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Chapter 2 - Review of Literature
Chapter 2 - Review of Literature
2. REVIEW OF LITERATURE
2.1. NANOTECHNOLOGY
Nanotechnology is a multidisciplinary field, as it combines the knowledge from
different disciplines: chemistry, physics, and biology amongst others (Schmid, 2006;
Schmid, 2010). Nanotechnology is the art and science of manipulating matter at the
atomic or molecular scale and holds the promise of providing significant improvements
in technologies for protecting the environment. While many definitions for
nanotechnology exist, the U.S. Environmental Protection Agency (EPA) uses the
definition developed by the National Nanotechnology Initiative (NNI). According to
National Nanotechnology Initiative of the USA, nanotechnology is defined as: research
and technology development at the atomic, molecular, or macromolecular levels using a
length scale of approximately one to one hundred nm in any dimension; the creation and
use of structures, devices and systems that have novel properties and functions because of
their small size; and the ability to control or manipulate matter on an atomic scale
(USEPA, 2007). The technology has excellent prospects for exploitation across the
medical, pharmaceutical, biotechnology, engineering, manufacturing, tele-
communications and information technology markets.
2.2. HISTORY AND DEVELOPMENT OF NANOTECHNOLOGY
It is difficult to describe the history of nanotechnology which, according to R. D
Booker is due to two principal reasons: (1) Ambiguity of the term “nanotechnology” and
(2) Uncertainty of the time span corresponding to the early stages of nanotechnology
development. The term nanotechnology is explained by a wide spectrum of various
technologies that nanotechnology covers, which are based on various types of physical,
chemical and biological processes, realized at nanolevel.
The strictly established time span for the beginning of nanotechnology
development is explained by the fact that nanotechnology has its backgrounds in the
distant past when people used it without knowledge of it (Tolochko). The difference
between these ancient examples of “nanotechnology” and the current situation is the
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2.3. NANOPARTICLES
Nanotechnology is getting developed at several levels: materials, devices and
systems. The nanomaterials level is the most advanced at present, both in scientific
knowledge and in commercial applications (Salata, 2004). Nanoparticles are less than a
few 100 nm. This reduction in size brings about significant changes in their physical
properties with respect to those observed in bulk materials. They can be metallic, mineral,
polymer-based or a combination of materials (Rana and Kalaichelvan, 2013). Most of
these changes are related to the appearance of quantum effects as the size decreases, and
are the origin of phenomena such as the superparamagnetism, Coulomb blockade, surface
plasmon resonance, etc. The increase in the surface area to volume ratio is also a
consequence of the reduction in size. It leads to the appearance of surface effects related
to the high number of surface atoms, as well as to a high specific area, which are
important from the practical point of view (Salata, 2004).
2.4. PROPERTIES OF NANOPARTICLES
Once the particle size is reduced below 100 nm, the solid particles begin to
demonstrate unusual properties from the bulk material based on Quantum mechanics
(Bhusan, 2007). The surface related properties and the quantum properties play a
fundamental role in making the difference in the properties of the bulk material with that
of the nanoparticles (Roduner, 2006). They exhibit-
Size effects - Depending on the material used to produce nanoparticles, properties
like solubility, transparency, color, absorption or emission wavelength, conductivity,
melting point and catalytic behavior are changed only by varying the particle size.
Surface effects - Properties like dispersibility, conductivity, catalytic behavior
and optical properties alter with different surface properties of the particle.
If the surface properties are not controlled, nanoparticles quickly turn into larger
particles due to agglomeration. Most of the size dependent effects are then lost. For the
application of nanoparticles, it is therefore crucial to control their agglomeration
behavior. Dispersed nanoparticles are needed in order to retain their specific properties
for the technological applications as shown in (Plate 1) (Borm et al., 2006).
The nanoparticles exhibit various unique features like optical, structural, thermal,
mechanical and electromagnetic properties as described below.
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these building-block units into larger structures clearly the domain of chemistry (Borm et
al., 2006).
2.5.2. Applications of nanoparticles in Therapeutics, health and medicine
A confluence of nanotechnology and biology can address several biomedical
problems, and can revolutionize the field of health and medicine (Curtis and Wilkinson,
2001). Nanotechnology is currently employed as a tool to explore the darkest avenues of
medical sciences in several ways like imaging (Waren and Nie, 1998) sensing (Vaseashta
and Malinovska, 2005), targeted drug delivery (Langer, 2001) and gene delivery systems
(Roy et al., 1999) and artificial implants (Sachlos et al., 2006). Hence, nanosized organic
and inorganic particles are finding increasing attention in medical applications (Xu et al.,
2006) due to their amenability to biological functionalization. Based on enhanced
effectiveness, the new age drugs are nanoparticles of polymers, metals or ceramics,
which can combat conditions like cancer (Farokhzad et al., 2006) and fight human
pathogens like bacteria (Stoimenov et al., 2002; Sondi and Sondi, 2004; Panacek et al.,
2006; Morones et al., 2005; Baker et al., 2005).
Many nanoparticles like silver are useful as therapeutics due to their antimicrobial
properties. Polyisohexylcyanoacrylate nanoparticles, poly(lactic-co-glycolic acid)
(PLGA) nanoparticles, Gold nanoparticles, Chitosan nanoparticles, Cetyl
alcohol/polysorbate nanoparticles, Lipid nanocapsules, P (4-vinylpyridine) particles,
Chitosan-alginate nanoparticles, Poly (3-hydroxybutyrate-co-3 hydroxyoctanoate)
nanoparticles are some of the nanoparticles that can be effectively used for therapeutics
(Barraud et al., 2005; Cheng et al., 2010; Chithrani et al., 2010; Hee-Dong et al., 2010;
Koziara et al., 2004; Lamprecht et al., 2006; Ozay et al., 2010; Parveen et al., 2010;
Zhang et al., 2010).
Nanoparticles has also been modified for early detection of Alzheimer's disease
biomarkers in biological fluids as well as delivery of bioactive molecules directly to
brain.Although nanotechnology is expected to have a huge impact on the development of
“smart” drug delivery and devices against Alzheimer's disease, a crucial gap still to be
filled concerns the elucidation of its etiology, for which a great deal of effort is required
(Brambilla et al., 2011).
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concerns along with customer satisfaction have made functionally finished fabric a fast-
paced and fast growing industry. It soon became more important for antimicrobial
finished fabrics to protect the wearer from bacteria than it was to simply protect the
garment from fiber degradation (Yadav et al., 2006). The need for antimicrobial fabrics
goes hand-in-hand with the rise in resistant strains of microorganisms. Functional textiles
include everything from antimicrobial finished textiles, to durable, or permanent press
finished garments, to textiles with self-cleaning properties, and also textiles with
nanotechnology (Rajendran et al., 2010; El-Rafie et al., 2010). Coated antimicrobial
sutures have also been developed to aid fast would heal without microbial infection
(Dubas et al., 2011).
2.5.5.2. Dye and paint industries
Paint industries have also utilized the properties of nanoparticles. The appearance
and usefulness of nanoparticles brings many advantages and opportunities to paint and
coating industry. Addition of nanoparticles to coatings can upgrade many properties of
coating system and can produce multipurpose coatings with a little cost difference. They
have lots of advantages like, better surface appearance, good chemical resistance,
decrease in permeability to corrosive environment and hence better corrosion properties,
optical clarity, increase in modulus and thermal stability, easy to clean surface, anti-skid,
anti-fogging, anti-fouling and anti-graffiti properties, better thermal and electrical
conductivity, better retention of gloss and other mechanical properties like scratch
resistance, anti-reflective in nature, chromate and lead free, good adherence on different
type of materials (Khanna, 2008). Nanoparticles also aid in dye degradation and it has
been found that AgNPs are good, highly efficient and stable photocatalysts under ambient
temperature with visible light illumination for degrading organic compounds and dyes
(Wang et al., 2008).
2.5.5.3. Wastewater treatment
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,
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parasites and antibiotics. Basically four classes of nanoscale materials are being evaluated
as functional materials for water purification i.e., 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) (Tiwari et
al., 2008).
2.5.5.4. Energy/ Fuel cells/ Solar cells
Efficient production of solar fuels is an imperative for meeting future fossil-fuel-
free energy demands. Spencer et al., 2010 grafted light-harvesting molecules (polymer
coated gold nanoparticles where inorganic catalysts or light-harvesting porphyrin
molecules) to nanoparticles surfaces to make nanocells for the generation of fuel.
Nanoparticles when added to heat transfer fluids increase their performance. The solid
nanoparticles conduct heat better than the liquid. Nanoparticles work best because they
stay suspended in liquids longer than larger particles. They also have a much greater
surface area, which is where heat transfer takes place. The smaller the particle, the greater
is its ability to enhance heat transfer. Nano-additives, including nanoparticles and
nanopowder, could be utilized to enhance heat transfer from solar collectors to storage
tanks. Nanocrystalline nickel and metal hydrides have been investigated for use in
batteries. The nanostructured materials offer improvements regarding power density and
durability by controlling the charge diffusion and oxidation state on a nanoscale level.
Magnetic fluids, which have significant heat transfer capabilities when exposed to
magnetic fields, are being investigated as substitutes for existing coolants in transformers
for electrical supply (Strem Chemicals Inc., 2013).
2.6. METAL NANOPARTICLES
Metal nanoparticles are nanoparticles of metals like gold, silver, iron copper etc.
They are a focus of interest because of their huge potential in nanotechnology. Today
these materials can be synthesized and modified with various chemical functional groups
which allow them to be conjugated with antibodies, ligands, and drugs of interest and
thus opening a wide range of potential applications in biotechnology, magnetic
separation, and pre-concentration of target analytes, targeted drug delivery, and vehicles
for gene and drug delivery and more importantly diagnostic imaging (Mody et al., 2010).
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be sintered at a lower temperature. Also, as particles get smaller than the wavelength of
visible light, they not only become transparent but also emit special light by plasma
absorption. They show completely different electromagnetic or physicochemical
properties from their bulk counterparts, although they are made of the same materials.
AgNPs have attracted the attention of researchers because of their unique
properties, and proven applicability in diverse areas such as medicine, catalysis, textile
engineering, biotechnology, nanobiotechnology, bioengineering sciences, electronics,
optics, and water treatment. Moreover, AgNPs have significant inhibitory effects against
microbial pathogens, and are widely used as antimicrobial agents in a diverse range of
consumer products, including air sanitizer sprays, socks, pillows, slippers, respirators,
wet wipes, cosmetics, detergents, soaps, shampoos, toothpastes, air and water filters,
coatings of refrigerators, vacuum cleaners, bone cement, wound dressings, surgical
dressings, washing machines, food storage packaging, and cell phones. The flexibility of
silver nanoparticle synthetic methods and facile incorporation of AgNPs into different
media have interested researchers to further investigate the mechanistic aspects of
antimicrobial, antiviral and anti-inflammatory effects of these nanoparticles (Korbekandi
and Iravani, 2012).
2.7.2. Properties and Applications
AgNPs exhibit various properties and have been intensely used in various
applications. Given below are a important ones described in brief.
2.7.2.1. Antimicrobial activity
Silver is a metal known for its broad spectrum antimicrobial activity against Gram
positive and Gram negative bacteria, fungi, protozoa and certain viruses. The persistence
of antibiotic resistant bacteria has exploited the antimicrobial properties of silver and
silver-based compounds, including AgNPs (Nair and Laurencin, 2007). The mechanism
of cellular toxicity exhibited by metal nanoparticles is through the release of Reactive
Oxygen Species (ROS) (Nel et al., 2009). The antibacterial properties of AgNPs are
associated with its slow oxidation and liberation of Ag+ ions to the environment making it
an ideal biocidal agent. Moreover, the small size of these particles facilitates the
penetration of these particles through cell membranes to affect intracellular processes
from inside.
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dependent manner by the topical delivery of AgNPs. These NPs also exert positive
effects through their antimicrobial properties, reduction in wound inflammation and
modulation of fibrogenic cytokines.
2.7.3. Synthesis of silver nanoparticles
There are a large variety of methods that can be used to in the production of
nanoparticles, making use of techniques from both physics and chemistry. Among the
first ones, arc-discharge, high-energy ball milling, laser pyrolysis and laser ablation are
the most commonly used. Electrochemical and chemical vapor deposition, sonochemistry
and different wet chemistry routes (e.g. sol-gel, co-precipitation, inverse micelles, etc.)
are also widely employed (Melendi et al., 2008). With the development of new chemical
or physical methods, the concern for environmental contaminations is also heightened as
the chemical procedures involved in the synthesis of nanomaterials generate a large
amount of hazardous byproducts. Thus, there is a need for ‘green chemistry’ that includes
a clean, nontoxic and environment-friendly method of nanoparticle synthesis (Sharma et
al., 2007; Mukherjee et al., 2001). As an alternative to conventional methods, biological
methods are considered safe and ecologically sound for the nanomaterial fabrication
(Shankar et al., 2004a).
2.8. BIOSYNTHESIS OF SILVER NANOPARTICLES
In the chemically synthesized metal nanoparticles, the toxic chemicals and strong
reducing agents like sodium citrate which are involved in the synthesis process and
byproducts formed during the synthesis play a major role in producing the cytotoxic
effect (Seon et al., 2012). Capping agents or the stabilizing agents are reducing agents
like sodium citrate which gives more negative surface charge to the nanoparticles. This
negative surface charge also plays a pivotal role in the toxic effect of the chemically
synthesized gold nanoparticles (Seon et al., 2012). When the biologically synthesized
nanoparticles are considered and compared with that of chemically synthesized
nanoparticles, the cytotoxic effect is more for chemically synthesized nanoparticles
(Girilal, 2013). The least toxicity was observed for biologically synthesized silver
nanoparticles as it is a pure green synthesis method which does not involve the use of any
other toxic chemicals except corresponding metal halides like silver nitrate. Proteins and
enzymes play a major role in the biological synthesis process and these proteins also act
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nanoparticles synthesis is getting more popular because of the high reactivity of plant
extract and easy availability of plant materials. In a comparative in-vitro and in-vivo
toxicity study carried out by Girilal (2013), it has been concluded that biologically
synthesized AgNPs are less toxic to the chemically synthesized AgNPs. This method of
nanoparticles synthesis involves no toxic chemicals and has been termed as Green
chemistry procedure (Krishanaraj et al., 2012). An overview of various reports on AgNPs
synthesis by different plants is presented in (Table 1).
2.8.1. Mechanism of synthesis of biogenic silver nanoparticles
Synthesis of AgNPs using plant extracts is getting more popular (Li et al., 2007;
Song and Kim, 2009). Chandran et al. synthesized AgNPs by using the Aloe vera extract
at 24 h of incubation (Chandran et al., 2006). Similar study was carried out by Krishnaraj
et al, 2010 using leaf extracts of Acalypha indica. Interestingly, AgNPs were synthesized
rapidly within 30 min of incubation period. The aqueous silver nitrate solution was turned
to brown color within 30 min, with the addition of leaf extract. Intensity of brown color
increased in direct proportion to the incubation period (Krishnaraj et al., 2010).
The possible mechanism of biosynthesis of nanoparticles by biological system is
reductases and any other equivalent reductants as reported earlier (Shankar et al., 2004a).
The nitrate reductase from Fusarium oxysporum has been documented to catalyze the
reduction of AgNO3 to AgNPs utilizing NADPH as reducing agent Duran et al., 2005).
Several naphthoquinones and anthraquinones having very high redox potentials have
been reported from F. oxysporum that could act as an electron shuttle in metal reduction
(Newman and Kolter, 2000). Although such systems were not repeated in plant mediated
synthesis nanoparticles, the phytochemical constituents are attributed to the formation of
nanoparticles. Caffeine and theophylline present in tea extracts were also reported to
catalyze the synthesis of nanoparticles (Groning et al., 2001). Phyllanthin from
Phyllanthus amarus was also reported as the capping ligands in the synthesis of AgNPs
(Kasthuri et al., 2009). Quercetin and polysaccharides have been used for silver
nanoparticle synthesis (Egorova et al., 2000).
2.9. CHARACTERIZATION OF NANOPARTICLES
The technical application of nanoparticles mainly depends on their surface. It is
therefore crucial to the chemist to control the surface and thus the properties of single
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particles. However, the qualitative and quantitative analysis of the surface of a single
nanoparticle or a nanoparticle ensemble is challenging (Borm et al., 2006). The following
methods are employed to characterize the nanoparticles-
2.9.1. UV-Vis spectroscopy
The electronic structures of atoms, ions, molecules or crystals through exciting
electrons from the ground to excited states (absorption) and relaxing from the excited to
ground states (emission) are used for determination in UV-Vis spectroscopy. It deals with
the study of electronic transitions between orbitals or bands of atoms, ions or molecules
in gaseous, liquid and solid state (Jorgensen, 1962). Small metallic nanoparticles are
proven to have the property for absorption and scattering electromagnetic radiation. The
metallic nanoparticles are also known to exhibit different characteristic colors. The
absorption of electromagnetic radiation by metallic nanoparticles originates from the
coherent oscillation of the valence band electrons induced by an interaction with the
electromagnetic field (Faraday, 1857). These resonances are known as surface plasmons,
which occur only in the case of nanoparticles and not in the case of bulk metallic particles
(Papavassiliou, 1979). Hence, UV-Vis spectroscopy can be utilized to study the unique
optical properties of nanoparticles (Link and El-syed, 1999; Burda et al., 2000).
2.9.2. Fourier Transform Infrared (FT-IR) spectroscopy
In Fourier transform infrared spectroscopy, the vibrational technique involved is
the interactions of photons with species in a sample that results in energy transfer to or
from the sample via vibrational excitation or de-excitation is exploited for
characterization. These vibrational frequencies provide the information of chemical
bonds in the detecting samples. It deals with the vibration of chemical bonds in a
molecule at various frequencies depending on the elements and types of bonds. After
absorbing electromagnetic radiation the frequency of vibration of a bond increases
leading to transition between ground state and several excited states. These absorption
frequencies represent excitations of vibrations of the chemical bonds and thus are specific
to the type of bond and the group of atoms involved in the vibration. The energy
corresponding to these frequencies correspond to the infrared region of the
electromagnetic spectrum. The FT-IR measurement can be utilized to study the presence
of protein molecule in the solution, as the FT-IR spectra in the 1400 cm–1-1700 cm–1
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region provides information about the presence of –CO- and –NH- groups (Banwell and
McCash, 1996).
2.9.3. X-ray diffraction (XRD)
X-ray diffraction has been used to determine the crystal structure of solids,
including lattice constants and geometry, identification of unknown materials, orientation
of single crystals, defects, etc (Wang, 2000). The X-ray diffraction patterns are obtained
by measurement of the angles at which an X-ray beam is diffracted by the crystalline
phases in the specimen.
Bragg’s equation relates the distance between two hkl planes (d) and the angle of
diffraction (2θ) as:
nλ =2dsinθ,
where,
λ = wavelength of X-rays,
n = an integer known as the order of reflection
(h, k and l represent Miller indices of the respective planes) (Bragg and Bragg,
1949).
From the diffraction patterns, the uniqueness of nanocrystal structure, phase purity,
degree of crystallinity and unit cell parameters of the Nanocrystalline materials can be
determined.
X-ray diffraction technique is nondestructive and does not require elaborate
sample preparation, which partly explains the wide use of XRD methods in material
characterization. X-ray diffraction broadening analysis has been widely used to determine
the crystal size of nanoscale materials. The average size of the nanoparticles can be
estimated using the Debye–Scherrer equation:
D = kλ / βcosθ
where
D = thickness of the nanocrystal,
k is a constant,
λ = wavelength of X-rays,
β = width at half maxima of (111) reflection at Bragg’s angle 2θ (Rau, 1962;
Birks and Friedman 1946).
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1984) and antihelminthic activity (Kaleysa, 1974). The extracts of rhizomes have also
been used in the treatment of bronchitis, cough, respiratory ailments, diabetics, asthma
(Ramanayake and Visithuru, 1994) and arthritis (Ramanayake and Visithuru, 1994;
Arambewela et al., 1995). The rhizomes contain phytochemicals like polyphenols,
tannins, flavonoids, alkaloids, steroid glycosides that may act as reducing and stabilizing
agent in the green synthesis of biogenic AgNPs (Arambewela LSR and Arawwawala,
2010; Krishnaraj et al., 2010).
2.10.2. Antibacterial and antifungal activities of biogenic silver nanoparticles
Metal nanoparticles with bactericidal activity can be immobilized and coated on
to surfaces, which may find application in various fields, i.e., medical instruments and
devices, water treatment and food processing. Metal nanoparticles may be combined with
polymers to form composites for better utilization of their antimicrobial activity. The
antimicrobial properties of AgNPs are well-established (Sondi and Sondi, 2004; Kumar et
al, 2005; Jain and Pradeep, 2005; Cho et al., 2005) and several mechanisms for their
bactericidal effects have been proposed. The antimicrobial effects of metal nanoparticles
are attributed to their small size. Antimicrobial properties of silver and copper
nanoparticles were investigated using Escherichia coli (four strains), Bacillus subtilis and
Staphylococcus aureus (Ruparelia et al., 2008). In literature, lot of study has been done to
see the effect of AgNPs on bacteria (Lara et al., 2011; Illingworth et al., 2000; Lara et al.,
2010; Petrus et al., 2011; Ansari et al., 2011; Prakash et al., 2011; Egorova, 2011). Silver
and copper nanoparticles supported on various suitable materials, such as carbon,
polyurethane foam and polymers have also been effectively used for bactericidal
applications (Kumar et al, 2005; Jain and Pradeep, 2005).
Recently many reports clearly revealed the broad spectrum antibacterial activity
of AgNPs against both Gram positive and Gram negative bacteria including multi
resistant strains (Panacek et al., 2009). It is worth mentioning that AgNPs are performing
multiple modes of inhibitory action to microorganisms rather than single specific action
of antibiotics (Kim et al., 2008; Jo et al., 2009; Gogoi et al., 2006). Interestingly, AgNPs
are effective against Candida spp., Dermatophytes and a few phytopathogenic fungi
including Bipolaris sorokiniana and Magnapothe grisea [Panacek et al., 2006; Morones
et al.., 2005; Shrivastava et al., 2007). On the other hand, many phytopathogenic fungi
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are not explored although they are causing dreadful diseases on important crop plants and
thereby reducing the yield of agricultural products.
Hence the present study was aimed to determine the antibacterial activities of
biologically synthesized AgNPs against Gram positive and Gram negative bacteria and
antifungal activities against phyto-pathogenic fungi.
2.10.3. Application of biogenic silver nanoparticles on denim fabrics
In view of the textile industry's innovative history nanotechnology has found its
way into this sector quickly. The novel properties and low material consumption amount
has attracted global interest across disciplines and industries. The textile sector is no
exception (Rajendran et al., 2010). Clothing and textile materials are good media for
growth of microorganisms such as bacteria and fungi. According to recent reports,
microorganisms could survive on fabric materials for more than 90 days in a hospital
environment. Such a high survival rate of pathogens on medically used textiles may
contribute to transmissions of diseases in hospitals (Abdel-mohsen et al., 2012). These
textile materials have generated a considerable interest in the medical field where these
wide range of materials in the form of monofilament, multifilament, woven or nonwoven
structures are being used as sutures, bandages, scaffolds, wound dressing, masks, surgical
gowns and hospital linen, etc.
A lot of commercial medical textile products are available with antimicrobial
property wherein the growth of micro-organisms is controlled by treatment with
antimicrobial agents. Antimicrobial agents can also be integrated in textiles substrates to
make these rot proof, mildew stain proof and to prevent perspiration odor resulting from
microbial growth on textiles.The major classes of synthetic antimicrobial agents for
textiles include triclosan, metal and their salts, organometallics, phenols, quaternary
ammonium compounds and organosilicons, etc. (Purwar and Joshi, 2004). Antimicrobial
textiles using chitosan nanoparticles (Ali et al., 2011), ZnO nanoparticles (Rajendran et
al., 2010) AgNPs (Kulthong et al., 2010) etc are reported in the literature.
The current study was done to see the effect of AgNPs on denim fabrics. The
scope for denim wear is increasing tremendously every year and its worldwide market
share has increased unpredictably in the last few decades. Consumers’ needs are fine
tuned towards the latest developments and new styles; they are also aware of special
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finishes and process treatments given to the garment to make them eco-friendly and user
friendly (Sumithra and Raaja, 2012). The present study focuses on screening for the
antimicrobial activity of AgNPs and providing the denim fabric with antimicrobial finish.
2.10.4.Application of biogenic silver nanoparticles in photocatalytic dye
degradation
Textile dye effluents are dark in color having high BOD and COD content.
Besides these, other chemicals like caustic soda, mordant, soap etc are also present in
untreated dye effluent (Malviya et al., 2012). Dyes released from the textile processing
and dye stuff manufacturing industries result in an increase in organic load of natural
reservoirs. Generally, various dyes found in industrial effluents, ultimately, enter the
aquatic ecosystem and can create various environmental hazards (Gandhi et al., 2010).
The dyes are toxic and carcinogenic in nature and environmental contamination by these
toxic chemicals is emerging as a serious global problem. Colored solution containing
dyes from industrial effluents of textile, dyeing and printing industries may cause skin
cancer due to photosensitization and photodynamic damage (Kansal et al., 2008). The
chemical analysis of industrial waste water is essential to assess the degree of
environmental pollution or toxicity caused by the industrial effluents (Sarwar et al.,
2011). Currently textile effluents are treated by physicochemical methods that are often
quite expensive; in addition, these methods do not generally degrade the pollutants
thereby causing accumulation of dyes as sludge that creates a disposal problem
(Manikandan et al., 2012).
Physical and chemical methods of dye removal are effective only if the effluent
volume is small. This limits the use of physio-chemical methods, such as membrane
filtration and cucurbituril, to small-scale in situ removal. A limiting factor of these
methods is cost. This is true even in lab-scale studies, and methods, therefore, are unable
to be used by large-scale industry. Biological activity, in liquid state fermentations, is
incapable of removing dyes from effluent on a continuous basis. This is due to the time
period of a few days required for decolourisation-fermentation processes. In order for this
to be a viable option for industry, the dye-containing effluent must be held in large tanks
(Robinson et al., 2001). Sunlight is a natural energy source that is abundant and can be
exploited for degradation of dye effluent. Compared to other techniques, solar light was
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found to be faster in decolorizing dye in the presence of metal catalyst (Kansal et al.,
2008).
The acceleration of a chemical transformation in the presence of a catalyst with
light is called photocatalysis. The catalyst may accelerate the photoreaction by interaction
with the substrate in its ground or excited state and/or with a primary photoproduct,
depending upon the mechanism of the photoreaction and itself remaining unaltered at the
end of each catalytic cycle. The catalyst takes part in the redox reaction to form primary
oxidizing species in the photocatalytic oxidation processes-hydroxyl radical (¤OH) and
superoxide radical anions (O2¤-). These oxidative reactions would results in the
degradation of the pollutants as shown in the following oxidation of the pollutants via
successive attack by OH radicals
R + ¤OH → R’¤ + H2O
or by direct reaction with holes (Haque et al., 2012)
R + h+ → R¤+ → degradation products
Phaseolus vulgaris Linn. is a herbaceous annual plant grown worldwide. Brazil
and India are the largest producers of dry beans. Seed germination is a critical stage that
ensures reproduction and controls the dynamics of plant populations, thus it is a critical
test of probable crop productivity (Dash, 2012). This water is discharged from industries
directly into surrounding water bodies without any treatment and pollutes the water. This
water is again used for irrigation affecting the seed germination and overall growth of
plants (Sarwar et al., 2011).
In view of such perspectives, the present investigation was conducted to evaluate
the impact of photo catalytically degraded commercial textile dye effluent using biogenic
AgNPs.
2.10.5. Application of biogenic silver nanoparticles in wastewater treatment
An emerging technology for the abiotic degradation of recalcitrant compounds
involves the usage of zerovalent metal and bimetallic systems. Zerovalent metals have
been used for the reductive removal or transformation of organic compounds
(Vyjayanthi, 2012). 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
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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. It is suggested that these
may be used in future at large scale water purification (Tiwari et al., 2008).
Many studies have recently focused on using natural polymers as support for
catalyst preparation due to three important features: 1) formation of nanoparticles under
mild and eco-friendly conditions 2) certain supports themselves act as a reductant for the
conversion of metallic ions into their zerovalent forms 3) the resulting bio-inorganic
catalyst can be easily separated from the reaction medium which promotes its reusability
(Vyjayanthi, 2012). As per literature, studies have already been done to see the effect
pollutant treatment by chitosan hollow fibres and beads (Guibal 2005, Liu et al., 2010),
calcium alginate bead (Saha et al., 2010), Cobalt and Nickel nanoparticles inside poly (2-
acrylamido-2-methyl-1-propansulfonic acid) (p(AMPS)) hydrogel (Sahiner et al., 2010)
etc.
The focus in the current research is to incorporate biogenic AgNPs in calcium
alginate beads for the reductive remediation of recalcitrant pollutants.
2.10.6. Phytotoxic effects of biogenic silver nanoparticles on plants
Although nanotechnology is quite a recent discipline, there have already high
number of publications which discuss this topic. However, the safety of nanomaterials is
of high priority. Whereas toxicity focuses on human beings and aims at protecting
individuals, ecotoxicity looks at various trophic organism levels and intend to protect
populations and ecosystems. Ecotoxicity includes natural uptake mechanisms and the
influence of environmental factors on bioavailability (and thereby on toxicity) (Rana and
Kalaichelvan, 2013). Nanomaterials end up in the environment, that is, in water,
sediments, and soil (Oberdorster, 2004).
Phytotoxicity of nanoparticles has been demonstrated for Zn and ZnO as
inhibition of seed germination and root growth after 2 hr exposure to nanoparticle
suspensions in deionized water (Lin and Xing, 2007). Five types of nanoparticles
(multiwalled carbon nanotubes, aluminum, alumina, zinc, and zinc oxide) and six plant
species (radish, rape, ryegrass, lettuce, corn, and cucumber) were screened. Fifty percent
inhibition of root growth (the most sensitive parameter) was observed for nano-Zn and
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nano-ZnO at approximately 50mg/L for radish, and about 20 mg/ L for rape and ryegrass
whereas other nanoparticle-plant combinations showed weaker inhibition. Results have
shown that pure alumina particles significantly reduce the root elongation in all plant
species, thus potentially slowing the plants’ growth.
Nanoparticles in plants enter cellular system via roots and stomata, effect
transpiration, plant respiration, and photosynthesis, and interfere with translocation of
food material. The degree of toxicity is linked to this surface and to the surface properties
of these nanoparticles, rather than their mass. Hence, the most urgent needs for research
related to environmental impact of nanoparticles are to establish the degree of
environmental mobility and bioavailability. These parameters will decide whether
nanoparticles can be taken up and cause harm to various organisms especially plants
(Rana and Kalaichelvan, 2013).
Trigonella foenumgraecum Linn. (Fenugreek) is a legume, originally from
southeastern Europe and western Asia, but grown now mainly in India and also in certain
parts of Asia, northern Africa, Europe and the United States (Altuntas et al., 2005). It is a
winter season crop and grows well in low temperature. Fenugreek seeds are traditionally
used for the treatment of many diseases. Studies show that the seeds have antioxidant
properties. Many medicinal properties are attributed to fenugreek seeds and leaves
(Srinivasan, 2006). Fenugreek is known to have several pharmacological attributes such
as hypoglycaemic (Sharma and Raghuram, 1990; Zia et al., 2001), hypercholesterolaemic
(Stark and Madar, 1993; Srinivasan, 2006), gastroprotective (Suja Pandian et al., 2002),
chemo-preventive (Amin et al., 2005), antioxidant (Hettiarachchy et al., 1996;
Kaviarasan et al., 2007), laxative (Riad and El- Baradie, 1959) and appetite stimulation
(Petit et al., 1993). The plant is known to contain alkaloids (Jain and Madhu, 1988),
flavonoids (Kamal and Yadav, 1991), salicylate (Swain et al., 1985), and nicotinic acid
(Rajalaksmi et al., 1964).
There are reports of metal stress on this plant like lead and cadmium (Suganthi et
al., 2013; Swamy et al., 2011). Girilal (2013) showed that biogenic AgNPs showed lesser
toxicity when compared to chemically synthesized AgNPs in Solanum lycopersicum.
However, there are no reports on phytotoxic effect of bioaccumulation of biogenic
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AgNPs. Hence the current research was carried out to see the phytotoxic effects of
AgNPs on Trigonella foenumgraecum Linn. using biogenic AgNPs.
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