Behavior and Production of

Nanoparticles

Under supervision of

Prof/ Yasser Fathi Hussien

Head of Biomaterials Department
Dean of faculty of dentistry, Minia University

&
Dr/ Reem Gamal Hasan
Lecturer in Biomaterials Department

Seminar submitted to Dental Biomaterial Department in partial

fullfiment of the requirements of PhD in Dental Biomaterial
Department (first semester)

Prepared by /
Hager Abdullah Abdulhamid
2024

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Content:

❖ Introduction 3

❖ Behaviour of Nanoparticles 5

• Intrinsic Properties of Nanoparticles 8

• Electronic and Optical Properties 9

• Mechanical Properties 10

• Adhesion Properties 12

❖ Production of Nanoparticles 14

• Top / down approach 14

• Bottom / up approach 17

❖ References 20

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 Introduction
There has been a rapid increase in interest in nanotechnology and the use of
nanoparticles in commercial applications. However, there is little known of the fate
and behavior of engineered nanoparticles in the environment. The properties of
nanoparticles differ remarkably from small molecules and their chemistry and
synthesis necessitates that they be considered more like complex mixtures than
small molecules.

The ability of the molecules to attach to the surface of nanoparticles and

exchange with other molecules already placed there indicates that careful con-
sideration of the chemistry of nanoparticles and how it relates to their fate in
surface waters and sediments is key to predicting their final fate. We have set out to
briefly introduce at a basic level the properties and synthesis of nanoparticles and
then review the state of current under-standing relating to the fate and behaviour of
nanoparticles in the environments with particular focus on engineered
nanoparticles.

Although it is often tempting to consider nanoparticles as simple molecules,

they are in fact complex mixtures. Even in the simplest cases one must consider the
interactions of at least two different aspects of the material. Whilst they may
absorb light like a dye and appear to dissolve like any other small molecule, their
actual behaviour is often subtly different and is usually the result of the different
components of the material.

Any nanoparticle will have an exceptionally high surface area to volume

ratio, this is one of the reasons for some of their unusual properties. However, this
high surface area also means that the surface of any given nanoparticle is an
important component of the material. So even the simplest nanoparticle will have a
surface chemistry, which is distinctly different from that of the core material.
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 In the case of silica the material will have a core structure of SiO2 , but the
surface would have a chemistry more comparable to a formula Si(O) (2-x) (OH)(2x).
The result of this is that the outer layer of atoms in the particle has a different
composition from the rest of the particles.

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 1. Behaviour of Nanoparticles

The surface chemistry of the particle has a significant contribution with the
environment. Furthermore, the surface of the nanoparticle will be the first aspect
experienced either by the environment or by an organism.

In many cases the composition of the surface of the nanoparticle is directly

related to their final application. For example, a nanoparticle designed to interact
with biological systems will have suitable functional groups attached to its surface,
such as short chain peptides. In many cases the surface functionalization is critical
to producing nanoparticles that exhibit the correct properties. This is often due to
that many nanoparticles lose their unique properties once they have aggregated and
precipitated from suspension.

So efforts for correctly disperse nanoparticles in their media of choice by

preparing nanoparticles that have some coating that facilitates dispersion of the
particles.

In some cases these coatings are in the form of surfactants that form
transient Van-der-Walls interactions with the surface and exist in equilibrium with
the free surfactant molecule. In other cases a molecule or ion is bound to the
surface of the particle so imparting stabilization of the particle suspension.

A nanoparticle can therefore be split into two or three layers; a surface that
may often be functionalized, a shell material that may be intentionally added and
the core material. Often nanoparticles are only referred to by their core material
because this is the part of the nanoparticle that results in key properties for most
applications.

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 1.1. Intrinsic Properties of Nanoparticles

The fate, behaviour and the ecotoxicology of nanoparticles will be closely

related to their intrinsic properties. There are several aspects to nanoparticles which
can easily be dismissed in error due to their apparent ability to behave more like
molecules than larger colloidal suspensions.

1.1.1. Surface energy

Any collision event between two particles will result in agglomeration and
precipitation of the nanoparticles from solution. It is therefore necessary to
stabilize the dispersion of the nanoparticles by providing a barrier to close
approach of two particles.

These barriers are either based on charge or steric stabilisation of the colloid.
In the first case a charged surface is present which has associated counter ions and
some solvent molecules which are tightly bound to the surface of the particle. The
associated charge at the surface causes repulsion of like charges according to
coulombs law so providing a barrier to aggregation.

In steric stabilisation a relatively long molecule is tethered to the surface of

the particle. The long chain of the molecule will have a high affinity for the
solvent. The barrier to aggregation is therefore related to the relative interactions of
the polymer chain with itself and with the solvent.

In order for the particles to aggregate solvent must be eliminated from

between the two particles and from around the chains; this is unfavourable and
therefore presents a barrier to aggregation.

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 1.1.2. Catalysis

Any nanoparticle has a very high surface area to volume ratio. The surface
area to volume ratio scales with the inverse of the radius. This means that the
percentage of atoms available at the surface of a particle for catalysing a reaction
will also scale with the inverse of the radius of the particle. For example, a
nanoparticle of gold with a diameter of 5 nm will have 31% of its atoms at the
surface, whereas at 50 nm this drops to 3.4% and at 1 micron this falls to 0.2%.

In addition to the number of surface atoms available for reaction, these sites
may also vary from the bulk material because of variations in the lattice structure
at the surface of the particle. The result of this is that materials prepared in a
nanoparticle form can have much higher activity in catalytic processes than the
bulk material and in some cases materials which may be thought of as poor
catalysts, such as gold, can be found to have excellent catalytic properties when
prepared in a nanoparticle form.

1.2. Electronic and Optical Properties

The optical and electronic properties of NPs are inter-dependent to greater

extent. For instance, noble metals NPs have size dependent optical properties and
exhibit a strong UV–visible extinction band that is not present in the spectrum of
the bulk metal. This excitation band results when the incident photon frequency is
constant with the collective excitation of the conduction electrons and is known as
the localized surface plasma resonance (LSPR).

1.2.1. Magnetic Properties

Magnetic Nanoparticles are of great curiosity for investigators from an

eclectic range of disciplines, which include heterogenous and homogenous
catalysis, biomedicine, magnetic fluids, data storage magnetic resonance imaging
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(MRI), and environmental remediation such as water decontamination. The
literature revealed that NPs perform best when the size is <critical value i.e. 10–20
nm. At such low scale the magnetic properties of NPs dominated effectively, which
make these particle priceless and can be used in different applications.

The uneven electronic distribution in NPs leads to magnetic property. These

properties are also dependent on the synthetic protocol and various synthetic
methods such as solvothermal, co-precipitation, micro-emulsion, thermal
decomposition, and flame spray synthesis can be used for their preparation

1.3. Mechanical Properties

Understanding some basic mechanical properties of nanoparticles, such as

the hardness and the elastic modulus, will aid a lot in the proper design of particles
in specific applications, as well as evaluating their roles and action mechanisms. To
the authors' knowledge, the measurement of the mechanical properties of
microparticles has been developed for decades.

The micro indentation technique was used to test the hardness of

microparticles with indented areas of larger than 100 µm2 and a minimum indenter
size of 20 µm2. About ten years ago, nanoindentation was employed to measure the
elastic properties of particles (average size: 5 µm). The methods were aimed at
measuring the film of particles rather than individual particles. The deformation
behaviours of polystyrene microspheres (diameter: 20 µm) by using AFM against a
its surface. Since then, protocols of calculating the mechanical characteristics (e.g.,
the elastic modulus) of nanoparticles have developed rapidly, primarily by
measuring the particles' deformation with AFM.

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 Typically, quantitative computation of the elastic modulus of nanoparticles
requires the measurement of indentation by converting AFM force-displacement
curves into force-indentation curves instead of measuring the contact area radius.

In this way, the force–indentation curves can be obtained for the calculation of
the particles' elastic modulus by evaluating the slope of the loading region on the
curves with contact theories. The nanoparticles' hardness and elastic modulus often
deviate from their bulk materials' and some show obvious size-dependent
behaviours.

However, only the fracture properties rather than the elastic behaviour of ZnO
nanowires were affected by the surface effects due to the presence of surface
cracks and defects. Measuring the mechanical properties of individual
nanoparticles is very complex; many influencing factors could affect the finally
measured results. These factors include the uniform dispersion of nanoparticles on
an ideally hard substrate, the precise locating of particles and the proper
application of loads onto the particles, as well as the measurement of the minimum
particle deformation, etc.

1.4. Adhesion Properties

The adhesion and the friction of nanoparticles play important roles in

nanofabrication, lubrication, the design of micro/nano devices, colloidal
stabilization and drug delivery. AFM has been proved to be a powerful tool to
measure the adhesion and friction between a nanoparticle and a solid surface. The
AFM tip itself can also be thought of as a nanoparticle; then the adhesion force as
well as the friction force can be easily obtained by the cantilever's deflection.

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 The use of AFM is practically limited by the tip material and its geometric
shape. By attaching the particle to the force sensor in the microscope, the force
between a surface and a colloid particle was directly measured with AFM. Since
the properties of the attached particle, such as the size, the shape and the material
were controllable, the uncertainties in the force measurement caused by the
irregular shape of the AFM tip could be avoided.

1.5. Zeta potential (ZP) effect on NPs properties and Drug delivery

Zeta potential is a scientific term for electrokinetic potential in colloidal

systems, i.e., electric potential in the interfacial double layer at the location of the
slipping plane versus a point in the bulk fluid away from the interface.

This term expresses the potential difference between the dispersion medium
and the stationary layer of fluid attached to the dispersed particle. Although zeta
potential is not equal to the Stern potential or electric surface potential in the
double layer, it is often the only available path for the characterization of double-
layer properties.

Measurement of Zeta-potential is currently the simplest and most

straightforward way to characterize the surface of charged colloids, and
conclusions are easily drawn from the analysis of its data regarding concentration,
disturb Zeta potential can affect the pharmacokinetic properties of nano systems in
the body or may affect the phagocytosis of the nanoparticles in the blood stream.

Nanoparticles can be detected by electrostatic methods, by condensation on

particles to grow them until they are measurable optically, or by other methods.
Electrostatic methods require that the particles be charged and are not very
sensitive. To fully characterize the charge conditions of particles, zeta potential
measurements should be performed in distilled water and in the original dispersion

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medium of the suspension. Very often, ZP measurements are performed in buffers
of varying molarities, physiological salt solution other media.

Zp and Targeted Drug Delivery

Nanoparticle surface is a very important consideration in targeting drug

delivery. Indeed, once in the blood stream, conventional nanoparticles (no surface
medication) and negatively charged particles can be rapidly opsonized and
massively cleared by fixed macrophages.

It is well known that the reticuloendothelial system (RES), mainly the liver
and spleen, is a major obstacle to active targeting because of its ability to recognize
these systems, remove them from systemic circulation, and consequently, avoid the
effective delivery of the nano drug to organs other than those of the RES. Surface
modification of these polymer nanoparticulate systems with hydrophilic polymers
is the most common way to control the opsonization process and to improve the
surface properties, especially surface charge, of the system.

Effect of ZP on cellular uptake

Physicochemical properties, such as particle size, shape and surface charge,
play a key role in the cellular uptake of nanoparticles. The uptake of nanoparticles
by cells can be viewed as a two step process: first, a binding step on the cell
membrane and second, the internalization step . The attachment of nanoparticles to
cell membrane seems to be most affected by the surface charge of the particles.
Variation of the particle surface charge could potentially control binding to the
tissue and direct NPs to cellular compartments both in vitro and in vivo.

Cellular surfaces are dominated by negatively charged sulphated

proteoglycans molecules that play pivotal roles in cellular proliferation, migration,
and motility. Cell surface proteoglycans consist of a core protein anchored to the

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membrane and linked to one or more glycosaminoglycan side chains to produce a
structure that extends away from the cell surface.

Once inside the cell, degradation of polymers may occur, but targeting
specific intracellular organelles is possible depending on the surface charge and
attached ligands. Nanoparticles with higher surface charge bound strongly to the
cell membrane and showed a higher cellular uptake, where electrostatic
interactions between the anionic membrane and cationic nanoparticles facilitate the
uptake. After the adsorption of the nanoparticles on the cellular membrane, the
uptake occurs via several possible mechanisms such as pinocytosis, nonspecific or
receptor-mediated endocytosis or phagocytosis.

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 2. Production of Nanoparticles

The creation of nanoparticles may be approached through three primary

methods: chemical, biological, and physical techniques. The chemical and
biological techniques together are referred to as the bottom-up strategy, whereas
the physical approach is also known as the top-down approach. Another name for
the biological approach is "green systems of NPs." All of these strategies are
further divided into different kinds according on the techniques they use.

2.1. Top / down approach

Bulk materials are fragmented in top-down methods to create nano-

structured materials.

2.1.1. Mechanical Milling

The mechanical milling process uses balls inside containers and may be
carried out in various mills, which is an impact process with high energy.

Mechanical milling is a practical approach for creating materials at the

nanoscale from bulk materials. Aluminum alloys that have been strengthened by
oxide and carbide, spray coatings that are resistant to wear, nanoalloys based on
aluminum, nickel, magnesium, and copper, and a variety of other nanocomposite
materials may all be created mechanically. A unique class of nanoparticles known
as ball-milled carbon nanomaterials has the potential to meet the needs for energy
storage, energy conversion, and environmental remediation.

2.1.2. Electrospinning

It is used to create nanofibers from various materials, most often polymers.

A technique for creating fibers called electrospinning draws charged threads from
polymer melts or solutions up to fiber sizes of a few hundred nanometers. Coaxial

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electrospinning was a significant advancement in the field of electrospinning.
Core-shell and hollow polymer, inorganic, organic, and hybrid materials have all
been developed using this technique.

2.1.3. Laser Ablation

A microfeature can be made by employing a laser beam to vaporize a single

material. Laser ablation synthesis produces nanoparticles by striking the target
material with an intense laser beam. Due to the high intensity of the laser
irradiation used in the laser ablation process, the source material or precursor
vaporizes, causing the production of nanoparticles. Laser ablation is an
environmentally friendly for producing noble metal nanoparticles.

2.1.4. Sputtering

Sputtering Microparticles of a solid material are expelled off its surface

during the phenomenon known as sputtering, which occurs when the solid
substance is assaulted by intense plasma or gas particles. The sputtering method is
intriguing because it is more affordable than electron-beam lithography, and the
composition of the sputtered nanomaterials is similar to the target material with
fewer contaminants.

2.1.5. Electron explosion

In this technique, a thin metal wire is subjected to a high current pulse that causes
an explosion, evaporation, and ionization. The metal becomes vaporized and
ionized, expands, and cools by reacting with the nearby gas or liquid medium. The
condensed vapor finally forms the nanoparticles.

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 2.1.6. Sonication

The most crucial step in the creation of nanofluids is sonication. After the
mixture has been magnetically stirred in a magnetic stirrer, sonication is performed
in an ultrasonication path, ultrasonic vibrator, and mechanical homogenizer. Probe
sonication is highly effective for processing nanomaterials (carbon nanotubes,
graphene, inks, metal oxides, etc.)

2.1.7. Pulsed wire discharge

This is the most used method for creating metal nanoparticles. A pulsating
current causes a metal wire to evaporate, producing a vapor that is subsequently
cooled by an ambient gas to form nanoparticles.

2.1.8. Arc discharge

Two graphite rods are adjusted in a chamber with a constant helium pressure
during the Arc Discharge procedure. It is crucial to fill the chamber with helium
because oxygen or moisture prevents the synthesis of fullerenes. Arc discharge
between the ends of the graphite rods drives the vaporization of carbon rods.
Achieving new types of nanoparticles depends significantly on the circumstances
in which arc discharge occurs.

2.1.9. Lithography

Typically uses a concentrated beam of light or electrons to create

nanoparticles, a helpful technique. Masked and maskless lithography are the two
primary categories of lithography. Without a mask, arbitrary nano-pattern printing
is accomplished in maskless lithography. Additionally, it is affordable and easy to
apply.

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 2.2. Bottom-up approach

Tiny atoms and molecules are combined in bottom-up methods to create nano-
structured particles

2.2.1. Chemical vapor deposition

Through a chemical process involving vapor-phase precursors, a thin coating

is created on the substrate surface during CVD.

Precursors are deemed appropriate for CVD if they exhibit sufficient

volatility, high chemical purity, strong evaporation stability, cheap cost, a non-
hazardous nature, and long shelf life. Additionally, its breakdown should not leave
behind any contaminants. CVD is an excellent approach to creating high-quality
nanomaterials. It is also well-known for creating two-dimensional nanoparticles

2.2.2. Sol-gel process

A wet-chemical approach, called the sol-gel method, is widely utilized to

create nanomaterials. Metal alkoxides or metal precursors in solution are
condensed, hydrolyzed, and thermally decomposed. The result is a stable solution
or sol. It may take a few days for the solvent to be removed and for the phase to
change during the mature stage, which is necessary to enable the growth of solid
mass.

To create nanoparticles, the unstable chemical ingredients are separated. The

generated material is environmentally friendly and has many additional benefits
thanks to the sol-gel technique. The uniform quality of the material generated, the
low processing temperature, and the method’s ease in producing composites and
complicated nanostructures are just a few of the sol-gel technique’s many
advantages.

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 2.2.3. Co-precipitation

It is a solvent displacement technique and is a wet chemical procedure.

Ethanol, acetone, hexane, and non-solvent polymers are examples of solvents.
Polymer phases can be either synthetic or natural. By mixing the polymer solution,
fast diffusion of the polymer-solvent into the non-solvent phase of the polymer
results.

Interfacial stress at two phases results in the formation of nanoparticles.This

method’s natural ability to produce high quantities of water-soluble nanoparticles
through a straightforward process is one of its key benefits.

2.2.4. Inert gas condensation/molecular condensation

Metal NPs are produced using this method in large quantities. Making fine
NPs using the inactive gas compression by causing a metallic source to disappear
in an inert gas. At an attainable temperature, metals evaporate at a tolerable pace.

Copper metal nanoparticles are created by vaporizing copper metal inside a

container containing argon, helium, or neon. The atom quickly loses its energy by
cooling the vaporized atom with an inert gas after it boils out. Liquid nitrogen is
used to cool the gases, forming nanoparticles in the range of 2–100 nm.

2.2.5. Green/biological synthesis

The synthesis of diverse metal nanoparticles utilizing bioactive agents,

including plant materials, microbes, and various biowastes like vegetable waste,
fruit peel waste, eggshell, agricultural waste, algae, and so on, is known as “green”
or “biological” nanoparticle synthesis. Developing dependable, sustainable green
synthesis technologies is necessary to prevent the formation of undesirable or
dangerous byproducts.

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 The green synthesis of nanoparticles also has several advantages, including
being straightforward, affordable, producing NPs with high stability, requiring little
time, producing non-toxic byproducts, and being readily scaled up for large-scale
synthesis.

2.2.6. Biological synthesis using microorganisms

Microbes use metal capture, enzymatic reduction, and capping to create

nanoparticles. Before being converted to nanoparticles by enzymes, metal ions are
initially trapped on the surface or interior of microbial cells. Use of
microorganisms (especially marine microbes) for synthesis of metalic NPs is
environmental friendly, fast and economical. Several microorganisms are used in
the synthesis of metal NPs.

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