeting against cancer

cells with reduced side effects. Table  20.2 shows some promising nano-­
phytochemicals and their anticancer potential against some cancers.
414 A. Jafri et al.

20.2.1.1  Broccoli Gold Nanoparticles

Broccoli (Brassica oleracea) is a cruciferous vegetable that is potentially protective

against some cancers (Steinmetz and Potter 1991a, b). Broccoli phytochemicals are
loaded with polyphenols, glucosinolates (GLs), vitamin C, carotene, folic acid, and
fibers (Conaway et al. 2001; Mahn and Reyes 2011). These constituents enhance
antioxidant activities and stimulate phase-2 detoxification enzymes (Tang et  al.
2006; Qazi et al. 2010). Broccoli-loaded gold nanoparticles (B-Au NPs) were syn-
thesized and were analyzed against some cancerous cells, such as MDA-MB-231,
SkBr3, and T47D cells of breast carcinoma, PC-3 cells of prostate carcinoma, and
U266 cells of myeloma to evaluate the anti-cancerous activity (Khoobchandani
et al. 2013). The findings revealed that the conjugated B-Au NPs possessed excel-
lent anti-cancerous effects against breast carcinoma, prostate carcinoma and
myeloma cells.

20.2.1.2  Gold Quercetin Nanoparticles

Quercetin is a predominant flavone that possesses antioxidant and antiinflammatory

properties and provides valuable health benefits to humans (Aguirre et al. 2011). It
is isolated from many food items such as leafy vegetables, citrus fruits, red wine,
green tea, apples, berries, onions, and Ginkgo biloba (Davis et al. 2009). A previous
study reported the synthesis of gold-quercetin nanoparticles (GQ NPs) and its anti-
cancer activity against liver carcinoma (Ren et  al. 2017). The GQ NPs regulated
abnormal proliferation, colony formation, and cell migration in liver cancer cells,
and subsequently inhibited cancer progression. GQ NPs encouraged apoptosis in
liver carcinoma cells by activation of caspases (3, 9) and expression of cytochrome
c (Cyto-c). The study showed that GQ  NPs impair the caspase/Cyto-c pathway,
obstruct NF-κB/COX-2 and Akt/ERK1/2, and suppress AP-2β/hTERT signaling
pathways.

20.2.1.3  Curcumin Nanoparticles

Curcumin has both anticancer and cancer prevention properties. Curcumin is a natu-
ral bioactive polyphenolic constituent, found in turmeric, with properties to inhibit
proliferation and metastasis in a wide range of cancers (Joe et al. 2004). However,
poor solubility in water has limited the systemic bioavailability of curcumin when
administered orally. To overcome the solubility and bioavailability restrictions of
curcumin, it was loaded on various types of nanoparticles. Methoxy polyethylene
glycol (mPEG) and polycaprolactone (PCL) co-polymers enhanced the anti-­
cancerous activity of curcumin with efficient loading capability and sustainable
release in A549 cells of lung epithelial carcinoma. This curcumin-loaded nanopar-
ticle effectively enters into lung carcinoma A549 cells and interacts with the nucleus
to encourage apoptosis (Yin et  al. 2013). Poly lactic-co-glycolic acid curcumin
20  Efficacy of Nano-phytochemicals Over Pure Phytochemicals Against Various… 415

Table 20.2  Promising nano-phytochemicals and their anticancer potential against some cancers
Sample Nano-­ Source of
no. phytoconstituents phytochemical Mode of action References
1. Broccoli Broccoli Anticancer action against Khoobchandani
nanoparticle MDA-MB-231, SkBr3, et al. (2013)
and T47D cells of breast
carcinoma, PC-3 cells of
prostate carcinoma, and
U266 cells of myeloma
2. Quercetin Leafy vegetables, Inhibits growth in hepatic Davis et al. (2009),
nanoparticle citrus fruits, red carcinoma cells, Ren et al. (2017)
wine, green tea, modulates caspase
apples, berries, activities, upregulates
onions, Ginkgo cytochrome c, obstructs
biloba NFκB/COX-2 and Akt/
ERK1/2 expression
3. Curcumin Turmeric Inhibits phosphoinositide Yin et al. (2013),
nanoparticle (Curcuma longa) 3-kinase pathway, Yallapu et al.
suppresses tumor burden, (2014),
induced apoptosis,, Esfandiarpour-­
enhanced therapeutic Boroujeni et al.
ability (2017)
4. Selaginella Selaginella Inhibits growth in A549 Syaefudin et al.
doederleinii doederleinii cells of human lung (2016)
nanoparticle Hieron carcinoma
5. Nigella sativa Nigella Upregulates miR-34 a,d, Bhattacharya et al.
nanoparticles represses Rac1 mRNA (2015), Ganea
protein expression, et al. (2010),
enhances antiproliferative Dehghani et al.
and apoptotic properties (2015)
6. Honokiol Magnolia Antiproliferative effect Cheng et al.
nanoparticle officinalis against osteosarcoma (2016), Li et al.
cells, induces apoptosis, (2008)
inhibits proliferation of
tumors and prevents
angiogenesis, micro-­
vessel generation. and
cell-cycle arrest
7. Silibinin Silybum marianum Suppresses cell Ebrahimnezhad
nanoparticle proliferation, inhibits et al. (2013),
hTERT expression, Amirsaadat et al.
prevents metastasis and (2017), Xu et al.
angiogenesis in breast (2013)
cancer cells
8. Ursolic acid Epicuticular Encourages anticancer Baishya et al.
nanoparticles waxes of apples, activity, promotes (2016), Jiang et al.
peels of fruits, lysosomal destruction, (2017)
herbs and spices enhances ROS
such as rosemary augmentation, promotes
and thyme apoptosis in MCF-7 cells
of breast carcinoma
(continued)
416 A. Jafri et al.

Table 20.2 (continued)
Sample Nano-­ Source of
no. phytoconstituents phytochemical Mode of action References
9. β-Lapachone Bark of the Activates anti-cancerous Jeong et al. (2009)
nanoparticle Lapacho tree and radiotherapeutic
efficacy
10. Ferulic acid Vegetable sources, Reduces cancer cell Zhao and
nanoparticles oat flours, wheat, proliferation, promotes Moghadasian
rice intracellular ROS (2008), Kumar and
production, enhances Pruthi (2014)
DNA damage, lipid
peroxidation, and
encourages apoptosis

nanoparticles (PLGA-CUR NPs) showed tumor regression properties against pros-

tate carcinoma cells by inhibiting colony formation and cell growth in prostate can-
cer cell xenografted mice (Yallapu et al. 2014). PLGA-CUR NPs conjugated with
epidermoid growth factor receptor were targeted to GE11 peptides in breast carci-
noma cells in vitro and in a tumorous mice model. It extended the epidermal growth
factor receptor (EGFR) expression in MCF-7 cells of breast carcinoma and reduced
the phosphoinositide-3 kinase pathway, suppressed tumor growth, suppressed can-
cer cell proliferation, and improved drug clearance from the circulation (Jin et al.
2017). Curcumin-loaded magnetic nanoparticles were also significantly taken up in
MDA-MB-231 cells of human epithelial breast carcinoma. These nanoparticles
showed strong anticancer activity via strong penetration power into the cell by
endocytosis (Yallapu et al. 2012). The uploaded curcumin magnetic nanoparticles
exhibited strong magnetic resonance properties and potentially enhanced the anti-
cancer targeting capacity of curcumin.
Nano-curcumin effectively decreased the level of miRNA-21, β-catenin, and the
expression of E6/E7 HPV oncoproteins in a mouse cervical cancer model (Zaman
et  al. 2016). Also, curcumin-loaded silica nanoparticles (Dinda et  al. 2012) and
curcumin-loaded folate-modified chitosan nanoparticles (Esfandiarpour-Boroujeni
et al. 2017) have significant anticancer effect against HepG2 cells of hepatocellular
carcinoma and MCF-7 cells of breast carcinoma, respectively.

20.2.1.4  Selaginella doederleinii Leaf Nanoparticles

Selaginella doederleinii Hieron possesses several bioactive phytochemicals and has

been extensively used in traditional herbal medicine for curing rheumatoid arthritis
and various cancers, specifically lung cancer, cervical cancer, choriocarcinoma, and
nasopharyngeal carcinoma (Abdille et al. 2005; Ishii et al. 2005; Wang et al. 2015).
Selaginella leaf extract nanoparticles (SDNPs) reduced the viability of lung carci-
noma A549 cells and were least toxic to normal Chang liver cells (Syaefudin et al.
2016). The findings revealed the apoptotic potential of SDNPs and the targeted drug
delivery system without affecting the normal Chang cells.
20  Efficacy of Nano-phytochemicals Over Pure Phytochemicals Against Various… 417

20.2.1.5  Nigella sativa Nanoformulation

Nigella sativa, commonly known as nigella, kalonji, black caraway, and black
cumin, is broadly used as a traditional medicine universally (Heiss and Oeggl 2005).
Thymoquinone is one of the major active phyto-constituents present in Nigella
sativa and possesses various pharmacological properties: antimicrobial, antiinflam-
matory, antipyretic, hypoglycemic, analgesic, and antioxidant (Ali and Blunden
2003). Previous studies reported the anticancer and antimutagenic activity of thy-
moquinone in Caco-2, HT-29, HCT-116, DLD-1, and LoVo cancerous cells (Gali-­
Muhtasib et  al. 2006). The encapsulated thymoquinone (TQ) nanoparticles (TQ
NPs) were synthesized with the help of biodegradable polyvinyl pyrrolidone (PVP)
and polyethylene glycol (PEG) (less than 50 nm in size) and significantly enhanced
anticancer efficacy by increasing bioavailability and solubility (Bhattacharya et al.
2015) of TQ. In vitro study in MCF-7 cells of breast carcinoma and in vivo tumor-­
bearing mice demonstrated that PEG-TQ NPs enhance miR-34a, repress Rac1
mRNA protein expression, prevent cell migration, and hinder angiogenesis. TQ
loaded with modified molecular micelles, PLGA nanoparticles, and chitosan myris-
tic acid nanogel exhibited more antioxidant and antiproliferative effectiveness at
low doses with controlled release as compared with pure TQ against MCF-7 cells
and MDA-MB-231 of breast carcinoma (Ganea et al. 2010; Dehghani et al. 2015).
These findings showed that TQ NP have a more potent apoptotic effect than pure TQ.

20.2.1.6  Honokiol Nanoparticle

Honokiol is a polyphenol, a lignan obtained from the medicinal plant Magnolia

officinalis (Li et  al. 2008). It possesses multifactorial pharmacological properties
and is widely used to treat stomach upset, inflammation, nervous disturbance, and
anxiety (Chiang et al. 2006; Kim and Cho 2008; Deng et al. 2008; Fried and Arbiser
2009). It also showed antineoplastic and apoptotic effectiveness against various
cancerous cells (Yuan et  al. 2009; Steinmann et  al. 2012; Avtanski et  al. 2013;
Cheng et al. 2014; Subramaniam et al. 2015). Honokiol-loaded synthesized nano-
formulation co-polymer micelles with monomethoxy polyethylene glycol and
­polycaprolactone (HK-MPEG/PCL) increased bioavailability and solubility. The
anticancer activity of HK-MPEG/PCL showed reduced tumor growth and apoptotic
induction in a cancer nude mouse model and prevented angiogenesis (Cheng et al.
2016). Another study on honokiol-loaded co-polymer synthesized with folate and
polyethyleneimine nanoparticles (HK NPs) significantly prevented metastasis, pro-
liferation, tumor growth, angiogenesis, and cell-cycle progression (Gou et al. 2010).
The developed HK NPs potentially encouraged apoptosis of HNE-1 cells of naso-
pharyngeal carcinoma as compared to pure honokiol.
418 A. Jafri et al.

20.2.1.7  Silibinin-Loaded Nanoparticle

Silibinin is a natural antioxidant and a polyphenolic flavonoid found in Silybum

marianum, also known as silybin or milk thistle (Davis-Searles et al. 2005). It pos-
sesses multifactorial pharmacological effects such as hepato-protective, antioxi-
dant, and anticarcinogenic activities. Silibinin encourages apoptosis via inhibiting
cell-cycle progression, preventing proliferation, impairs angiogenesis, and enhanc-
ing immune stimulation in several cancers (Mateen et al. 2010; Nejati-Koshki et al.
2012; Surai 2015). Some previous studies demonstrated that silibinin arrested the
cancer cycle and inhibited the growth, progression, and angiogenesis of tumorous
cells (Singh et  al. 2006; Liang et  al. 2014). Silibinin-loaded nanoparticles with
PLGA-PEG co-polymer were synthesized to evaluate the anticancer potential and
expression of the hTERT gene in T47D cells of breast carcinoma and A549 cells of
lung carcinoma. The findings showed that hTERT expression more efficiently
reduced the cell viability of both cancerous cells with the increasing concentrations
of nano-silibinin as compared to the pure silibinin (Ebrahimnezhad et  al.  2013;
Amirsaadat et al. 2017). The silibinin-loaded phosphatidylcholine lipid nanoparti-
cles significantly reduced the growth and angiogenesis of breast carcinoma (Xu
et al. 2013). These findings suggested that nano-form silibinin was a more efficient
anticancer agent than pure silibinin.

20.2.1.8  Ursolic Acid Nanoparticle

Ursolic acid is a plant-derived triterpenoid that is present in epicuticular waxes of

apples, fruit peels, herbs, and spices such as rosemary and thyme (Shanmugam
et al. 2013). Ursolic acid has multifactorial pharmacological properties, such as
antiinflammatory (Chattopadhyay et al. 2002), antidiabetic (Jang et al. 2010), anti-
epileptic, anticancer (Tannock 2011), and liver protective (Shanmugam et  al.
2011; Prasad et al. 2011) elements. Ursolic acid-based mesoporous silica nano-
spheres (UAMSN) were synthesized with the help of pH-sensitive chitosan and
folic acid for the targeted drug delivery of tumor cells (Jiang et al. 2017). Enhanced
apoptotic effects of ursolic acid-encapsulated PLGA nanoparticles (UA-NPs)
were found in B16F10 mouse melanoma cells as compared with pure ursolic acid
(Baishya et al. 2016). Folate and chitosan-based nanocarriers for the delivery of
ursolic acid (­ FA-CS-UA-­NPs) were studied for in vitro MCF-7 cells of breast car-
cinoma and in an in vivo tumor xenograft mouse model (Jin et al. 2016). The find-
ings revealed FA-CS-UA-­ NPs penetrated into the cells via endocytosis and
encouraged apoptosis. The FA-CS-­UA-NPs had the potential to localize into the
mitochondria, induce excessive reactive oxygen species (ROS), and enhance
apoptosis in cancerous cells.
20  Efficacy of Nano-phytochemicals Over Pure Phytochemicals Against Various… 419

20.2.1.9  β-Lapachone Nanoparticle

Beta-lapachone is a quinone that is abundant in the bark of Tabebuia avellanedae

(Lapacho tree) and has potent anti-cancerous properties (Pardee et al. 2002). It gen-
erates apoptosis via modulating NADPH quinone oxidoreductase-1 (NQO1) in can-
cerous cells (Blanco et al. 2007). Lapachone-loaded silver nanoparticles (Lap Au
NPs) were synthesized and targeted on anti-EGFR antibody through intravenous
injection of Lap Au NPs to tumor-bearing xenografted mice, showing an enhanced
tumor suppression effect as well as enhanced radiotherapeutic efficacy (Jeong
et al. 2009).

20.2.1.10  Ferulic Acid Nanoparticles

Ferulic acid is a phenolic phytochemical found in vegetable sources, oat flours,

whole grain wheat, and rice (Zhao and Moghadasian 2008; Kumar and Pruthi 2014).
A ferulic acid-loaded synthesized PLGA nanoparticle (FA-PLGA-NP) enhances
apoptosis in NCI-H460 cells of lung carcinoma as compared to its pure form (Merlin
et al. 2012). The FA-PLGA-NPs encourage apoptosis via decreasing cell prolifera-
tion, generating excessive intracellular ROS, enhanced DNA damage, and lipid
peroxidation.

20.3  Conclusion

Numerous studies on phytochemicals have shown significant anticancer potential

but some limitations. Studies on nano-phytochemicals, both in vitro and in animal
models, showed enhanced bioavailability, improved cellular uptake, reduced doses,
and enhanced solubility, overcoming the limitations of pure phytochemicals.
Further, the potent anticancer nano-phytochemicals without side effects that are not
destructive to normal cells are still to be investigated. The ongoing research on
nano-phytochemicals opens a new avenue for cancer cure by following promising
phytochemicals with the advanced approaches of nanotechnology.

Acknowledgments  The authors Asif Jafri and Md Arshad acknowledge the support of Uttar
Pradesh Council of Science and Technology, Lucknow, India (File No. CST/SERPD/D-299). Asif
Jafri is also grateful to the Council of Scientific and Industrial Research, India for the award of
Senior Research Fellowship (File No. 09/107 (0393)/2018- EMR-I).
420 A. Jafri et al.

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Index

A Bioactives
Actinobacteria, 71 reverse-phase evaporation process, 388
Active antimicrobial effect, 30 SLN preparation techniques, 395
Advanced photo-oxidation process supplementary trustworthy technique, 390
(APOP), 303 Biodegradability, 334
Advanced wastewater treatment technologies Biodiesel fuel, 289, 290
APOP, 303 Biological synthesis, MNPs, 128, 129, 131
AVF technology, 303 Bio-lubricants
coke oven (CO) by-product, 304 MQL technique, 339
membrane filtration, 303 oxidation stability, 342
microbial fuel cells, 304 vegetable oils (see Vegetable oils-based
nanotechnology, 303 lubricants)
NTSs, 304 Biomass, 289
urban sanitation, 304 Biomimetic biosensors, 113
urine separating process, 304 Biomolecules, 90, 91, 93, 99
Agglomeration, 345, 346, 352 Bionanoelectronics, 315
Agrifood sector, 276 Biopolymer, 170
Alcohol dehydrogenase, 176 Bio-recognition element, 112
Antibacterial agents, 43 Bioreduction process, 129
Antimicrobials, 33 Biosensing techniques, 110
Apoptotic induction, 413 Biosensors, 28, 111
Aptamer, 197 aptasensors, 113
Aptasensors, 113 biomimetic, 113
Arbuscular mycorrhiza (AM) fungi classification, 111
Ag NPs, 59 electrochemical, 114
efficiency, 58 enzymatic, 112
Fe3O4 NPs, 60 genosensors, 112
ZnO NPs, 58 immunosensors, 111
Atomic force microscopy (AFM), 236, 237 magnetic, 115
Automatic variable filtration (AVF), 301, 303 optical, 114
piezoelectricity, 115
thermometric, 115
B whole cells, 112
Bak proteins, 388 Blood-brain barrier (BBB), 328, 390
Beta-lapachone, 419 Bovine serum albumin (BSA), 165

© Springer Nature Switzerland AG 2020 425

I. Bhushan et al. (eds.), Nanomaterials and Environmental Biotechnology,
Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-34544-0
426 Index

Broccoli (Brassica oleracea), 414 SEM, 236

Buckyball molecule, 316, 318 TEM, 236
Buckyballs, 316 ultrastructure, 235
and silicon, 316 size and distribution
formulation-related variables, 234
LD, 235
C PCS, 234
C16EO5 (polyoxyethylene cetyl ether) PDI, 234
surfactants, 389 surface charge, 237
C18EO5 (polyoxyethylene stearyl ether) Chemical and biological nanoparticles, 26
surfactants, 389 Chemotherapeutics, 189
Calcium phosphate nanoparticles Chemotherapy, 325
(CaP), 399–400 Chip flowing, 333
Cancer nanomedicine, 325 Chitin, 163
Canola oil, 353, 358, 361 Chitosan
Cantilever biosensors, 115 acidic solution, 166
Carbon nanotubes (CNTs), 57, 66, 171, 202, alpha-amylase, 173
208, 289, 307, 318 α-glucosidase, 172
agriculture sector, 76 β-galactosidase, 170
chlorophyll, 75 BSA, 165
CNTFETs, 259 cellulase, 171
coated, 72 coprecipitation, 166
cyanobacteria, 75 glucoamylase, 172
electronics, 259 immobilization techniques, 164
gene expression, 72 laccase, 173
gram-positive bacteria, 76 lipase, 174
graphene (see Graphene) literature surveys, 164
microbial community, 76 molecular weight, 163
model parameter description, pectinase, 173
259, 260 reactivity and solubility, 163
MWCNTs, 72, 267 sodium tripolyphosphate, 166
photosynthesis, 75 TPP, 166
plant growth processes, 73 xylanase, 172
soil microbial community, 76 Chitosan nanoparticle, 171
SWCNTs, 72, 267 Cholesterol, 388, 389
uncoated, 72 Chronoamperometric transduction
Carboxymethyl-β-cyclodextrin-decorated technique, 114
chitosan (CMCD-g-CS), 393 Clean and safe water, 201
Cell-cycle progression, 418 Clottocytes, 323
Cell-penetrating peptide (CPP), 393 Coalescence, 27
Cellulase, 171 Cold HPH, 227, 228
Ceramic CNT nanocomposite, 146 Conductometric technique, 114
Ceramic matrix nanocomposites (CMNC), Coolants, 336, 338, 340, 368
142, 143 Cosmetic products, 278
Characterization, SLN Covalent binding, 167
drug encapsulation and loading Cross-linked enzyme crystals
capacity, 238 (CLECs), 167
drug localization and release, 238–240 Cross-linking, 167
nanocarriers, 233 Cryogenic cooling, 337
particle size and distribution, 233, 234 Crystalline silicon, 281
shape and surface morphology Curcumin, 414
AFM, 236, 237 Cutting fluids
EM, 236 Canola oil, 353
microscopic techniques, 235 chemical (synthetic fluids), 336
Index 427

in conventional machining free energy status, 27

air/vapour/gas cooling, 338 ionic strength and pH, 28
cryogenic cooling, 337 nano-sized droplets, 27
high temperatures, 336 thermal processing, 28
high-pressure coolant delivery Encapsulation, 180
technique, 338 Encapsulation efficiency (EE), 223, 233, 238
MQL, 339 Energy consumption, 272
nano-enriched cutting fluids, 339 Energy efficiency, 272
solid lubricant/coolant, 337 Entrapment, 168
dry machining, 334 Environmental biosensors
emulsifiable oils, 336 conventional techniques, 109
mineral oil-based, 333 EDCs, 120
in modern industry, 333 environmental contaminants, 121
MQL system (see Minimum quantity human activities, 108
lubrication (MQL)) industrialization, 120
neat cutting oils, 335 nanotechnology and biosensing
primary function, 333 techniques, 109
purchasing cost, 334 pathogens, 116
role, nanoparticles (see Nanoparticles) pesticides, 116
semisynthetic fluids, 336 pollutants, 109, 117–119
water-soluble fluids, 336 toxins, 120
Environmental contamination, 272
Environmental monitoring, 115
D Enzymatic biosensor, 112
Deposition technique, 150 Enzyme immobilization, 166
Digestive processes, 30 Enzyme-linked immune sorbent assay
Dioleoyl phosphatidylethanolamine (ELISA), 196
(DOPE), 389 Enzyme stability, 169
Double electron layer tunneling transistors Essential oils (EOs)
(DELTTs), 262 active packaging, 22
Double emulsion method, 230, 231 encapsulation, 23
Drug carriers, 391, 396 fabrication techniques, 24
Drug delivery, cancer lipid-based encapsulation, 19
GNPs-Dox-Lac, 190 lipophilic chemical components, 25
HCPMi, 191 polymers, 21
liposomal PEG, 190 synthesis and application, 24
nanovaccines, 191 European Framework Program, 254
Drug delivery systems, 277, 412
Dry machining, 334, 338–340, 346, 361, 362
Dye-doped nanomaterials, 212 F
Dye-sensitized solar cells (DSSCs), 283, 284 Fabricated nanoparticles
Dynamic light scattering (DLS), 234 agriculture-based industries, 204
characterization, 205
food processing, 204
E nanoparticles synthesis, 204
Electrochemical genosensors, 121 Fabrication of metallic NMs, 89, 97
Electrochemical transducers, 114 approaches, 88, 89
Electron microscopy (EM), 235, 236 physical approaches, 89
Electrospinning, 308 Ferulic acid, 419
Electrostatic model, 321 Field emission devices, 263
Emulsions, 19 Field-effect biosensor mechanism, 114
commercial applications, 27 Field-effect transistor (FET), 320
emulsifier type, 27 characteristics, 320
food and agricultural industries, 26 electrical properties, 320
428 Index

Flash memory manufacturers, 278 Green synthesis, 203

Fluorine-doped tin oxide (FTO), 285 biological/bioreduction, MNPs, 128, 129
Food sector, 30 economically, 130
Fossil fuel consumption, 272 using plant extracts, 130
Fourier-transform infrared spectroscopy
(FTIR), 192
Freund’s complete adjuvant (FCA), 390 H
High-memory density devices, 278
High-pressure homogenization (HPH)
G cold HPH, 227, 228
Gastrointestinal tract, 32 forces and cavitation stress, 226
Gelatin nanoparticles, 190 hot homogenization technique,
Genetic engineering, 381 226, 227
Genosensors, 112 large-scale production, SLNs, 222
Genosensors and aptasensors, 113 Honokiol, 417
Genotoxicity, 33 Hot homogenization technique, 226, 227, 395
Geothermal energy, 291 Hybrid hall effect (HHE) devices, 263
Global food security, 17 Hybrid polymer-type PV devices, 286
Global warming, 273 Hydrogen energy
Glucoamylase, 172 fuel cells, 287
Gold heat and electricity, 288
applications, 88 Hydrogen fuel cell, 288
characterization, 97, 98 Hyper-cell-permeable micelles (HCPMi), 191
fabrication trends using plant system, 93
factors/parameters, optimal fabrication, 96
mechanism of fabrication, 96 I
phyto-mediated synthesis, 94–96 Immobilized enzymes
potential uses, 88 covalent binding, 167
Gold nanoparticles, 71, 399 cross-linking, 167
hepatitis, 193 entrapment method, 168
MTB, 194 inorganic resources, 168
Graphene stability, 169
applications, 257, 258 support, 168
aromatic molecule, 260 Immunosensors, 111
atomic structure, 260, 261 In situ polymerization, 152
characteristics, 259 In situ process, 150
cutoff frequency, 258, 259 Indium tin oxide (ITO), 283
discovery, 260 Industrial effluent
limitation, 257 advanced oxidation process, 302
linear dispersion, 258 characteristics, 300
logic transistors, 257 skimming devices, 302
potential applications, 266 textile dyeing, 300
properties, 261 Industrial wastewater
electronic, 261 pollutants, 300
mechanical, 261 sedimentation techniques, 302
optical, 261 treatment methods, 300
storing H2 gas, 262 water pollution, 299
thermal, 261 Inorganic materials, 168
2D nanomaterials, 261 Inorganic nanocarriers, 396
structure, 260 Inorganic nanoparticles, 396
Green chemistry, 90 Integrated circuit technology (IC technology),
Green cutting fluids, 338 251, 253
Greener fabrication, NMs, 90 International Energy Agency (IEA), 279
Greenhouse gas (GHG) emissions, 272 Invertase, 172
Index 429

J academic research, 42
Journal of Nanoscience and antibacterial and catalytic activity, 43
Nanotechnology, 318 application, 43
biological uptake, 46
catalytic activity, 43
L cell interfere, 46
Lab-on-chip technology, 328 green synthesis
Laccase, 173 biological/bioreduction, 128–130
Laser diffraction (LD) spectroscopy, 235 using plant extracts, 130
Lateral flow assay (LFA), 197 microorganism, 42
Lawrence Livermore National Laboratory oxidative stress, 46
(LLNL), 329 potential application, 128
Lipase, 174 quantum dots, 46
Lipid-based nanoparticles, 21 synthesis, 42
Lipid emulsion, 222 toxicity, 44
Lipids, 224 toxicological effects, 47
oily/waxy materials, 223 Micelles, 20
Liposome-mediated encapsulation, 20 Microemulsions, 229, 230
Liposomes, 20 Microorganisms, 128
advantages, 389 biological synthesis, MNPs, 129
circulation time, 388 nanoparticle synthesis, 130–135
description, 388 Microwave-assisted technique, 230, 231
hydrophilic agents, 388 Minimum quantity lubrication (MQL)
niosomes, 389 biodegradable vegetable oils, 339
pulmonary delivery of insulin, 388 cutting fluid application
versatile carriers, 388 external, 340
Liquid-phase processes, 150 internal, 340
Lysozyme, 396 description, 339
lubricant, 339
nanoparticle-enriched cutting
M drilling, 346–350
Machining processes, 333–335, 337 grinding, 348–358
Macromolecules, 382, 394–396, 400 milling, 363–368
Magnetic biosensors, 115 turning, 354–363
Magnetic nanoparticles (NPs), 193 near-dry machining/micromachining, 339
Melt processing, 152 Molecular electronics, 315
Membrane contactor technique, Multi-walled carbon nanotubes (MWCNTs),
231, 232 72, 267, 334, 347, 349, 351, 352,
Mesoporous silica nanoparticles 355, 362, 366
(MSNs), 396–399 electrolyte leakage index, 74
Metal-based nanoparticles, 42 gene expression, 72
Metal-CNT nanocomposites, 151 seed germination and growth, 72
Metal matrix composite, 144 Mycobacterium tuberculosis (MTB), 194
Metal matrix nanocomposites (MMNC), 142,
144, 147–149
benefits, 144 N
chemical method, 144 Nanoactuators, 324
Metal NMs Nanobiosensor, 29
chemical/green chemistry approaches, 90 bioreceptor, 28
fabrication (see Fabrication of organic, 29
metallic NMs) Nanoblades, 288
nanotechnology, 88 Nanobombs, 325
phyto-mediated fabrication, 91–93 Nanobots, 323, 324
Metallic nanoparticles (MNPs), 41, 45, 194 Nanocarbon materials, 283
430 Index

Nanocarriers, 190, 221–223, 233, 236, Nanolubrication

242, 243 ball bearing/rolling/sliding effect, 344
cellular uptake, 382 mending mechanism, 344
delivery of bioactives, 381, 382 polishing mechanism, 344
gold, 399 tribofilm formation, 344
inorganic, 396 Nanomaterial ingestion, 32
MSN, 398 Nanomaterial particles, 277
preparation, 388 Nanomaterials, 286
protein delivery, 393 classification, 275
Nanocatalysts, 212, 308 drug delivery systems, 277
Nanocoatings, 281 graphenes, 255
Nanocomposite technology, 288 nanocoatings, 255
Nanocomposites, 141, 142 nanocomposite, 255
ceramic matrix nanocomposites, 143 nanorods, 255
ceramics, 142, 145 nanoscience, 275
CMNC, 143 nanotubes, 255
material matrix, 142 physicochemical properties, 209–211
metal matrix nanocomposite, 144 protective coatings, wood, 278
nanosize, 143 sporting instruments/gadgets, 275
polymer resin, 143 thin films, 255
types, 142 water purification systems, 277
Nanocurcumin, 191 Nanomedicines, 195, 278, 382–387, 393
Nano-cutting fluids, 334, 343 Nanometal oxides, 44, 212
Nano-droplet-enriched cutting fluid Nanometer scale, 273
(NDCF), 361 Nano-neuroelectronic systems, 329
Nanoelectronic devices, 320 Nanoparticles (NPs), 1, 41, 164
Nanoemulsions, 27 Ag nanoparticles, 4, 8
Nanoencapsulation technology agglomeration, 345
bioactive materials, 22 application, 56, 347
biological properties, 19 application, systems, 128
chemical preservatives, 18 bottom-up method, 165
chitosan, 21 carbon nanotubes, 7
chronic and acute toxicity, 17 cell membrane, 2
emulsions, 19 chemical and physical interactions, 2
EO formulations, 18 CMCD-g-CS, 393
fungi, 17 in cutting fluids
gums, 22 adhesion and stress concentration, 343
lipid-based encapsulation, 19 mechanism of
lipids, 18 nanolubrication, 344–345
liposome, 20 nanofluid stability, 346
mammalian system, 18 nanofluids, preparation, 345–346
micelles, 20 thermal conductivity, 343
photodegradation, 18 inorganic materials, 165
physical and chemical stability, 26 mechanism, 7
polymers, 21 metallic nanoparticles, 4
SLNs, 20 metals, 1
Nanoengineering field, 253 MQL-assisted drilling, 349–350
Nanofiber, 308 photosynthetic activity, 4
Nanofiltration, 307 physical property, 6
Nanofluid stability, 346 physicochemical changes, 7
Nanoform phytochemicals, 412–419 phytotoxicity, 3, 5, 8
Nanoformulation, 191 plants and microbes, 56
Nano-ginseng, 192 vs. plant growth, 56–57
Index 431

plant species, 3 photocatalysis, 308

ROS, 8 research field, 254
stress conditions, 9 risk, 311
scatterings, 127 RTDs, 263
vs. soil microorganisms, 57–58 sensing and monitoring, 309
vs. symbioses (see Symbioses) SETs, 263
synthesis (see Synthesis, NPs) SLDs, 263
toxicity, 60 tunneling microscope discovery, 253
TiO2 nanoparticles, 6 Nanotooling, 262
top-down method, 165 Nanotubes, 29, 317
translocation, 7 BCN, 255
Nano-phytochemicals biological systems, 319
action, cancers, 408–412 boron nitride, 255
advantages, 412–419 cell-transistor interface, 321
anticancer properties, 407 CNTs, 255
cancer, 412–419 DNA, 255
curcumin, 414 FET, 320
Nanopolymers, 276 gallium nitride, 255
Nanoprocessing, 262 inorganic, 255
Nanorobotics, 323 nanobioelectronics, 321
Nanorods, 255 serotonin receptors, 322
Nanoscale science, 252 silicon, 255
Nanoscience, 253, 273, 275 SWNTs, 319
Nanosensors, 33 tunneling and titania, 255
Nanostructure science-based technology, 254 Nanovaccines, 191
Nanostructures, 262 Nanowire sensors, 327
Nanotechnology, 1, 87, 88, 127, 202, 274, Nanowires (NWs), 326
381, 412 Natural treatment systems (NTSs), 304
adsorption, 307 Neutral proteinase, 175
advantages, 256–257 Nigella, 417
advantages and disadvantages, 309 Nigella sativa, 417
biocompatible nanocomposites, 390 Niosomes, 389, 390
characterization, graphene material, 264 Nitric oxide-loaded nanoparticles, 194
CNT-based FEDs, 263 Nitrogen fixers, 59, 60
definition, 256 Novel Drug Delivery System, 221
DELTTs, 262 Nucleic acids, 112
description, 252
discovery of fullerenes, 254
economic cost-effectiveness, 312 O
emerging technologies, 253 Ocean tidal projections, 291
graphene (see Graphene) Optical biosensors, 114
HHE, 263 Organs-on-chips, 328
impact, 253 Osteointegration process, 194
methods, 263 OVA (ovalbumin), 398
nail on the little finger, 252 Oxidation stability, lubricant, 342
nanocatalysts, 308
nanofiber, 308
nanofiltration, 307 P
nanomaterials, 306 Palladium
nanosensors, actuators and displays, 262 applications, 88
nanostructures, 262 characterization, 97, 98
NEMS and MEMS devices, 262 fabrication trends using plant system, 93
origin, 252 factors/parameters, optimal fabrication, 96
432 Index

Palladium (cont.) phyto-mediated synthesis, 94–96

mechanism of fabrication, 96 potential uses, 88
phyto-mediated synthesis, 94–96 P-o-C technologies, 196
potential uses, 88 Polluted water/wastewater, 208
Palladium-coated gold nanoparticles, 213 Polycyclic aromatic hydrocarbons
Particulate carriers, 390 (PAHs), 306
Patch-clamp electrode, 322 Polydispersity index (PDI), 234
Pectinase, 173 Polyethylene glycol (PEG), 192
PEGylated liposome (PEG-LS), 190 Polymer-based nanocomposite, 156
PEGylation, 388 Polymer-CNT nanocomposites, 153, 155, 157
Penicillin G, 176 Polymer nanocomposites, 151
Personalized medicine, 195, 196 layered materials, 152
Pharmaceutical industry, 407 melt processing, 152
Pharmaceutical nanocarriers, 223 polymer-CNT nanocomposites, 155
pH-dependent nanotools, 192 polymerization, 152
Phosphate solubilizer, 59, 60 solution blending, 153
Phospholipids, 389 Polymer solar cells, 286
Phosphorus fertilizer, 67 Polymeric nanoparticles, 390–394
Photocatalysis, 280, 308 Polymeric particles, 23
Photon correlation spectroscopy (PCS), Polymers, 391
234, 235 Polymetallic nanoparticles, 204
Photosynthesis, 70 Polyvinylpyrrolidone (PVP), 71
Photovoltaic (PV) cells, 280 Powder metallurgy, 145
Physical pollutants, 299 Pressurized coolant, 338
Physicochemical detector, 110 Probiotics
Phytochemical-based nanodrugs encapsulated capsules, 180
nano-ginseng, 192 encapsulation, 180
pH-based formulations, 193 functions, 179
Phytochemicals properties, 179
binary function, 90 Protein delivery, 393, 399
bio-fabrication, 91 Proteinticles, 196
plant system, 91, 98–99 Proteobacteria, 71
Piezoelectricity, 115 Proteolysis of enzyme, 167
Plant-based fabrication, metallic NMs, 91, 92
Plant growth-promoting bacteria
(PGPR), 57 Q
Plant interaction, 1 Quantum dots (QDs), 309
Plant-mediated nanoparticles, 207–208 Quantum effects, 164
Plants Quantum tunneling, 251
biological systems, 90 Quercetin, 192, 414
extracts, 90
fabrication, metallic NMs, 93
mechanism of fabrication, R
metallic NMs, 96 Reactive oxygen species (ROS), 120
NM fabrication, 91 Receptor-mediated endocytosis, 393, 398
plant system, 91, 99 Redox electrolyte, 285
species for green synthesis, 130, 131 Renewable energy, 272
Plastic deformation, 333, 336 PV devices, 281
Platinum role, 279
applications, 88 solar energy, 279
characterization, 97, 98 Reservoir system, 390
fabrication trends using plant system, 93 Resonance tunneling devices (RTDs), 263
factors/parameters, optimal fabrication, 96 Respirocytes, 323
mechanism of fabrication, 96 Reverse Micelle Method, 165
Index 433

S pulmonary, nasal and ocular

Scaling, 251 application, 241–242
Scanning electron microscopy (SEM), 236 transdermal and topical use, 241
Selaginella doederleinii Hieron, 416 as carriers for peptides and proteins
Semiconductor films, 284 drugs, 243
Serratiopeptidase, 176 characterization (see
Shelf life, 18, 23, 26, 30 Characterization, SLN)
Shoot regeneration, 67 colloidal carriers, 221
Silibinin, 418 composition
Silica, 396 lipids, 223–224
Silica noparticles, 396–399 SACs, 224, 225
Silicates, 396 selection of emulsifiers, 223
Silicon nanowires (Si NWs), 327 description, 221, 394
Silicon wafer technology, 284 double emulsion method, 230, 231
Silver drugs/bioactives, 395
applications, 88 hot homogenization technique, 395
characterization, 97, 98 large-scale production, 222
fabrication trends using plant system, 93 lipid nanoparticle, 243–244
factors/parameters, optimal fabrication, 96 membrane contactor technique, 232
mechanism of fabrication, 96 microemulsion based technique, 229, 230
phyto-mediated synthesis, 94–96 microemulsions, 222
potential uses, 88 peptides, 396
Silver (Ag) nanoparticles, 212 physicochemical properties, 222
Silver ions, 46 potential applications, 221
Silver nanoparticles, 212 SCF technology, 232–233
Silybin/milk thistle, 418 solvent emulsification/
Single-electron transistors (SETs), 263 evaporation, 228–229
Single-walled carbon nanotubes (SWCNTs), stability, 244
72, 267, 319 Solid lubricants, 337, 363
and MWCNTs, 74 Solid lubrication, 337
immobilization, 75 Solid-phase lipid nanoparticles (SLNs), 20
photosynthetic activity, 74 Solid-phase processes, 145
SLN preparation Solution-blending technique, 152, 153
HPH (see High-pressure Solvent evaporation technique, 229
homogenization (HPH)) Spin logic devices (SLDs), 263
ultrasound dispersion/ultrasonication, 228 Submerged arc nanoparticle synthesis system
Soil microbes, 70 (SANSS), 345
Soil microbial community, 71 Sunscreens, 194
biotic and abiotic stress, 66 Supercritical fluid (SCF) technology,
chemical fertilizer, 66 232–233
chlorophyll activity, 66 Surface active compounds (SACs)
physicochemical properties, 66 preparation and stabilization, 224, 225
Solar energy, 272 surfactant properties, 224
Solar photovoltaic cell, 280 Surface engineering, 262
solar power plants, 286 Sustainability, 272
Solar thermal energy, 280 Symbioses
Solar thermal technologies, 280 vs. Ag NPs, 59
Sol-gel process, 143 vs. CeO2 NPs, 59
Solid lipid nanoparticles (SLNs) vs. Fe3O4 NPs, 60
advantages, 222, 394 vs. ZnO NPs, 58–59
application Synthesis, NPs
in gene delivery, 242 green synthesis (see Green synthesis)
oral delivery, 240 using microorganisms, 130–135
parenteral delivery, 240 Synthetic materials, 169
434 Index

T oxidation stability, 342

Thermal conductivity, 282 physicochemical properties, 343
Thermal processing, 28 pour point, 342
Thermometric biosensors, 115 principal component, 341
Thymoquinone, 417 viscosity, 341
Tidal energy, 291 viscosity index, 341
Titanium dioxide (TiO2), 308 Vitamin B12 (VB12), 393
Top-down approach, 203 Voltage-dependent anionic channel
Traditional fossil fuels, 271 (VDAC), 388
Transduction mechanisms, 113
Transmission electron microscopy (TEM), 47,
206, 236 W
Tripartite interaction, 56, 61 Wastewater
Tripolyphosphate (TPP), 166 classification, 299
“Trojan horse effect”, 31 food industries, 302
Tunneling transistor, 262 physical pollutants, 299
Two-phase processes, 150 stream, 300
Wastewater treatment, 202,
212–214
U advanced technologies (see Advanced
Ultraviolet (UV) radiation, 194 wastewater treatment
Ursolic acid, 418 technologies)
Ursolic acid-based mesoporous silica biological treatment, 301
nanospheres (UAMSN), 418 conventional methods, 301
US Environmental Protection Agency nanotechnology (see Nanotechnology)
(US EPA), 47, 108 processes, 300
technology, 301
Wind energy, 290
V
van der Waals forces, 29
van der Waals interaction, 167 X
Vasoactive intestinal peptide (VIP), 390 Xylanase, 172
V-chip method, 196
Vegetable oil-based lubricants
edible and nonedible, 341 Z
flash point, 342 Zinc, 399