CHAPTER 1: INTRODUCTION TO NANOMATERIALS

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1.1 Introduction to Nanomaterials

Nanotechnology is an emerging technology which is an amalgamation of different aspects of

science and technology that includes disciplines such as electrical engineering, mechanical

engineering, biology, physics, chemistry, and material science. Nanotechnology has potential

applications in the fields of information and communication technology, biotechnology, and

medicinal technology. Nanotechnology is an important field of modern research dealing with

synthesis, strategy and manipulation of particle‟s structure ranging from approximately 1 to 100

nm in size [1]. Nanomaterial is any material with any external dimension in the nanoscale in size

range from approximately 1–100 nm or having internal structure or surface structure in the

nanoscale (ISO 2015). Or nanomaterial is defined as a natural, incidental or manufactured

material containing particles, in an unbound state or as an aggregate or as an agglomerate and

where, for 50% or more of the particles in the number size distribution, one or more external

dimensions is in the size range 1 nm–100 nm (European commission, 2011).

Nanomaterials were first used by humans in ancient times, without actually knowing about it.

Some examples of nanomaterials are found in Gothic churches across Europe, where gold

nanoparticles (Au NPs) of different sizes and compositions gave bright colors to stained glasses

[2]. The properties of nanomaterials are critically dependent on size, shape and dimensionality of

materials [3]. Therefore, all these properties are responsible for the wide application of

nanoparticles in the field of human health care and other applications. Promising new

technologies based on nanotechnology are being utilized to improve diverse aspects of medical

treatments like diagnostics, imaging, and gene and drug delivery [4]. Nanobiotechnology

represents the intersection of nanotechnology and biotechnology, which is an emerging field

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dedicated to creation, improvement, and utility of nanoscale structures for advanced

biotechnology [5].

Generally, nanomaterials are classified based on their dimensionality, morphology, composition,

uniformity, and agglomeration. Due to the reduction in the spatial dimension, or confinement of

particles or quasi particles in a particular crystallographic direction within a structure generally

leads to changes in physical properties of the system in that direction. Hence classification of the

nanostructured materials and systems essentially depends on the number of dimensions which lie

within the nanometer range. There are four types of nanomaterials based on dimensionality.

These are (i) Zero dimensional nanomaterials (0 D NMs), systems confined in three dimensions

e.g., nanoparticles, nanograins, nanoshells, nanocapsules, nanorings, fullerenes, colloidal

particles, activated carbon, nanoporous silicon, graphene clusters, short carbon chains, nano

cones and quasi crystals; (ii) One dimensional nanomaterials (1 D NMs), systems confined in

two dimensions, e.g., nanorods, nanofilaments, helicoidal carbon nanotubes, quantum wires,

graphene nanoribbons and nano wires; (iii) Two dimensional nanomaterials (2 D NMs), systems

confined in one dimension, e.g., discs, platelets, ultrathin films, super lattices, haeckelite surface,

graphene surface and quantum wells; and (iv) Three dimensional nanomaterials (3 D NMs), all

dimensions are not within the nanoscale range, e.g., 3 D graphite crystal, 3 D schwarzite crystal,

carbon nanofoams and 3 D nanotube networks [6]. The main importance of these materials is

that, size can influence the physicochemical properties.

1.2 Properties of Nanomaterials

Bulk materials have consistent physical properties regardless of their size; however, among

nanoparticles the size often dictates the physical and chemical properties. Metal and

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semiconductor nanomaterials have physical properties that are significantly different from their

bulk counterparts [7]. Small size of nanomaterials can alter their electrical, magnetic, structural,

morphological and chemical properties, enabling them to interact in unique ways with cell

biomolecules and enabling their physical transport into the interior structures of cells.

Nanoparticles have unique physical properties due to their large surface area to volume ratio,

color, melting point, and absorption of solar radiation. Due to its large surface area to volume

ratio zinc oxide nanoparticles (ZnO NPs) have been found to have superior UV blocking

properties compared to its bulk substitute [8]. Bulk gold is used as jewellery and is yellow in

color, however, if it is shrunk into nanoparticles it will be red colored in spherical shape and

colorless in ring shape. Au NPs melts at much lower temperatures about ~300 °C (for 2.5 nm

size) than the gold bulk which melts at 1064 °C [9]. Due to their smaller size, nanoparticles

absorb greater amount of solar radiation in photovoltaic cells than thin films of continuous sheets

of bulk material. Nanoparticles also often possess unexpected optical properties as they are small

enough to confine their electrons and produce quantum effects. One example of this is that Au

NPs appear deep red to black in solution. Au NPs solution is resulted from the increased

diameter of Au NPs, and the changes of resonance absorption peak and resonance scattering

[10]. Additional, important physical property of nanoparticles is their ability to form suspensions

[11]. This is possible since the interaction of the particle surface with the solvent is strong

enough to overcome density differences. In bulk materials this interactions usually result in a

material either sinking or floating in a liquid. Magnetization property is among other properties

that are unique due to quantum confinement in semiconductor particles, surface plasmon

resonance in some metal particles and superparamagnetism in magnetic materials [12]. At

elevated temperatures, nanoparticles possess the property of diffusion. Sintering can take place

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at lower temperatures, over shorter time scales than for larger particles. Although this does not

affect the density of the final product, there is a chance of agglomeration. Diffusion coefficient

obtained by changing the temperature has an influence on the hydrodynamic radius of the

particles [13]. Hard nanoparticles such as, clay nanoparticles when incorporated into polymer

matrices increase reinforcement, leading to stronger plastics. These nanoparticles are hard, and

impart their properties to the polymer (plastic). Nanoparticles have also been attached to textile

fibers in order to create smart and functional clothing. Metal nanoparticles are used as

reinforcement in alloys for application in light weight construction with in the aerospace sector

and increasingly in the automotive sector to strengthen steel. For instance, iron carbide is used to

make steel harder. Semi-solid or soft nanoparticles such as liposome have been manufactured

for clinical applications as delivery systems for anticancer drugs, antibiotics and antifungal drugs

and vaccines.

Silver has been widely employed for many years in human history. Silver is the only element

whose plasmon resonance can be tuned to any wavelength in the visible spectrum [14]. Silver

nanoparticles (Ag NPs) are the most widely used nanomaterial in healthcare today, with total

annual worldwide production estimated to be in the range of 500 tons [15]. This element has

many applications, it has superior antimicrobial, antifungal, and antiviral properties. Ag NPs

have been demonstrated to exhibit antimicrobial properties against bacteria with close

attachment of the nanoparticles themselves to the microbial cell and the activity being size

dependent [16]. Fundamental studies showed that Ag NPs exhibit a rare combination of valuable

properties, namely, unique optical properties associated with the surface plasmon resonance,

catalytic activity, high electrical double layer capacitance, etc.

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Different types of inorganic metal oxides have been synthesized and studied, such as TiO 2, CuO,

and ZnO. Nanoparticles are of interest because of the new properties, such as, chemical

reactivity and optical behavior that they exhibit compared with larger particles of the same

materials. For example, TiO2 and ZnO become transparent at the nanoscale, however are able to

absorb and reflect UV light, and have found application in sunscreens. Of all these metal oxides,

ZnO NPs is of maximum interest because they are inexpensive to produce, easy to prepare and

safe to use [17]. ZnO NPs has been prefered as one of the best heterogeneous photocatalyst when

compared to TiO2 based on its high efficiency, low cost and generally low toxicity [18]. US FDA

has enlisted ZnO as GRAS (generally recognized as safe) metal oxide [19]. There are variety of

structures of nanometric ZnO and are classified based on their dimensionality with potential

applications in many fields of nanotechnology. Zinc oxide can occur in 1 D, 2 D and 3 D

structures. 1 D structures make up the largest group, including nanorods [20, 21], nanoneedles

[22], nanohelixes, nanosprings, nanorings [23], nanoribbons [24], nanotubes [25], nanobelts [26],

nanowires [27, 28] and nanocombs [29]. Zinc oxide can be obtained in 2 D structures, such as

nanoplate/nanosheet and nanopellets [30, 31]. Examples of 3 D structures of zinc oxide include

flower, dandelion, snowflakes, and coniferous urchin-like [32, 33].

ZnO NPs has unique properties, such as good transparency, strong room-temperature

luminescence, high electron mobility, wide bandgap of 3.3 eV in the near-UV spectrum, a high

excitonic binding energy (60 meV) at room temperature, higher quantum efficiency, chemical,

photochemical stability [34-37], piezoelectric and pyroelectric properties [38]. Due to its UV

filtering properties, it has been extensively used in cosmetics as sunscreen lotions [7, 39]. ZnO

NPs is known as II–VI semiconductor [40], since Zn and O belong to groups II and VI in the

modern periodic table, respectively. ZnO exhibits three crystallize structures, namely wurtzite,

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zinc-blende and sometimes rock-salt, Figure 1.1 [41, 42]. The hexagonal wurtzite structure

possesses crystallite lattice constant spacing a = 0.325 nm and c = 0.521 nm, the ratio c/a ≅ 1.6

that is very close to the ideal value for hexagonal cell c/a = 1.633. Each tetrahedral Zn atom is

surrounded by four oxygen atoms and vice versa. The structure is thermodynamically stable in

an ambient environment, and usually illustrated schematically as a number of alternating planes

of Zn and O ions stacked alongside the c-axis. Zinc-blende structure is metastable and can be

stabilized via growth techniques [42–45].

Figure 1.1 Crystallize structures of ZnO NPs (a) rock-salt, (b) zinc-blende and (c) wurtzite
[41]

Metal oxide NPs are among the nanomaterials widely studied by researchers for the purpose of

wide applications. Nanobiotechnology based techniques of synthesis of biological NPs has the

potential to deliver clean manufacturing technologies. These new clean technologies have

significantly reduced environmental pollution and decreased the hazards to human health that

could result from the use of toxic chemicals and solvents which are currently used in

conventional industrial fabrication processes [45]. Iron oxides exist in many forms. The most

common are magnetite (Fe3O4), maghemite (γ-Fe2O3), and hematite (α-Fe2O3) [46], Figure 1.2.

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The optical properties of Fe3O4 NPs are associated with their crystal structure. Magnetite

crystallizes in the inverse cubic spinel structure which can be written as (Fe3+)A(Fe2+Fe3+)BO4,

where A is the tetrahedral and B is the octahedral side. The magnetite crystal belongs to the

cubic space group Fd3m. Sadat et al. [47] have reported the energy bands of the Fe3O4 NPs, in

which the valence band of the O(2p) to the empty Fe(4s) in Fe3O4 is separated by 4-6 eV.

Furthermore, crystal field bands of the octahedral and tetrahedral sites appeared between these

bands. Therefore, as a result of excitation electron transfer from O(2p) to the crystal field eg

which requires energy of 3.1 eV, transfer from t2g to the eg requiring 2.2 eV, transfer from e to

the t2 requiring 0.9 eV or from O(2p) to the t2 (1.8 eV) [48] may occur.

Figure 1.2 Crystal structure and crystallographic data of (a) hematite, (b) magnetite and

(c) maghemite (the black ball is Fe2+, the green is Fe3+ and the red ball is O2-) [49]

Co-precipitation is one of the most common synthesis methods of Fe3O4 NPs. In co-precipitation

reaction, iron sources from FeCl3 and FeCl2 (2:1 ratio) react in the presence of NaOH as

precipitating agent according to the following reaction:

Fe2+ + 2Fe3+ + 8OH- → Fe3O4 + 4H2O

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Wei et al. [50] reported synthesis of Fe3O4 NPs by a co-precipitation method using sodium

citrate and oleic acid as modifiers. The magnetic behavior was changed by the modification and

the surface effect decreased the saturation magnetization of Fe3O4 NPs. In addition, it showed

excellent dispersion ability, which should be ascribed to the great reduction of high surface

energy and dipolar attraction of the nanoparticles.

Graphene is a single layer of carbon atoms densely packed in a honeycomb crystal lattice. The

exceptional properties of graphene, such as high surface area (2630 m2/g), good chemical

stability, and graphitized basal plane structure, allow it to have strong π–π interactions with the

aromatic moieties present in dyes [51, 52]. The structure of graphene oxide is represented in

Figure 1.3. Carbon nanomaterials have small particle size and are difficult to separate from

aqueous solutions as a matter of fact if exposed to the environment; they may bring serious

health and environmental problems [53]. Therefore different forms of graphene such as oxidized

or reduced forms can be hybridized with Fe3O4 NPs. These graphene hybridized Fe3O4 NPs are

easily separated by external magnetic bars after usage in water purifications for example.

Magnetite-reduced graphene oxide (rGO/Fe3O4) nanocomposites are best adsorbents of magnetic

solid-phase extraction. The combination of graphene sheets and magnetic Fe3O4 NPs offers

rGO/Fe3O4 distinguished properties such as good dispersity, large surface area, strong

superparamagnetism and excellent extraction ability [54]. Chandra et al. [55] synthesized

rGO/Fe3O4 nanocomposite through co-precipitation method for the removal of toxic chemical

arsenic from water samples. Similarly, in this particular study rGO/Fe3O4 nanocomposite is

synthesized by green method for the removal of organic dye pollutant from contaminated water.

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Figure 1.3 Structure of graphene oxide [56]

1.3 Overview of synthesis of Nanomaterials

Nanomaterials have been prepared by two different approaches i.e., top-down and bottom-up

[57]. In top-down method the starting material is reduced and reshaped in size either by physical

(e.g., mechanical techniques, such as, machining and grinding) or chemical means (e.g., by

lithographic techniques), which is known as top-down approach [58]. The main limitation with

top-down approach is that it results defect on the surface structure of the nanomaterials [59]. The

afformentioned effect in the surface structure can bring serious impact on physical properties and

surface chemistry of the metallic NPs due to the high aspect ratio. On the other hand, in bottom-

up approach small building blocks are assembled into a larger structure. The manufacturing of a

structure atom-by-atom, molecule-by-molecule, or cluster-by-cluster in a controlled manner that

is largely regulated by thermodynamic means such as self-assembly is known as bottom-up

approach [60]. In the later approach, the nanostructured building blocks (i.e, nanoparticles) are

first formed and, afterwards, assembled into the final material via chemical, physical or

biological synthesis procedure(s), Figure 1.4.

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 Figure 1.4 Schematic representation of top-down and bottom-up approaches [61]

The synthesis of metal and metal oxide NPs is accomplished by various types of physical,

chemical and biological synthetic routes. Most of these methods are still in the development

stage and the problems so far experienced are stability, aggregation of nanoparticles,

nanoparticles crystal growth control, morphology, size and size distribution. Generally, there are

different types of nanomaterials in the form of clusters, colloids, rods, thin films, tubes, wires,

nanoparticles etc. However, the synthesis mechanism of nanomaterials can be categorized as one

of the following three types of methods viz. physical, chemical and biological. Here only few

representative examples and their procedure methods, advantages and disadvantages are

mentioned, Figure 1.5.

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Figure 1.5 Types of nanomaterial synthesis methods

1.3.1 Physical vapour deposition

Physical vapor deposition (PVD) describes a variety of vacuum deposition methods which can

be used to produce thin films and coatings. PVD is characterized by a process in which the

material goes from a condensed phase to a vapor phase and then back to a thin film condensed

phase. PVD processes are environmentally friendly vacuum deposition techniques consisting of

three fundamental steps; (i) vaporization of the material from a solid source assisted by high

temperature vacuum or gaseous plasma, (ii) transportation of the vapour in vacuum or partial

vacuum to the substrate surface, and (iii) condensation onto the substrate to generate thin films.

[62]. PVD has several advantages such as coatings formed by PVD may have improved

properties compared to the substrate material; all types of inorganic materials and some types of

organic materials can be used; and the process is environmentally friendly compared to many

other processes such as electroplating. However, PVD has also some disadvantages; including

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problems with coating complex shapes; high process cost and low output and complexity of the

process [63].

1.3.2 Laser ablation

In laser ablation, nanoparticles are fabricated by nucleation and growth of laser vaporized species

in a background gas. Extremely rapid quenching of vapor results highly pure quantum sized

nanoparticles, i.e. less than 10 nm. Different types of nanoparticles, such as semiconductor

quantum dots, carbon nanotubes, nanowires and core shell nanoparticles are synthesized by this

method [64]. Nanotubes fabricated by laser vapourization are purer than those created by other

method such as discharge method [65]. In 1995, Smalley and co-workers produced carbon

nanotubes using laser ablation technique [66]. In the laser ablation technique, a high power laser

is used to vaporize carbon from a graphite target at high temperature. This technique can produce

both single walled nanotubes (SWNTs) and multi walled nanotubes (MWNTs). In order to

generate SWNTs, metal particles as catalysts must be added to the graphite targets similar to the

arc discharge technique. The quantity and quality of produced carbon nanotubes depend on

several factors such as the amount and type of catalysts, laser power and wavelength,

temperature, pressure, type of inert gas, and the fluid dynamics near the carbon target. The laser

is focused onto a carbon targets containing 1.2% of cobalt/nickel with 98.8% of graphite

composite that is placed in a 1200 °C quartz tube furnace under the argon atmosphere (~500

Torr). These conditions were achieved for production of SWNTs in 1996 by Smalley‟s group

[64]. In such technique, argon gas carries the vapors from the high temperature chamber into a

cooled collector positioned downstream. The nanotubes will self-assemble from carbon vapors

and condense on the walls of the flow tube. The diameter distribution of SWNTs from this

method varies about 1.0 to 1.6 nm. Carbon nanotubes produced by laser ablation were purer

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(90% purity) than those produced in the arc discharge process and have a very narrow

distribution of diameters. The main advantages of laser ablation include; properties of

nanoparticles depend strongly on size and size uniformity, and it can generate size and shape

controlled nanoparticles by post processing. However, some of the disadvantages include; small

production yield; high input energy requirement and small laser-irradiating area for evaporating

the target materials [67].

1.3.3 Sputter deposition

Sputter deposition is a technique used to deposit thin films on substrates. The technique is based

on ion bombardmen of a source material, i.e., the target. Ion bombardment results in a vapor due

to a purely physical process, i.e., the sputtering of the target material. Most commonly sputter

deposition uses magnetron source for growing thin films in which positive ions present in the

plasma of a magnetically enhanced glow discharge bombard the target [68]. Sputtering is a

convenient method for preparing films. By sputtering, different elementary materials are ionized

or heated to form the plasma before depositing on substrates. Sputtering can be employed for

preparing the nanoparticles embedded in the thin films, or so called granular films. High voltage

current is applied between the cathode and the anode in atmosphere of inert and active gases

leads to glow discharge. The ions during the process of discharge bump the target that serves as

the cathode, so that the atoms of the target materials could evaporate from the surface. The

cooling and the condensation in inert gases and/or the reaction in active gases of the evaporated

atoms result in the formation of nanoparticles and nanocapsules or thin films. This method has

many advantages. No crucible is needed, particles of metals with a high melting point can be

prepared, the evaporation surface can be large, particles of alloys can be synthesized using active

gases, granular thin films can be prepared, the narrow size distribution of the particles can be

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controlled well and nanocomposite materials can be produced if several different materials are

used as targets. The voltage, current, gas pressure, and target are the most important factors,

which affect the formation of nanoparticles [69]. However, disadvantages of sputter deposition

are mentioned as follows. Sputtering rates are low compared to those that can be attained in

thermal evaporation; in many configurations, the deposition flux distribution is non-uniform,

requiring moving fixturing to obtain films of uniform thickness; sputtering targets are often

expensive and material use may be poor; most of the energy incident on the target becomes heat,

which must be removed; in some cases, gaseous contaminants are "activated" in the plasma,

making film contamination more of a problem than in vacuum evaporation; and in reactive

sputter deposition, the gas composition must be carefully controlled to prevent poisoning the

sputtering target [70] . There are various types of sputter deposition such as ion-beam sputtering,

reactive sputtering, ion-assisted deposition, high-target-utilization sputtering, and gas flow

sputtering.

1.3.4 Cathodic arc deposition

Cathodic arc deposition is a plasma-based technology for the fabrication of films. In this

technique, an electric arc is used to vaporize material from a cathode target. The vaporized

material then condenses on a substrate, forming a thin film. The process can be carried out either

at high vacuum or in a low pressure gaseous environment and films, such as metals, ceramics,

diamond like carbon, semiconductors and superconductors are formed [71]. The benefit of the

cathodic arc deposition process arises from the high deposition energy of the condensing atoms,

which is essential in film growth to promote adhesion and also to disrupt columnar growth. The

estimates of the energies required for high quality film growth, based on ion-surface interaction

theory, indicate that energies of the order of 25-100 eV are also desirable for activating surface

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atom displacements whilst maintaining good crystallinity of the underlying bulk layers. The

disadvantage of cathodic arc deposition process is the formation of macroparticles, the size of

which lies in the ranges of 0.1-10 microns in growing films. The main limitations with

macroparticles contamination are that, it can increase the surface roughness and microholes in

the coating and cause abrupt changes of microstructure and texture [72].

1.3.5 High energy ball milling

Ball milling is a simple and efficient method for making various nanocrystalline powders [73].

High-energy planetary, ball and vibratory mills are used for grinding [74]. In ball milling, a

powder mixture is placed in the ball mill which is subjected to high-energy collision from the

balls. For example, mechanical alloying can produce fine, uniform dispersions of oxide particles

(such as Al2O3, Y2O3, ThO2) in nickel-base super alloys that could not be made by conventional

powder metallurgy methods [75]. In high energy ball milling a magnet is placed close to the cell

to apply a strong magnetic pulling force on the magnetic milling balls, and therefore the impact

energy is much higher than the conventional ball milling energy. Hard and brittle ceramic

materials can be ball-milled into nanoparticles to produce nanocrystals, non crystals, and

pseudocrystals. Powders of 500 nm sizes can be milled into several nm by strong vibrations

when mixed with tungsten-carbide (WC) spheres. The drawback of ball milling is the surface

contamination of the products and non-uniformity of the structure but is a simple method.

Sometimes an addition of 1 2% of methanol or phenol can prevent diffusion and solid reaction

of the nanoparticles.

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1.3.6 Melt mixing

In melt mixing, nanoparticles are formed in glass. Melted metals are cooled at very high cooling

rates (105-106 K/s) to form amorphous metallic glasses. Therefore, mixing molten streams of

metals with turbulence at high velocity can form nanoparticles. For instance, molten stream of

Cu-B and molten stream of Ti can form nanoparticles of TiB2. To synthesize polymer-CNT

nanocomposite by using melt mixing follows; mechanical mixing of CNTs with prepolymer melt

followed by extrusion, injection or compression moulding.

1.3.7 Chemical vapor deposition

Chemical vapor deposition (CVD) is a chemical process in which gaseous molecules transform

into a solid material, in the form of 0 D, 1 D, 2 D and 3 D NSMs, on the surface of a substrate. In

a CVD process; the substrate is exposed to one or more volatile precursors, which react and/or

decompose on the substrate surface to produce the desired deposit [18]. The basic CVD process

consists five steps, (i) a predefined mix of reactant gases and diluent inert gases are placed into

the chamber by the mass flow controller at a specified flow rate, (ii) the gas species move to the

surface site, (iii) the reactants get adsorbed on the surface site, (iv) the reactants undergo

chemical reactions with the substrate to form the NSMs, and (v) the gaseous reaction products

are desorbed and evacuated from the chamber. Some advantages of CVD include, production of

extremely dense and pure materials with possible manipulation at the atomic or nanometer

scales; films are highly uniform and have good reproducibility and adhesion with acceptable

deposition rates; crystal structure, surface morphology and orientation of the products can be

manipulated; it is less costly; The rate of deposition can be readily adjusted, e.g., low deposition

rates are favored for the growth of epitaxial thin films for microelectronic applications, while

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high deposition rates are preferred for the deposition of thick protective coatings [76]. To the

contrary, CVD has also some disadvantages, it uses usually toxic, corrosive, flammable, and/or

explosive precursor gases; it is difficult to deposit multicomponent materials with well-

controlled stoichiometry using multisource precursors; high level of sophistication in the reactor

or vacuum system in CVD will inevitably increase the cost of production [76].

1.3.8 Sol-gel technique

The sol-gel process (chemical solution deposition) is a wet chemical synthesis approach that can

be used to generate nanoparticles by gelation, precipitation, and hydrothermal treatment. Such

methods are used primarily for the fabrication of materials starting from a chemical solution (or

sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or

network polymers [77]. As an example, sol-gel method is used to synthesize Ag NPs by mixing

the AgNO3 solution with tetraethylorthosilicate (Si(OC2H5)4, ethanol and water then with a few

drops of HNO3 as a catalyst. The mixed solution is dispersed and dried. In addition, the dried

gels are reduced at a temperature of 400 °C for 30 min in hydrogen gas [78]. The main

advantages with the sol-gel process includes, the use of relatively low temperatures; it can create

very fine powders; and produces compositions not possible by solid-state fusion. However, there

are some disadvantages in the sol-gel process. These raw materials are very costly, e.g., MgO

powder (98% purity) costs $30/kg. Similarly, magnesium ethoxide (Mg(OC2H5)2), a chemical

source for making MgO, costs about $200/kg [79].

1.3.9 Hydro/solvothermal method

This method uses high pressures and temperatures over a prolonged range of time in order to

synthesize nano morphologies in a closed system/autoclave. Hydrothermal synthesis method

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uses water as a solvent while solvothermal synthesis method employs other solvents with the aim

to reduce the temperature and pressure required for the heterogeneous chemical reaction. These

methods are important technologies with regard to the production of semiconductor nanowires at

low temperatures [80]. Some advantages of Hydro/solvothermal synthesis method, include most

of the materials that are involved can be induced to solubility via heat and pressure applied to the

system up to its critical point; it offers a significant enhancement to the chemical activities of the

reactant, the possibility to replace the solid-state synthesis, and materials, which may not be

obtained via solid-state reaction but may be prepared through hydro/solvothermal synthesis;

products of intermediate state, metastable state and specific phase may be easily produced, and

novel compounds of metastable state and other specific condensed state may be synthesized;

simplified and precise control of the size, shape distribution, and crystallinity of the end product

via the adjustment of parameters such as reaction temperatures and time, the types of solvents,

surfactants and precursors can be achieved; substances that are low in melting points and high in

vapor pressures and tendency towards pyrolysis will be obtained. However, the disadvantages of

hydro/solvothermal synthesis method include: the need of expensive autoclaves; safety issues

during the reaction process and impossibility of observing the reaction process [81, 82].

1.4 Green synthesis of Nanomaterials

Synthesis of nanoparticles from the evaluation of green chemistry perspective considers three

main criteria. These criteria are (i) the choice of best solvent, (ii) using environmentally benign

reducing agent, and (iii) nontoxic material for the stabilization of the nanoparticles. However,

most of the synthetic methods reported to date give more emphasis on organic solvents [83]. The

use of eco-friendly and renewable materials for specific reducing and protecting agents, glucose

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and starch, as well as a benign solvent medium, results for plentiful advantages such as

environmental safety, ready integration of these nanomaterials and biologically relevant systems

[84].

The application of the twelve principles of green chemistry in nanoparticle synthesis is a

relatively new emerging issue concerning the sustainability. This field has received great

attention in recent years due to its capability to design alternative, safer, energy efficient, and less

toxic routes towards synthesis [85]. In the early 1990s the US environmental protection agency

(EPA) coined the phrase Green Chemistry „To promote innovative chemical technologies that

reduce or eliminate the use or generation of hazardous substances in the design, manufacture and

use of chemical products‟. The EPA, in association with the American chemical society (ACS),

developed green chemistry into a set of twelve guiding principles. The 12 principles of green

chemistry are represented in Figure 1.6.

Figure 1.6 The twelve principles of green chemistry by Anastas and Warner [86]

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Still, it is easy and best to cure waste from the beginning than to treat or clean up waste after it

has been created (Prevention). Therefore, synthesis methods should be designed to produce

maximum percent yield, i.e., all starting materials should proceed into the final product. The

atom economy concept proposed by Trost [87] is one of the most useful tools available for

design of reactions with minimum waste. The concept is that for economic and environmental

reasons reactions should be designed to be atom efficient, i.e. as many of the reacting atoms as

possible should end up in useful products (Atom economy).

Nonetheless, the principles in Figure 1.6 can be summarized into the following six short

summary points. These are, (i) the maximum amounts of reagents used in a reaction must be

converted to useful product (atom economy), (ii) production of waste should be minimized

through reaction design, (iii) non-hazardous raw materials and products should be used and

produced wherever promising, (iv) processes should be designed to be inherently safe, (v)

greater consideration should be given in using renewable raw materials, and (vi) processes

should be designed to be energy efficient.

The first real proof that the chemical industry was serious about environmental concerns came

with the „responsible care‟ concept, which was developed by the Canadian chemical producers

association in 1989 and has been adopted since by many industry association members

throughout the world [88]. Recently a convergence among the three disciplines of biological

based technologies, green chemistry, and nanotechnology has been reported. The aim of this new

discipline is to create new manufacturing processes and nanomaterials that reduce or eliminate

the use of hazardous substances [86]. One of the major goals of green chemistry is to

demonstrate that adoption of the principles, by industry, can create a competitive advantage [89].

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Bio-assisted methods, biosynthesis or green synthesis provides an environmentally benign, low-

toxic, cost-effective and efficient protocol to synthesize and fabricate nanoparticles. In biological

methods, the precursor sources are living organisms such as plants, bacteria, algae, fungus, yeast,

and actinomycetes, Figure 1.7. Nowadays, researchers have turned to biological method of

synthesis of nanoparticles as a prefered alternative method compared to chemical and physical

methods due to the accumulation of intra- or extra-cellular inorganic materials in both unicellular

and multicellular organisms [90, 91].

Figure 1.7 Biological sources used for green synthesis of nanomaterials [90]

These bio-organisms contain valuable phytoconstituents such as proteins, amines, aminoacids,

polyphenols, sugars, ketones and aldehydes which act as reducing and capping agents [92-95].

Plants have many types of phytoconstituents; primary constituents, such as amino acids, sugar,

proteins, purines, pyrimidines, nucleic acids, and chlorophyll. Secondary constituents, such as

22
alkaloids, terpenes, flavonoids, lignans, steroids, curcumines, saponins, polyphenols, and

glucosides can be mentioned. These primary and secondary metabolites are constantly involved

in the redox reaction to synthesize eco-friendly nanosized particles [96].

In green synthesis methods, plant phytoconstituents such as thiols and amines can be used as

capping agents, various other biomolecules can be used as surfactants and capping agents [97,

98]. Therefore, the increased environmental concern issues have motivated researchers to avoid

the use of harmful chemicals that may pose a significant ecological threat to the environment. In

addition, nanomaterials synthesized via physical and chemical means are not used for medical

applications due to the involvement of toxic chemicals during their synthesis. Consequently,

researchers have started to search for innovative alternatives, with a focus on green approaches,

which will be more eco-friendly and environmentally viable [99].

The biological syntheses of nanoparticles are being carried out by different macro-microscopic

organisms; such as plant, bacteria, fungi, seaweeds and microalgae. The biosynthesized

nanomaterials have been effectively controlling the various endemic diseases with less adverse

effect. Living organisms are composed of thousands of different kinds of inorganic and organic

molecules. Organic molecules are principally composed of six elements: carbon, hydrogen,

oxygen, nitrogen, phosphorous, and sulfur, and contain trace amounts of certain metallic and

other non metallic-metallic elements [100]. Plant contains abundant natural compounds such as

alkaloids, flavonoids, saponins, steroids, tannins and other nutritional compounds. These natural

products are derived from various parts of plant such as leaves, stems, roots, shoots, flowers,

barks, seeds and pods. Recently, many studies have proved that the plant extracts act as a

potential precursor for the synthesis of nanomaterial in non-hazardous ways. Since the plant

extract contains various secondary metabolites, it acts as reducing and capping agents for the

23
bioreduction reaction to synthesize novel metallic NPs. The biological synthesis of metallic NPs

is inexpensive, single step and eco-friendly method [101]. Biosynthesis methods are by far more

important than other classical synthesis procedures due to the availability of more biological

entities and eco-friendly procedures. The rich biodiversity and easy availability of plant entities

have been highly explored for the nanomaterials synthesis [102]. Many biomolecules in plants

such as proteins/enzymes, amino acids, polysaccharides, alkaloids, alcoholic compounds, and

vitamins could be involved in bioreduction, formation and stabilization of metal NPs. Reduction

potential of ions and reducing capacity of plants which depend on the presence of polyphenols,

enzymes, and other chelating agents present in plants have critical effects on the amounts of NPs

production [90]. Moreover, it has been reported that green synthesis approaches that use different

botanical products are reliable, simple, environmentally benign, and cost-effective alternatives

[103, 104].

Legumes are important sources of proteins, carbohydrates, dietary fiber, and minerals consumed

worldwide. They are generally well adapted to a wide range of climates and environmental

conditions. Legumes have been an important source of protein in many parts of the world, both

for animal and human nutrition [105, 106]. The legume crop Dolichos lablab L. has two

varieties; Dolichos lablab var. lignosus (field bean) and Dolichos lablab var. typicus (Indian

bean/lablab bean) [107]. Dolichos lablab var. typicus contain lectins sugar in the form of

galactose specific [100, 108], mannose/glucose specific [109], crude lipid, crude protein,

insoluble dietary fibre, soluble dietary fibre, ash, carbohydrate, amino acids: threonine, serine,

glutamic acid, proline, glycine, alanine, valine, methionine, cystine, isoleucine, leucine, tyrosine,

phenylalanine, histidine, lysine, and arginine [110].

24
Metal NPs produced by plants are more stable when compared to those produced by other

organisms. Plant extracts are able to reduce metal ions faster than fungi or bacteria [88, 90].

Synthesizing Ag NPs using plant organisms have the following advantages; (i) plant extract is

eco-friendly, it can be used as (ii) reducing and (iii) capping agents. Metal and semiconductor

NPs are of important due to their potential applications in emerging areas of nanoscience and

technology [111, 112]. Different sources of materials can be used as precursors during biological

synthesis of nanomaterials.

1.4.1 Biogenic synthesis of nanoparticles using isolated pure compounds of plants

The plant extract based green chemistry process has recently been emerged as one of the active

areas of current nano biotechnological research due to the involvement of low cost, higher

reducing potential, zero contamination and reduced or less environmental impact. Some plant

metabolites that are involved in biogenic synthesis of nanoparticles are apiin, ascorbic acid, citric

acid, cyclic peptide, ellagic acid, epicatechin gallate, euphol, galangin, gallic acid, phyllanthin,

tannin, pinocembrin, retinoic acid, sorbic acid, and theaflavin have been identified as responsible

compounds for the biogenic synthesis of nanoparticles. The plant extract based synthesis

methods have followed precise green chemistry procedures and plant extracts have continued to

be a source of novel bioreductants that can produce nanoparticles with controlled size, shape, and

greater stability [113]. Using natural extracts of plant parts is a very eco-friendly, cheap process

and it does not involve usage of any intermediate base groups. It takes very less time, does not

involve usage of costly equipment, precursor, gives a highly pure and quantity enriched product

free of impurities [114]. Plants are the most preferred source of nanoparticles synthesis because

they lead to large-scale production, stability, various shape and size of nanoparticles [114]. Bio-

25
reduction involves reduction of metal ions or metal oxides to zero valence metal NPs with the

help of phytochemicals like polysaccharides, polyphenolic compounds, vitamins, amino acids,

alkaloids, and terpenoids secreted from the plant [114, 115]. Biological method is one of the

more beneficial and advantageous methods, since plant extract is used as reducing and capping

agents for the synthesis of nanoparticles due to their reducing properties [116]. The

phytochemical constituents present in plant extract can be directly used for synthesis and capping

of Ag NPs [117]. Trisodium citrate is the sodium salt of citric acid, a naturally occurring

compound that is mainly found in citrus fruits. It can thus be found in high abundance and can be

considered as ecologically safe and biodegradable. Citrate has been widely used as reducing

agent for the preparation of Ag and Au NPs [118]. Pinto W et al. [119] have reported synthesis

of 5 nm sized Ag NPs in the presence of citrate ions by borohydride as a reducing agent. Citrate

was used to stabilize Ag NPs for one year with little oxidation while keeping the nanoparticle

solutions protected from light at 4 °C. Ascorbic acid has been extensively used as both a

reducing and capping agent and can be considered as a green reagent due to its environmentally

friendly and non-toxic character [118]. Kasthuri J et al. [120] reported synthesis of 39 nm quasi-

spherical Ag NPs by using apiin as the reducing and capping agents via electrostatic interaction

between carbonyl group and metal ion. The size and shape of the nanoparticles were controlled

by varying the ratio of metal salts to apiin compound in the reaction medium. Mallick et al. [121]

have used methoxypolyethylene glycol (MPEG) as a strong reducing and capping agents to

synthesize colloidal silver with a controlled particle growth. Cai et al. [122] used polydopamine

(PDA) as both metal ion chelating and reducing agent to synthesize Ag NPs in situ on the

sericin/polyvinyl alcohol (PVA) composite film. The PDA coating and Ag NPs modification do

not alter the structure of the silk sericin (SS)/PVA film. The prepared Ag NPs-PDA-SS/PVA

26
film had good hydrophilicity, hygroscopicity, mechanical performance, stability, environment

friendly and it had a long-term stable antibacterial activity against both gram-positive and gram-

negative bacteria. Gahlawat et al. [123] used glycolipoprotein to synthesize Ag NPs that had

remarkable antibacterial activity against Vibrio cholerae and inexpensive alternative approach to

treat the infection of the Vibrio cholerae during in vivo therapy of secretory diarrhea. Bar et al.

[124] used latex of Jatropha curcas as reducing as well as capping agent to synthesize Ag NPs.

It was reported that smaller particles were mostly stabilized by the cyclic octapeptide, i.e.

curcacycline A and cyclic nonapeptide, i.e. curcacycline B. On the other hand the larger and

uneven shaped particles were mainly stabilized by the curcain, an enzyme present in the latex.

Herrera-Becerra et al. [125] reported a simpler, consistent, and environmentally friendly method

of synthesis of Fe3O4 NPs using gallic acid and tannic acid. Tannins produced nanoparticles

smaller than 10 nm at pH = 10 which was confirmed with high-resolution transmission electron

microscopy. The phenolic-OH groups in tannins played a role as both the reducing and capping

agent.

1.4.2 Synthesis of nanomaterials by microorganisms

According to Syed B et al. [126], silver nano bactericides of size range 20 to 60 nm were

synthesized using a novel endophyte, Aneurinibacillus migulanus for bactericidal activity against

both gram-positive and gram-negative pathogens. Ghorbani [127] reported the biosynthesis of

Ag NPs employing the bacterium Salmonella typhirium through the reduction of aqueous Ag+

ion and the growth culture supernatants of bacteria in the bright conditions. Saravanan et al.

[128] reported extracellular biosynthesis of highly stable silver bionanoparticles from culture

supernatant bacterial strain Bacillus megaterium (NCIM 2326) by bio-reduction of silver ion, for

27
antibacterial efficacy on multi drug resistant clinical pathogens; Streptococcus pneumoniae and

Salmonella typhi. El-Kassas et al. [129] have reported a completely green biosynthetic method of

Fe3O4 NPs by reduction of ferric chloride solution and aqueous algal extracts of two seaweeds

i.e. Padina pavonica L and Sargassum acinarium L for bioremoval of lead from aqueous

solution. AbdelRahim et al. [130] reported cheap, non polluting and safe biological method of

synthesis of spherical, mono-dispersed and stable Ag NPs by using mycelial aqueous extract of

Rhizopus stolonifer that had an average size and surface plasmon band of 9.47 nm and 420 nm,

respectively. Mukherjee et al. [131] used a novel biological method for synthesis of Ag NPs

using fungus Verticillium. Aqueous Ag+ ions were bioreduced by the fungus Verticillium on the

surface of the mycelia leading to the formation of Ag NPs of fairly well-defined dimensions and

tolerable monodispersity of size 25 ± 12 nm. However, the metal ions were not toxic to the

fungal cells and the cells continued to multiply even after biosynthesis of the Ag NPs. Simple

and eco friendly chemical reaction was used to biometrically synthesize Ag NPs using Hypnea

musciformis at room temperature for photocatalytic degradation of methyl orange dye [132].

In this dissertation, biological method is used as means of synthesis of different types of

nanoparticles and nanocomposite using plant extract of Dolichos lablab L.

1.5 Significance of plant mediated synthesis of Nanomaterials

Nanomaterials can be synthesized by using chemical method as reducing agents which however,

later become accountable for various biological risks due to their general toxicity; engendering

the serious concern to develop environment friendly processes. Therefore to stay away from risks

and bring environmental benign synthesis method; biological approaches are coming up to fill

the void; for instance green synthesis using biological molecules derived from plant sources in

28
the form of extracts is exhibiting superiority over chemical and/or biological methods. These

plant based biological molecules undergo highly controlled assembly for making them suitable

for the metal NPs synthesis [133]. The biosynthesized nanomaterials have been effectively

controlling the various endemic diseases with less adverse effect. Plant contains abundant natural

compounds derived from various parts of plant such as leaves, stems, roots, shoots, flowers,

barks, seeds and pods. The biological synthesis of metallic NPs is inexpensive, single step and

eco-friendly method. Nanomaterials synthesized by green approach can be applied in large scale

production in industry. Nanomaterials produced from plant extract can be applied in drug-

delivery and environmental pollution prevention. The plants are used successfully in the

synthesis of various nanoparticles such as cobalt, copper, silver, gold, palladium, platinum, zinc

oxide and magnetite [133].

1.6 Application of Nanomaterials

The use of nanotechnology for the development and production of nanomaterials is nowadays

becoming a tremendous opportunity to offer a more sustainable approach in the applications of

medicine in health center and in the environmental protection. The demand for pure water is

increasing due to population growth at the same time as water supplies are being stressed

through increment in contamination and salinization of fresh waters, due to anthropogenic and

climate changes. Regularly harmful organic dye pollutants are discharged into the environment

from various industries [134]. Organic dyes are mostly used in textile, paper, leathers, food,

cosmetics, and printing industries. However, these dyes become major source of environmental

pollution if released directly into dry land and rivers without pre-treatments. Various industries

such as textiles, printing and rubber use methylene blue (MB) for the purpose of dyeing [134-

29
136]. Rhodamine (RhB) dyes belong to a class of dyes called xanthene dyes and are used as dye

laser materials [137], in biology as a staining fluorescent dye, sometimes in combination with

auramine O, as the auramine-rhodamine stain to demonstrate acid-fast organisms, notably

mycrobacterium [138]. Both RhB and quinacridone magenta (PR122) are used to make the

bright pink watercolor, known as opera rose [139]. Crystal violet (CV) is mostly released from

the effluents of textile, paint, medical and biotechnology industries into the aquatic environment.

Ingesting dyes by humans can cause an adverse effect on human health such as pain, vomiting,

skin irritation, severe headaches, acute diarrhoea, mutagenic, carcinogenic, mitotic, allergic

dermatitis and central nervous system illness [140-142]. Organic dye polluted water has been

treated by using various common technological treatment techniques such as condensation,

ultrafiltration, membrane separation, and adsorption [143, 144]. Nonetheless, these methods

often transfer organic pollutants to other phases and unable to completely degrade to nontoxic

substances [145-147]. During organic pollutants degradation, advanced oxidation processes

(AOPs) takes place with magnificent advantages, which have the potential to completely oxidize

organic compounds to CO2, H2O, and other inorganic substances [148-150]. During the past

decade, out of the AOPs photocatalytic degradation of organic dye pollutants using

semiconductor catalysts such as TiO2, ZnO, Fe2O3, Bi2WO6, H2WO4·H2O/Ag/AgCl, Ag2O, and

SrTiO3 have been examined extensively [151, 152].

Novel applications of nanoparticles and nanomaterials are growing rapidly on various fronts due

to their completely new or enhanced properties based on size, their distribution and morphology.

It is swiftly gaining renovation in a large number of fields such as health care, cosmetics,

biomedical, food and feed, drug-gene delivery [153], environment, health, mechanics, optics,

chemical industries, electronics, space industries, energy science, catalysis, light emitters, single

30
electron transistors, gas sensing [154, 155], nonlinear optical devices, CO2 capturing [156] and

photo-electrochemical applications [133], chemical and biological sensing [157]. These

biological synthesized nanomaterials have potential applications in different areas such as

treatment, diagnosis, development surgical nanodevices and commercial product manufacturing

[158].

Metal and semiconductor nanoparticles have great promising value in the emerging application

areas of nanoscience and technology. The reduction of materials to the nanoscale can frequently

alter their electrical, magnetic, structural, morphological and chemical properties, enabling them

to interact in unique ways with cell biomolecules and enabling their physical transport into the

interior structures of cells. Nanoscale particles typically possess a larger percentage of atoms at

the material‟s surface, which can lead to increased surface reactivity [129], and can maximize

their ability to be loaded with therapeutic agents to deliver them to target cells. Ag NPs are

particularly attractive because of their remarkable physico-chemical properties. For example,

their plasmonic response is extremely efficient because interband transitions are restricted to the

UV region, resulting in huge absorption coefficients and can generate intense electromagnetic

fields, which are useful for surface-enhanced spectroscopy [158]. Additionally, Ag NPs display

high electrical and thermal conductivity [159], catalytic activity [160], and non-linear optical

behavior [161]. They also possess strong bactericidal and fungicidal activity [162], which has

been extensively exploited in a range of consumer and pharmaceutical products such as soaps,

pastes, food, textiles, water filtration systems, antimicrobial paints, ointments and gels for topical

use, packaging paper for food preservation, fabrics for clinical clothing, bandages, cotton swabs,

and anticancer drugs [163].

31
Inexpensive and biological method of synthesis of protein capped Ag NPs by using aqueous

mycelial extract of Rhizopus stolonifer was reported by Nel A et al. [164]. Gudikandula et al.

[165] have synthesized Ag NPs using extracellular biosynthetic method from culture filtrate

extract of two white rot fungi which showed strong antimicrobial potential against gram-positive;

Bacillus subtilis (MTCC 441), Staphylococcus aureus (MTCC 96), Micrococcus luteus (KUCCC

4), Staphylococcus (KUCC 7) and gram-negative; Escherichia coli (MTCC 443), Pseudomonas

putida (KUCCC 12), Klebsiella pneumoniae (MTCC 109), Klebsiella aerogenes (MTCC 98)

afterwards. Arciniegas-Grijalba et al. [167] synthesized ZnO NPs by using sol-gel method in a

controlled and reproducible manner which demonstrated an antifungal effect on Erythricium

salmonicolor, a pathogen that causes the coffee crop disease known as pink disease. However,

cetyltrimethyl ammonium bromide (CTAB) which was used as surfactant during the synthesis

procedure is toxic if ingested by humans [167].

ZnO NPs have a range of applications to utilize in new light-emitting devices, solar cells,

biosensors, and photocatalysts [168, 169]. ZnO NPs show an extraordinary antibacterial property

due to its expanded specific surface area as the reduced particle size lead to enhanced particle

surface reactivity. The bio-safe material, ZnO can acquire photo-oxidizing and photocatalysis

impacts on chemical and biological species [169]. In comparision to ZnO NPs synthesized by

chemical means; green synthesized ZnO NPs show vigorous antibacterial effect at a very low

concentration [171, 172]. Nanoscale sized NPs can bring changes to the chemical, mechanical,

electrical, structural, morphological, and optical properties of NPs to interact in a unique manner

with cell biomolecules and hence encourage the physical exchange of NPs into the inner cellular

structures [173]. ZnO NPs has a broad-spectrum application such as, drug delivery, anticancer,

antidiabetic, antibacterial, antifungal and agricultural properties [174-177]. ZnO NPs are

32
considered as one of the effective futuristic water purification methods. Mishra et al. [178]

reported simple green routes for synthesis of Ag NPs using purified alpha amylase, aqueous leaf

extracts of ashoka and neem. The synthesized Ag NPs showed antiplasmodial activity with IC50

of 3.75, 8 and 30 μg/ml, respectively.

Cancer is a major public health problem in the world. Despite cancer patients have benefited

from the existed cancer therapy protocols, cancer therapy still remains great challenges. Because

of the great potential application of nanotechnology in cancer, cancer nanotechnology is

emerging as a new field of interdisciplinary research. Ag NPs and ZnO NPs showed potent

antidiabetic activity on male albino rats (experimental). Both nanoparticles induce a significant

reduced blood glucose, higher serum insulin, higher glucokinase activity higher expression level

of insulin, insulin receptor, GLUT2 and glucokinase genes in diabetic rats [179]. Similarly, in

other study, green synthesized Ag NPs and ZnO NPs showed potent anti-hyperglycemic

properties as compared to the Momordica charantia extract and CeO2 NPs and likewise

improved different entanglements of diabetes [180].

Therefore, the significance of this thesis is to develop an advanced, cost effective and

environmentally benign synthesis of nanoparticles and nanocomposite for the scope of

extraordinarily efficient water treatment technologies and health cure. In this dissertation

different nanomaterials such as Ag NPs, ZnO NS, Fe3O4 NPs and rGO/Fe3O4 nanocomposite are

synthesized for the application of water treatment, removal of organic dye pollutants via

photocatalytic degradation and batch adsorption techniques, bactericidal for both gram-positive

(Bacillus subtilis; Staphylococcus aureus) and gram-negative (Escherichia coli; Shigella

flexneri), anticancer activity against human liver cancer (Hep G2) and catalytic reduction of 4-

Nitrophenol (4-NP) to 4-Aminophenol (4-AP).

33
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