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Application of Nanoparticles in Waste Water Treatment

Article in World Applied Sciences Journal · January 2008

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World Applied Sciences Journal 3 (3): 417-433, 2008
ISSN 1818-4952
© IDOSI Publications, 2008

Application of Nanoparticles in Waste Water Treatment

1
Dhermendra K. Tiwari, 2J. Behari and 3Prasenjit Sen
1,2
School of Environment Science, Jawaharlal Nehru University, 110067, New Delhi, India
3
Schools of Physical Science, Jawaharlal Nehru University, 110067, New Delhi, India

Abstract: In the area of water purification, nanotechnology offers the possibility of an efficient removal of
pollutants and germs. Today nanoparticles, nanomembrane and nanopowder used for detection and removal
of chemical and biological substances include metals (e.g. Cadmium, copper, lead, mercury, nickel, zinc),
nutrients (e.g. Phosphate, ammonia, nitrate and nitrite), cyanide, organics, algae (e.g. cyanobacterial toxins)
viruses, bacteria, parasites and antibiotics. Basically four classes of nanoscale materials that are being
evaluated as functional materials for water purification e.g. metal-containing nanoparticles, carbonaceous
nanomaterials, zeolites and dendrimers. Carbon nanotubes and nanofibers also show some positive result.
Nanomaterials reveal good result than other techniques used in water treatment because of its high surface
area (surface/volume ratio). It is suggested that these may be used in future at large scale water purification.
It is also found that the coliform bacteria treated with ultrasonic irradiation for short time period before Ag-
nanoparticle treatment at low concentration, enhanced antibacterial effect. In future, combination of both
may be the best option for treatment of waste water.

Key words: Nanoparticle dendrites zeolite ceramics nanosilver nanorod nanofiber synergic effect
• • • • • • •

minium inhibitory concentration

INTRODUCTION as chlorine and it’s derivatives, Ultraviolet light [6],

Boiling, Low frequency ultrasonic irradiation [7],
Today most of the countries are facing drinking Distillation, Reverse Osmosis, Water sediment filters
water problems and conditions are very severe (fiber and ceramic) Activated carbon, Solid block,
especially in developing countries. The world is facing Pitcher and faucet-mount filters, Bottled water, Ion
formidable challenges in meeting rising demands of exchange water Softener, Ozonisation, Activated
clean water as the available supplies of freshwater are alumina 'Altered' Water. Halogens such as chlorine (Cl)
depleting due to (i) extended droughts, (ii) population and bromine (Br) are well known and widely used as
growth, (iii) more stringent health based regulations and antibacterial agents, but the direct use of halogens as
(iv) competing demands from a variety of users [1, 3, bactericides has many problems because of their high
4]. Clean water (i.e., water that is free of toxic toxicity and vapour pressure in pure form. The most
chemicals and pathogens) is essential to human health. common cation in water affecting human and animal
In countries such as India, 80% of the diseases are due health is NH4+. In drinking water ammonia removal is
to bacterial contamination of drinking water. The World very important to prevent oxygen depletion and algae
Health Organization [2] recommended that any water bloom and due to its extreme toxicity to most fish
intended for drinking should contain fecal and total species [8]. It can be replaced with biologically
coliform counts of 0, in any 100 mL sample. When acceptable cations, like Na+, K+ or Ca2+ in the zeolite.
either of these groups of bacteria is encountered in a During the past few decades, several investigations
sample, immediate investigative action should be taken. have been carried out concerning the use of synthetic
The removal or inactivation of pathogenic and natural zeolites, polymer films and metal ions (Ag+,
microorganisms is the last step in the treatment of Cu++, Zn++, Hg++, Ti+++, Ni++, Co++) as bactericides for
wastewater [3]. The protection of water treatment water disinfection [9-16].
systems against potential chemical and biological Research is underway to use advance
terrorist acts is also becoming a critical issue in water nanotechnology in water purification for safe drinking.
resources planning [4, 5]. Nanotechnology, the deliberate manipulation of matter
Today a number of techniques are used for at size scales of less than 100 nm, holds the promise
treatment of water i.e. chemical and physical agent such of creating new materials and devices which take

Corresponding Author: Dr. J. Behari, School of Environment Science, Jawaharlal Nehru University, 110067, New Delhi, India
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 World Appl. Sci J., 3 (3): 417-433, 2008

nickel, zinc), Nutrients (e.g. Phosphate, ammonia,

nitrate, nitrite), Cyanide Organics, Algae (e.g.
Cyanobacterial toxins) Viruses, Bacteria, Parasites,
antibiotics and Biological agents are used for terrorism.
Innovations in the development of novel technologies
to desalinate water are among the most exciting and
seem to have promis [22]. Opportunities and challenges
of using nanomaterials in the purification of surface
water, groundwater and industrial wastewater streams is
a matter of continuing concern. Misconceptions and
One of the many impressions that people have about the
future of nanotechnology is the expectation that
nanoparticles can be used to kill harmful organisms,
repair body tissue, in water quality improvment and to
cure disease.
Recent applications of nanoparticulate silver have
included open wound and burn treatment and
preliminary studies have shown that a 20 ppm silver
colloidal suspension (~30 nm diameter) in purified
water has a 100% cure rate for malaria [23]. Titanium
dioxide, especially as nanoparticulate anatase, is also an
interesting antibacterial, with notable photocatalytic
behavior. But ultrafine anatase has also been identified
as cytotoxic and in-vivo studies have shown that it can
be severely toxic in the respiratory system [24, 25].
Fig. 1:Schematic of a composite nanomaterial packed Nanocapsules and nanodevices may present new
bed reactor for purification of water possibilities for drug delivery, gene therapy, medical
Contaminated by mixtures of (i) metal ions, (ii) diagnostics, antimicrobial activity etc. The effect of
Organic solutes and (iii) bacteria [20] particle size on the adsorption of dissolved heavy
metals to iron oxide and titanium dioxide nanoparticles
advantage of unique phenomena realized at those length is a matter laboratory-scale experiments. Iron oxide and
scales, because of their high reactivity due to the large titanium dioxide are good sorbents for metal
surface to volume ratio [17]. Nanoparticles are expected contaminants. Spherical aggregates of nanoparticles
to play a crucial role in water purification [18]. The that have a similar size and shape to the resin beads
environmental fate and toxicity of a material are critical already used in water purification. ligands, fulvic acids,
issues in materials selection and design for water humic acids and their aggregates have a significant
purification. No doubt that nanotechnology is better impact on contaminant mobility, reactivity and
than other technique used in water treatment but today bioavailability. Nanoparticles can also be designed and
the knowledge about the environmental fate, transport synthesized to act as either separation or reaction media
and toxicity of nanomaterials [19] is still in infancy. for pollutants.
Advances in nanoscale science and engineering The high surface area to mass ratios of
suggest that many of the current problems involving nanoparticles can greatly enhance the adsorption
water quality could be resolved or greatly diminished capacities of sorbent materials. Nanotechnology is a
by using nonabsorbent, nanocatalysts, bioactive deliberate manipulation of matter at size scales of less
nanoparticles, nanostructured catalytic membranes, than 100 nm holds the promise of creating new
submicron, nanopowder, nanotubes, magnetic materials and devices which take advantage of unique
nanoparticles, granules, flake, high surface area metal phenomena realized at those length scales. In addition
particle supramolecular assemblies with characteristic to having high specific surface areas, nanoparticles also
length scales of 9-10 nm including clusters, have unique adsorption properties due to different
micromolecules, nanoparticles and colloids have a distributions of reactive surface sites and disordered
significant impact on water quality in natural surface regions. Their extremely small feature size is of
environment [20]. Nanotechnology used for detection the same scale as the critical size for physical
of pesticides [21] chemical and biological substances phenomena for example, the radius of the tip of a crack
including metals (e.g. Cadmium, copper, lead, mercury, in a material may be in the range 1-100 nm. The way a

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 World Appl. Sci J., 3 (3): 417-433, 2008

crack grows in a larger-scale, bulk material is likely to

be different from crack propagation in a nanomaterial
where crack and particle size are comparable.
Fundamental electronic, magnetic, optical, chemical
and biological processes are also different at this level.

NANOPARTICLE IN WASTE WATER

TREATMENT

Four classes of nanoscale materials that are being

evaluated as functional materials for water purification:
(1) dendrimers (2) metal-containing nanoparticles, (3)
zeolites and (4) carbonaceous nanomaterials. These (A)
have a broad range of physicochemical properties that
make them particular attractive as separation and
reactive media for water purification. Characterization
of the interactions of the nanoparticles with the
bacterial contaminant by Atomic Force Microscopy
(AFM), Transmission Electron Microscopy (TEM) and
laser confocal microscopy show considerable changes
in the integrity of the cell membranes, resulting in the
death of the bacteria in most cases.

Dendrimer in water treatment: Reverse Osmosis

(RO) membranes have pore sizes of 0.1-1.0 nm and
thus are very effective at retaining dissolved inorganic
and organic solutes with molar mass below 1000 Da
(B)
[26]. Nanofilter (NF) membranes removing hardness
(e.g., multivalent cations) and organic solutes with
Fig. 2:The dendrimer attaches to multiple receptors on
molar mass between 1000-3000 Da (e.g., natural
cell membranes or other biological structures
organic material) [26]. However, high pressures are
required to operate both RO and NF membranes. such as a virus
Conversely, Ultrafine (UF) membranes require lower
pressure (200-700 kPa). Unfortunately, they are not surface of the molecule. Chemical and/or physical
very effective at removing dissolved organic and properties, such as reactivity, complex or salt
inorganic solute with molar mass below 3000 Da. formation, hydrophilicity and so forth can be varied and
Advances in macromolecular chemistry such as the optimized. As a proof of concept study, Diallo et al.
invention of dendritic polymers are providing (2005) tested the feasibility of using dendron-enhanced
unprecedented opportunities to develop effective UF ultrafiltration (DEUF) and poly (amidoamine)
processes for purification of water contaminated by (PAMAM) Dendrimers with Ethylene Diamine (EDA)
toxic metal ions, radionuclide, organic and inorganic core and terminal NH2 groups to recover Cu (II) ions
solutes, bacteria and viruses. from aqueous solutions. On a mass basis, the Cu (II)
Dendrite polymers, which include random binding capacities of the PAMAM dendrimers are
hyperbranched polymers, dendrigraft polymers, much larger and more sensitive to solution pH than
dendrons and dendrimers, are relatively monodispersed those of linear polymers with amine groups.
and highly branched macromolecules with controlled To obtain a dendrimer structure, several dendrons
composition and architecture consisting of three are reacted with a multifunctional core to yield a
components: a core, interior branch cells and terminal dendrimers. Using two key synthetic strategies, over
branch cell [27] and tissue silver levels with 10% silver. one hundred compositionally different dendrimer
Dendrimers are symmetrical and spherical families have been synthesized and over 1000
macromolecules, comprising a relatively dense shell differentiated chemical surface modifications have been
composed of a core, branching sites and terminal reported [28-37]. The first strategy, utilizes highly
groups that usually form a well-defined surface. Their functionalized cores and branched monomers to create
interior may be similar or very different from the phosphorus dendrimers.Several variations of the
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general synthetic scheme, which are interchangeable, proved to be effective antimicrobial agents in vitro. Due
have been developed, allowing multiplication of the to the atomic/molecular level dispersion of the guest in
number of terminal surface groups from 48 to 250 in a dendrimer host, the activity is retained if the
one step. These dendrimers require just one step per microorganism is able to contact with the organized
generation performed in a minimum volume of solvent, silver domains of the nanocontainers. Macroscopically,
allow facile purification (i.e., simple washings) and the silver remained conjugated to the dendrimer in the
produce environmentally benign byproducts such as form of ions, stable metallic silver clusters or silver
water and nitrogen [38, 39]. The second approach is compounds. Because the dendrimer host is soluble, it is
based on dclickT chemistry, i.e., the nearperfect able to deliver the immobilized silver in the agar
reliability of the Cu (I)-catalyzed synthesis of 1, 2, 3- medium by its own diffusion. The silver clusters remain
triazoles from azides and alkynes to produce active because of their extremely high surface area.
dendrimers with various surface groups in high purity Reaction with chloride and sulfate ions neither blocks
and excellent yield. As early as 1984, PAMAM the diffusion of the silver nor the activity against S.
dendrimers were the first complete dendrimer family to aureus, Ps. aeruginosa and E. coli. The protected silver
be synthesized and characterized followed by and silver compounds displayed high antimicrobial
commercialization in 1990 [40, 41]. They are activity in several cases without the loss of solubility.
synthesized by the divergent method, involving a two- However, the diffusion of dendrimers can be totally
step iterative reaction sequence that produces prevented if common cellulose membranes are used.
concentric shells of branch cells (generations) around a
central initiator core. This PAMAM core-shell Metal nanoparticle: Nanoparticles have two key
architecture grows linearly in diameter as a function of properties that make them particularly attractive as
added generations, while the surface groups amplify sorbents. On a mass basis, they have much larger
exponentially at each generation. Poly (amidoamine) surface areas than bulk particles. Nanoparticles can also
PAMAM dendrimers are obtained by the iterative be functionalized with various chemical groups to
branching of L-alanine repeat units. Due to their increase their affinity towards target compounds. It has
biofriendly nature [42-45] and unique carrier properties, been found that the unique properties of nanoparticles
they show promise to outperform other polymeric to develop high capacity and selective sorbents for
materials for medical applications. Diffusion of metal ions and anions. Characterization of the
dendrimers through membranes is the function of interactions of the nanoparticles with the bacteria by
generation (due to their spherical and monomodal atomic force microscopy (AFM), Transmission
character) and appropriately selected membranes may Electron Microscopy (TEM) and laser confocal
retain dendrimer hosts with 100% selectivity. microscopy showed considerable changes in the
PAMAMs are also stable and soluble in water. integrity of the cell membranes, resulting in the death of
PAMAM dendrimers have a very low tendency to foul the bacteria in most cases. Phototalytic nanomaterials
commercially available regenerated cellulose (RC) allow ultraviolet light also used to destroy pesticides,
membranes [22]. They also have much smaller intrinsic industrial solvents and germs.
viscosities than linear polymers with the same molar Stoimenov et al. showed that MgO nanoparticles
mass because of their globular shape [27]. Dendritic and magnesium (Mg) nanoparticles are very effective
polymers exhibit many features that make them biocides against Gram-positive and Gram-negative
particularly attractive as functional materials for water bacteria (Escherichia coli and Bacillus megaterium)
purification. These ‘soft’ nanoparticles, with sizes in and bacterial spores (Bacillus subtillus) [18].
the range of 1-20 nm, can be used as high capacity and Magnesium oxide nanoparticles or magnesia
recyclable water soluble ligands for toxic metal ions, nanoparticles (MgO), nanodots or nanopowder are
radionuclide and inorganic anions [46]. Dendritic spinel, high surface area particles. Nanoscale
polymers can also be used as (i) recyclable magnesium oxide nanoparticles or magnesia particles
unimolecular micelles for recovering organic solutes are typically 5-100 nanometers (nm) with specific
from water [47] and (ii) scaffolds and templates for the surface area (SSA) in the 25-50 m2 g−1 range and
preparation of redox and catalytically active magnesium (Mg) nanoparticles, nanodots or
nanoparticles. nanopowder are spherical black high surface area
Dendritic polymers have also been successfully particles. Nanoscale magnesium particles are typically
used as delivery vehicles or scaffolds for antimicrobial 20-60 nanometers (nm) with specific surface area
agents such as Ag (I) and quaternary ammonium (SSA) in the 30-70 m2 g−1 range. Preparation of
chlorides [14, 48]. Poly (amidoamine) dendrimer magnesium oxide (MgO) nanoparticles to absorb large
(PAMAM) based silver complexes and nanocomposites amounts of halogen molecules up to 20 % by weight
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 World Appl. Sci J., 3 (3): 417-433, 2008

Fig. 3:(A) Divergent approach using dlegoT chemistry towards highly functionalized phosphorous dendrimers. (B)
Convergent approach towards triazole dendrimers using dclickT chemistry [32, 33, 38, 39, 42, 43 American
Chemical Society 2003]

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making them safer to handle and measured their various monometallic nanoparticles e.g. Au, Ag,
bactericidal activity on three representative strains of Pt, Pd [54] and Sugar-assisted stable monometallic
bacteria and bacterial spores [18]. These MgO nanoparticles can be synthesized in the laboratory.
nanoparticle particles are allowed to contact certain Gold (Au) nanoparticles, nanodots and nanopowder
bacteria and spore cells. Bacteriological test data, are brown spherical high surface area metal particles.
Atomic force microscopy (AFM) images and Nanoscale gold particles are typically 20-100
Transmission electron microscopy (TEM) images are nanometers (nm) with specific surface area (SSA)
provided, which yield insight into the biocidal action of in the 1-3 m2 g−1 range. Nanoparticles of gold coated
these nanoscale materials. The tests show that these with palladium are very effective catalysts for
materials are very effective against Gram-positive and removing tri-chloroethane (TCE) from groundwater
Gram-negative bacteria. 2,200 times better than palladium alone.
Ag (I) and silver compounds have been used as Zinc oxide nanoparticles have been used to remove
antimicrobial compounds for coliform found in waste arsenic from water, even though bulk zinc oxide can
water [49]. Silver (Ag) nanoparticles, nanodots or not absorb arsenic. Some adsorption processes for
nanopowder are spherical or flake high surface area wastewater treatment have utilized ferrites and a variety
metal particles having high antibacterial activity of iron containing minerals, such as akaganeite,
[50, 51] are used in wound. Nanoscale silver particles feroxyhyte, ferrihydrite, goethite, hematite,
are typically 1-40 nanometers (nm) with an average lepidocrocite, maghemite and magnetite. Adsorption of
particle size of 2-10 micron range with a specific organics to the nanoparticle media was extremely rapid.
surface area of approximately 1 m2 g−1. Applications More than 90% of the organics is adsorbed within
for silver nanocrystals include as an anti-microbial, 30 minutes. The isotherm studies indicated that, on a
anti-biotic and anti-fungal agent when incorporated surface area basis, the adsorption capacities of the
in coatings, nanofiber, first aid bandages, plastics, nanoparticle media were significantly (>2 folds) higher
soap and textiles, in treatment of certain viruses, in than the ferric oxide media typically used in water
self cleaning fabrics, as conductive filler and in treatment [55]. The smaller size of magnetic
nanowire and certain catalyst applications. It has been nanoparticles, which are 2-3 orders of magnitude
reported that Ag nanoparticles were active biocides smaller than a bacterium, provides extra benefits
against Gram-positive Gram-negative bacteria compared to magnetic beads. When their surface is
including Escherichia coli, Staphylococcus aureus, appropriately elaborated, magnetic nanoparticles can
Klebsiella pneumoniae and Pseudomonas aeruginosa also provide efficient binding to the bacteria because
[49, 52]. Stable Ag nanoparticles of narrow size [53], their high surface/volume ratio simply offers more

Fig. 4: The TEM images of the metal nanoparticles (Au, Ag, Pd and Pt) formed by fructose reduction [54]

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contact area. Ferrite is a generic term for a class of for metal ion removal. The high surface area to mass
magnetic iron oxide compounds. Ferrites posses the ratios of nanoparticles can greatly enhance the
property of spontaneous magnetization and are adsorption capacities of sorbent materials. In addition
crystalline materials soluble only in strong acid. Iron to having high specific surface areas, nanoparticles
atoms in iron ferrite (FeO.Fe2O3) can be replaced by also have unique adsorption properties due to
many other metal ions without seriously altering its different distributions of reactive surface sites and
spinel structure.Various ferrites and natural magnetite disordered surface regions. The effect of particle size
were used in batch modes for actinide and heavy metal on the adsorption of dissolved heavy metals to iron
removal from wastewater. Iron (Fe) nanoparticles, oxide and titanium dioxide nanoparticles will be
nanodots or nanopowder are spherical or faceted high studied in laboratory-scale experiments. Iron oxide and
surface area metal nanostructure particles. Nanoscale titanium dioxide are good sorbents for metal
iron particles are typically 20-40 nanometers (nm) with contaminants.
specific surface area (SSA) in the 30-50 m2 g−1 range. Reduction of transition metal salts is the oldest,
Other recent studies have demonstrated the easiest and still a widely used method for the
magnetic enhanced removal of cobalt and iron from preparation of metal nanoparticles. As far as magnetic
simulated groundwater. The magnetic field-enhanced metals are concerned, the most common reducing
filtration/sorption process differs significantly from agents are borohydride derivatives, extensively studied
magnetic separation processes used in the processing of by Klabunde et al. This method provides an easy route
minerals and more recently, for water treatment and to nanoparticles of Fe, Co and Ni as well as to alloys
environmental applications. Conventional processes use such as Fe/Pd. The drawback of the method is however
for example, fine stainless steel wool to form a the incorporation of boron into the particles which leads
magnetic matrix within a flow field of a solution to a modification of the magnetic properties of the
containing mineral particles to be separated. For this particles. Cobalt particles were for example prepared
reason, in order for such processes to remove metal ions with the microemulsion method in the binary system
and nanoparticles from solution, precipitating or of DDAB (di-dodecyldimethylammonium bromide)/
flocculating agents must first be added to effect toluene by reduction of CoCl2 with NaBH4. The
formation of large particles. In contrast, the magnetic average particle size of the samples could be varied
filtration/sorption process is unique because metals are from 1.8 to 4.4 nm by controlling the concentration of
removed in most conventional wastewater treatment CoCl2 in the solution of DDAB in toluene.
processes in the form of metal hydroxides since they
have low solubility. As noted above, ferric hydroxide is Zeolite: Zeolites are effective sorbents and ion-
often added to scavenge a wide variety of heavy metal exchange media for metal ions. NaP1 zeolites (Na6Al6
contaminants. The use of iron ferrite and magnetite in Si10O32, 12H2O) have a high density of Na+ ion
wastewater treatment has a number of advantages over exchange sites. They can be inexpensively synthesized
conventional flocculent precipitation techniques by hydrothermal activation of fly ash with low Si/Al

Fig. 5: Several examples of zeolite LTA microparticles that have been fragmented by laser-induced fracture [58]

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ratio at 150°C in 1.0-2.0 M NaOH solutions [55]. NaP1 crosslinking and alkylation followed by methylation in
zeolites have been evaluated as ion exchange media order to increase degree of amino group substitution
for the removal of heavy metals from acid mine [63]. Because of its positive charge and hydrophobicity,
wastewaters. Alvarez-Ayuso et al. reported the PEI nanoparticles have attracted attention as possible
successful use of synthetic NaP1 zeolites to remove antimicrobial agents. Studies on PEI nanostructured
Cr(III), Ni(II), Zn(II), Cu(II) and Cd(II) from metal compounds are made to evaluate its antibacterial
electroplating wastewater [57]. Nonporous ceramic properties as a function of hydrophobicity, molecular
oxides with very large surface areas (1000 m2 g−1) and weight, particle size and charge that can play a
high density of sorption sites that can be functionalized significant role in antibacterial effect of the tested
to increase their selectivity toward target pollutants. compound. The antibacterial activity is evaluated
Zeolite nanoparticles are prepared by laser-induced against Streptoccocus mutants cariogenic bacteria.
fragmentation of zeolite LTA microparticles using a Various PEI nanoparticles from 100nm to 1 micron in
pulsed laser. Zeolite nanoparticle formation is attributed diameter are prepared having different degree of cross-
to absorption of the laser at impurities or defects within linking, particle size and zeta potential that are achieved
the zeolite microcrystal generating thermoelastic stress by alkylation with a bromoalkane followed by
that mechanically fractures the microparticle into methylation. Their antibacterial effects are examined
smaller nanoparticle fragments. Experimentally, it is against Streptoccocus mutans in direct contact with
found that nanoparticles have a wide size and bacteria. One important feature of the antibacterial
morphology distribution. Large nanoparticles (>200 agent is to maintain antibacterial activity over a long
nm) are typically irregularly shaped crystals of zeolite time. However, only the PEI nanoparticle samples
LTA, whereas small nanoparticles (<50 nm) tend to be including long chain alkyls demonstrated high
spherical, dense and amorphous, indicative of antibacterial effect against Streptoccocus mutants for
destruction of the original LTA crystal structure. more than four weeks [62].
Increasing the laser energy density irradiating the
sample was found to be a trade-off between increasing STRATIGES FOR NANOPARTICLE SYNTHESIS
the amount of fragmentation and increasing the amount
of structural damage to the zeolite crystal. It is Nanomaterials are, of course, abundant in nature as
suggested that in the presence of strongly absorbing living organisms operate basically at a nanoscale level.
defects, plasma formation is induced resulting in Anotechnologists seek to produce and utilize both novel
dramatically higher temperatures. On the basis of these nanomaterials and some natural nanomaterials in larger
results it is concluded that the optimal laser processing quantties and within a more consistent size range.
conditions are 355 nm and 10 mJ/pulse laser energy for Numerous techniques are used to fabricate different
our LTA samples (Figure-5) [58]. nanomaterials. Nanoparticles can be produced from
larger structures (top down) by use of ultrafine grinders,
Carbonaceous nanoparticle: Carbonaceous lasers and vaporization followed by cooling. For
nanomaterials can serve as high capacity and selective complex particles, nanotechnologists generally prefer to
sorbents for organic solutes in aqueous solutions. synthesize nanostructures by a bottom-up approach by
A number of polymers that exhibit antibacterial arranging molecules to form complex structures with
properties were developed for this purpose including new and useful properties.
soluble and insoluble pyridinium-type polymers
which are involved in surface coating, [59] azidated Self assembly: Manipulation of physical and chemical
poly (vinyl chloride) [60] which can be used to conditions such as pH, temperature and solute
prevent bacterial adhesion of medical devices, PEG concentrations can induce selfassembly of molecules to
polymers that can be modified on polyurethane form fibrous nanostructures [63]. Vesicles, called
surfaces and also prevent initial adhesion bacteria polymerosomes, that may be useful for encapsulation,
to the biomaterial surfaces [61] and polyethylene can also be self assembled by slow evaporation of an
mine (PEI) [62] that exhibit high antibacterial and organic solvent [64].
antifungal activity. High activity of polycationic
agents is related to absorption of positive charged Layer by layer deposition: Platforms for bilayer
nanostructures onto negative by charged cell surfaces membranes that can be used for protein analysis can be
of the bacteria. This process is thought to be responsible fabricated by layering of sodium silicate and poly
for the increase of cell permeability and may disrupt the (allylamine hydrochloride) on gold followed by
cell membranes. calcinations in a furnace. Lipid bilayers can fuse to the
Cross linked polycations are prepared as silicate layer and be used to detect specific proteins
nanoparticles. These are formed from PEI by [65].
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Preparation of functional nanoparticles by thermal

plasmas: Functional nanoparticles of silicide and
boride were prepared by induction thermal plasmas.
Silicide and rare-earth boride are attractive materials
because of their high melting temperature, high
electrical conductivity and low work function.
Therefore these nanoparticles would be applied for
electromagnetic shielding and solar control windows
with interaction with IR and UV light.
For the preparation of silicide, Si powders
premixed with metal powder (Mo, Ti, Co, Fe, Cr, or
Mn) are injected into the plasma. For the preparation of
rare-earth boride, premixed powders of rare-earth
oxide, B and C were introduced into the thermal
Fig. 6:LaB6 nanoparticles prepared from the La2O3B
plasma. In the thermal plasma, the injected powders are
powders injected into argon induction plasmas
evaporated and reacted with boron. After the
evaporation and reaction, the vapor is rapidly cooled
after the plasma flame. The nanoparticles are prepared
on condition that the vapor is quickly quenched by the
water-cooled copper coil. Another purpose is to
investigate the condensation mechanism of mixture
vapor of feed powders in thermal plasmas. The
characteristics of the prepared nanoparticles are
affected by the vapor pressure ratio of the constituent
materials. Investigation of physical and chemical
processes in thermal plasma processing is indispensable
for nanoparticle synthesis.

Gas phase synthesis and sol-gel processing: Major

efforts in nanoparticle synthesis can be grouped into
two broad areas: gas phase synthesis and sol-gel
processing. Nanoparticles with diameters ranging from
1 to 10 nm with consistent crystal structure, surface
derivatization and a high degree of monodispersity have
been processed by both gas-phase and sol-gel
techniques. Initial development of new crystalline
materials was based on nanoparticles generated by
evaporation and condensation (nucleation and growth)
in a subatmospheric inert-gas environment [66, 67].
Various aerosol processing techniques have been
reported to improve the production yield of
nanoparticles [68, 69].

Crystallization: Hydroxyapatite-aspartic acid (or- Fig. 7:TEM images for NaCl particles at furnace
glutamic acid) crystals were synthesized in the presence temperature of 500 and 600°C
of solutions containing different amounts of the amino
acids. Material, bringing in the consideration of the materials can form templates or scaffolding for
temporal stability of the structured materials [70]. inorganic components. These notions of a multilevel
material structure with strong interactions among levels
Biogenic strategy: The complexity of biological and interplay of perfection and imperfection forming
materials represents the achievement of structural order the final material.
over many length scales, with the full structure
developed from the "nested levels of structural Microbial synthesis: Living cells have been
hierarchy" [71], in which self-assembled organic harnessed to produce nanoparticles, for example, silver
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nanoparticles produced extracellularly by the fungus can be controlled by adjusting the pressure and the
Aspergillus fumigatus [72]. Gold and silver solution retention time in the cavitation chamber.
nanoparticles can also be produced by other fungi and a
number of bacterial species [73]. ANTIBACTERIAL EFFECT ENHANCED BY
ANTIBIOTIC-NANOPARTICLE INTERACTION
Biomass reactions: Gold nanorods and nanoparticles
with other shapes were produced by incubation of dead Ping Li et al. studied that the Ag nanoparticle
oat stalks with an acidic aqueous solution of gold ions shows enhanced antibacterial effect against E. coli used
(Au III) (1). Some living plants are also known to take with amoxicillin, a ß-lactum antibiotics [77]. When
up and sequester heavy metals (to prevent being amoxicillin and silver nanoparticles are combined, it
poisoned by these metals) and these plants may also be results in greater bactericidal efficiency on Escherichia
useful in producing nanoparticles of metals [73]. coli cells than when they were applied separately.
Nanosilvers and amoxicillin can kill bacteria with a
Alternative preparation method: Low temperature different mechanism. If bacteria have resistance to one
nanoparticle preparation methods have spanned a wide of them, another antimicrobial agent would kill the
range of systems. One that has been in existence for bacteria in a quite different way. This plays an
decades but has not been put into use in other industries important role especially when the bacteria gain
is the method of preparing silver halide particles. antimicrobial resistance.
Eastman Kodak in France, England and the United Till now, scientists have established the
States has utilized solution precipitation technology antibacterial mechanism of ß-lactam antibiotics
with well-controlled mixing and nucleation control to [78, 79]. The silver application on burning therapy has
produce a wide range of grain sizes. "Lippmann"-type existed for more than a century [80, 81]. Some
grains have a size of about 50 nm. There are other hypotheses indicated that catalytic oxidation of silver
methods of creating nanoparticles of organic materials ions, with nascent oxygen, reacts with bacterial cell
such as filter dye applications in photographic films and membranes, leading to cell death. More recently, it has
spectral sensitizing dyes for use in silver halide grains. been demonstrated that the bactericidal effect of silver
Ultrafine grinding media are used to almost sandpaper was caused by silver (I) chelation preventing DNA
organic crystals to nanoparticle ranges of 20-80 nm. from unwinding [82].
Similar technology has been utilized in both If the bacterium does not show any resistence, the
pharmaceutical preparations and ink jet applications synergistic effect may be caused by a bonding reaction
with good success [74]. One other exciting area is in between amoxicillin and nanosilver. Amoxicillin
polymer science, where dendrimer molecules, often 10 molecules contain many active groups such as hydroxyl
nanometers in diameter, are prepared synthetically and and amido groups. These groups react easily with
trying to use in water treatment. nanosilver by chelation. Amoxicillin molecules
themselves can bind each other through Vander-waals
Other strategies: Additional nanoparticle synthesis interaction and other weak bonds. Ultimately, the
techniques include sonochemical processing, cavitation antimicrobial groups come into being, which are made
processing, microemulsion processing and high-energy up of a nanosilver core and the surrounding amoxicillin
ball milling. In sonochemistry, an acoustic cavitation molecules (Fig. 8). Whenever antimicrobial groups act
process can generate a transient localized hot zone with on one point at the surface of the bacterial cells they
extremely high temperature gradient and pressure [75]. cause more destruction. Thus, the process of
Such sudden changes in temperature and pressure assist antimicrobial group forming is actually that of
the destruction of the sonochemical precursor (e.g., increasing the antimicrobial agents’
organometallic solution) and the formation of concentration.Vancomycin antibiotic bind with FePt-
nanoparticles. The technique can be used to produce a nanoparticles because of multivalent nature of the
large volume of material for industrial applications. In particle and helps to enhance the antibacterial nature of
hydrodynamic cavitation, nanoparticles are generated antibiotics (Fig. 9).
through creation and release of gas bubbles inside the A more probable cause of the synergistic effect
sol-gel solution [76]. By rapidly pressurizing in a may be the action of nanosilver’s drug carrier.
supercritical drying chamber and exposing to Phospholipids and glycoprotein, present in cell
cavitational disturbance and high temperature heating, membrane, which are all hydrophobic groups.
the sol-gel solution is mixed. The erupted Nanosilver, but not amoxicillin, is likely to approach
hydrodynamic bubbles are responsible for nucleation, the membrane of the target cells because amoxicillin
growth and quenching of the nanoparticles. Particle size molecules are hydrophilic and nanosilver is not.
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Fig. 8: The structure of amoxicillin and the bonding route for nanosilver chelated with amoxicillin [77]

Fig. 9: The structure of vancomycin and synthesis of vancomycin conjugated FePt nanoparticles [83]

Fig. 10: A diagram of the combination of nanosilver and amoxicillin reacted with cells extracellularly and
intercellularly [77]

Therefore, antimicrobial groups facilitate the transport filtrated twice and the cells were washed and suspended
of amoxicillin to the cell surface. in distilled water until the inocula reached
LB medium was used for growing Escherichia coli approximately 5.0×106 CFU. 15 LB medium tubes were
(DH5a) test strains at 37°C until approximately 105-106 prepared and test culture inoculated in highly sterilized
CFU of bacteria were reached. The cultures were 0.000, 0.150, 0.300, 0.375, 0.450 and 0.525 mg ml−1
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 World Appl. Sci J., 3 (3): 417-433, 2008

procedure was performed with 0, 5, 10, 15, 20, 25, 30,

35 and 40 µg ml- 1 of nanosilver. The minimal
inhibition concentrations (MICs) of amoxicillin and
nanosilver were calculated respectively. To get the MIC
of the mixture of amoxicillin and nanoparticles, the
cells of the bacteria were spotted into LB medium and
incubated under different conditions as follows: 0.150
mg ml- 1 amoxicillin +5 µg ml- 1 nanosilver and 0.150
mg ml- 1 amoxicillin +10 µg ml- 1 nanosilver instead of
amoxicillin or nanosilver alone. All assays were carried
out in three duplicates in an effort to eliminate other
random factors. Broth dilution experiments were
conducted at 37°C and performed in 204 well rinsed
Fig. 11: Effect of different conc. of amoxicillin put into plates. All stock solution was made in an LB agarose
5×106 CFU of Bacterial colonies plate and diluted twofold with the duplicates. The MICs
of amoxicillin and nanosilver, individually and jointly,
were determined. The MIC of amoxicillin tested in the
experiment shown in Fig. 11 is about 0.525 mg ml−1.
In Fig. 12, the MIC of nanosilver appeared to be
40 µg ml−1. Comparing the individual antibacterial
effect of amoxicillin or nanosilver with their
combination, the augmentative antibacterial efficiency
by the β-lactam antibiotic in combination with
nanosilver is quite obvious. Either the 0.15 mg ml−1
amoxicillin or the 5 µg ml−1 nanosilver alone had hardly
any effect on E. coli as demonstrated from this
experiment.

COMBINED EFFECT OF AG-

Fig. 12: Effect of different concentration of nanosilver NANOPARTICLE/ULTRASONIC RRADIATION
put into 5×106 CFU of Bacterial colony
Because ultrasound attacks the bacterial cell walls,
the bacterial cells release iso-enzymes that biocatalyst
hydrolytic reactions. This results in acceleration in the
breakdown of organic material into smaller readily
biodegradable fractions. Ultrasound treatment is one of
several technologies that promote hydrolysis of the
rate-limiting stage during sludge treatment. It can be
generated at a broad range of frequencies (35 and 130
KHz) and acoustic intensities [84]. The basic principal
of ultrasound is based on the destruction of both
bacterial cells membranes and difficult-to-degrade
organics. Because ultrasound attacks the bacterial cell
walls, the bacterial cells release various enzymes,
Fig. 13: Effect of amoxicillin and nanosilver, which catalyzed hydrolytic reactions and ultimately
individually and jointly, on 5×106 bacterial cell death. This results in acceleration in the breakdown
colonies: (a) 5 µg ml- 1 nanosilver; (b) 0.150 of organic material into smaller readily biodegradable
mg ml- 1 amoxicillin; (c) 0.150 mg ml- 1 fractions.
amoxicillin plus 5 µg ml- 1 nanosilver; (d)
0.150 mg ml- 1 amoxicillin plus 10 µg ml- 1 Synthesis of nanoparticle: The synthesis of Ag
nanosilver @citrate was done according to the literature procedure
[85]. Briefly, the synthesis involves the following
condition. Out of fifteen six tube were incubated with materials and methods: 25 mL of 0.005 M stock
amoxicillin, shaken at 37°C for 24 h. The same solution of silver nitrate in water was diluted to 125 mL

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 World Appl. Sci J., 3 (3): 417-433, 2008

(a) (b) (c)

(d) (e)

Fig. 14: (a) Culture growth on LB medium without any treatment (b) Bacterial growth after Ultrasonic treatment
with varying time interval at 35 KHz (c) in presence of varying concentration of Ag nanoparticle (d)
Treatment of both Ultrasonic waves (35 KHz) with time interval according to (a) and Ag nanoparticle (1017
molecules/cc) (e) Treated with both Ultrasonic waves (35 KHz) with time interval according to (a) and Ag
nanoparticle (1021 molecules/cc)

Fig. 15: CFU count of E. coli culture (isolated from waste water) after treatment with Ultrasonic waves at 35 KHz
in varying time interval (B) treated with varying concentration of Ag-nanoparticle

and heated until it begins to boil. Then 5 mL of 1% irradiation on E. coli cells isolated from waste water.
sodium citrate solution was added; heating continued The inocula of E. coli cell were prepared by growing
until the color was pale yellow. The solution was test strain in LB medium at 37°C until approximately
cooled to room temperature. 104-105 CFU reached.Prepared 24 test tube containing
10 ml LB broth + 100 µl culture of 105 cells ml−1, in
Microbiological test: Study is based on the combined each test tube. 20 culture tubes were treated for 5, 15,
antibacterial effect of Ag-nanoparticle and ultrasonic 25 and 35 min. at 35 KHz ultrasound frequency. Out of
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