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Rawat et al.
Review Article
Article Received on
09 May 2016,
ABSTRACT
Nanoparticles are the spearheads of the rapidly expanding field of
DOI: 10.20959/wjpps20167-7227
*Corresponding Author
Mohit Rawat
Assistant Professor,
Department of
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Graphical Abstract
INTRODUCTION
Nanotechnology can be defined as the understanding of phenomena and manipulation of
matter of matter at the atomic, molecular or macromolecular levels at dimensions between
approximately 1100 nanometer. Due to its small size, it produces structures, devices, and
systems with atleast one novel/superior characteristic property. These properties may differ in
important ways from the properties of bulk materials and single atoms and molecules.
Currently, there are two main approaches for the synthesis of nanomaterials and fabrication
of nanostructure: top down and bottom up approaches.
Top-down approach is a physical method and also refers to microfabrication method where
tools are used to cut, mill and shape materials into the desired shape and order. Integrated
circuits is an example. It include preparation by lithographic techniques, etching, grinding in
a ball mill, sputtering, etc. However, the most acceptable and effective approach for
nanoparticle preparation is the bottom up approach, where devices are grown from
smaller building blocks such as atoms or molecules by self assembly. In this way, it is
possible to control the size and shape of the nanoparticle depending on the subsequent
application through variation in precursor concentrations, reaction conditions (temperature,
pH, etc.), functionalizing the nanoparticle surface, using templates, etc. Thus, it produces
products with high precision accuracy. Colloidal dispersion is an example.
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Figure 1: Top-down and Bottom-up synthesis approaches. Reprinted from Sci. Tot.
Environ., Vol. 400 (1-3), Ju-Nam, Y. and Lead, J.R., Manufactured nanoparticles: An
overview of their chemistry, interactions and potential environmental implications,
pp396-414, Copyright 2008 with permission from Elsevier.
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Rawat et al.
highest electrical conductivity(higher than copper that is currently used in many electrical
applications)
thermal conductivity
Silver is stable in pure air and water. The presence of ozone or hydrogen sulfide or sulfur in
the air or water may result in silver tarnishing[5] due to the formation of silver sulfide. Silver
can be present in four different oxidation states: Ag 0, Ag2+, Ag3+. The former two are the
most abundant ones, the latter are unstable in the aquatic environment.[6] Silver has many
isotopes with
107
environment is dependent on the availability of free silver ions, investigations have shown
that these concentrations of Ag+ ions are too low to lead toxicity.[7] Metallic silver appears to
pose minimal risk to health, whereas soluble silver compounds are more readily absorbed and
have the potential to produce adverse effects.[8] The reduction in the size of silver to
nanosized silver increases its ability to control bacteria and fungi. Due to the large surface
area of nanomaterials leads to increased contact with bacteria and fungi which increases its
effectivity. Nanosilver, when in contact with bacteria and fungus, adversely affects the
cellular metabolism of the electron transfer systems and the transport of substrate in the
microbial cell membrane. Bacteria and fungi causes itchiness, infection, odor, sores, the use
of nanosilver repress the proliferation of bacteria and fungi. Nanosilver have been widely
used due to its antibacterial microbial activity for the development of products containing
siver include food contact materials (such as cups, bowls and cutting boards), odor-resistant
textiles, electronics and household appliances, cosmetics and personal care products, medical
devices, water disinfectants, room sprays, childrens toys, infant products and health
supplements.
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References
Patent [32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
Industrial Applications
Catalysis
The silver nanomaterials and silver nanocomposites are used as catalyst in many such as CO
oxidation, benzene oxidation to phenol, photodegradation of gaseous acetaldehyde and the
reduction of the p-nitrophenol to p-aminophenol.[41] To catalyze the reduction of dyes by
sodium borohydride (NaBH4), silver nanoparticles immobilized on silica spheres[42] etc.
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Electronics
Nanosilver has high electrical and thermal conductivity along with the enhanced optical
properties leads to various applications in electronics. In nanoelectronics, silver nanowires
are used as
optoelectronics,
Other
applications
include),
connectors), data storage devices, the preparation of active waveguides in optical devices
high density recording devices, intercalation materials for batteries, making microinterconnects in integrated circuits (IC) and integral capacitors etc.
Plant Extract Mediated Green Synthesis of Silver Nanoparticles
There is growing imposition of silver nanoparticles in the field of medicine, optics,
biotechnology, microbiology, environmental remediation and material science has lead to
increasing demand in chemical industry. For the production of silver nanoparticles, various
reducing agents are reported such as H2 gas[44], sodium borohydride[45], hydrazine[46],
ethanol[47], ethylene glycols[48], Tollens reagent[49], ascorbic acid[50] and aliphatic amines.[51]
Depending on the strength of the reducing agents the particle size can be controlled. Hence
umpteen number of toxic chemicals have been utilized to blend the silver nanoparticles as a
reducing and stabilizing agent and poly (ethylene glycol) block copolymers are used to
reduce the Ag+ ions into Ag nanoparticles in aqueous or non- aqueous solution. Although
these methods may successfully manufacture the well defined nanoparticles but they are quiet
expensive and dangerous to environment. Thus, the concept of green chemistry was
introduced to nanoparticles synthesis with the elimination or decline tradition of toxic
chemicals. In previous study, plants and herbs antioxidant are present as a phytochemical
constituents in seeds, stems, fruits and in leaves. The plant-based phytochemicals in the
synthesis of nanoparticles creates a meaningful symbiosis between natural/plant science and
nanotechnology. This connection provides a green approach to nanotechnology, referred to as
green nanotechnology or Green Synthesis. The major foredeal of using plant extracts for
silver nanoparticle preparation is that they are easily available, safe and nontoxic in most
cases, have a broad variety of metabolites that can aid in the reduction of silver ions and
quicker than microbes in the synthesis. The main mechanism considered for the route is
plant-assisted reduction due to phytochemicals. The main phytochemicals involved are
terpenoids, flavones, ketones, aldehydes, amides and carboxylic acids. Flavones, organic
acids and quinones are water-soluble phytochemicals that are responsible for the instant
reduction of the ions and formation of nanoprticles. Studies have revealed that xerophytes
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Figure 4: Ascorbic acid reduction mechanism of gold and silver ions to obtain Ag0 and
Au0 nanoparticles.
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Size(nm)
50100
31.83
25
2090
1628
22
717
1050
840
13
32
0.5
1030
1945
3050
2050
100110
16.4
1020
5 & 1030
35
<60
1030
>80
87, 99.8
50
20
57
35
3560
2580
2030
422
50350
1035
50150
2050
2580
1640
2550
3040
Plantss part
Leaves
Rhizome
Whole plant
Leaves
Fruit
Inflorescence
Leaves
Seeds
Leaves
Leaves
Leaves
Leaves
Leaves
Plant
Leaves
Seeds
Seeds
Leaves
Leaves
Leaves
Leaves
Leaves
Latex
Leaves
Seeds
Leaves
Peel
Leaves
Leaves
Leaves
Leaves
Leaves
Leaves
Leaves
Peel
Peel
Leaves
Leaves
Leaves
Leaves
Fruit
Shape
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical
Spherical & fcc
Spherical
Spherical
-
References
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
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Boerhaavia diffusa
Tea
Tribulus terrestris
Cocous nucifera
Aloe vera
Solanus torvum
Trianthema decandra
Argimone mexicana
Abutilon indicum
Cymbopogan citratus
Test microorganisms
Escherichia coli, Pseudomonas
aeruginosa, Klebsiella pneumonia
and Enterococcus faecalis
Aeromonas hydrophila, Pseudomonas
fluorescens and Flavobacterium
branchiophilum
E. coli
Streptococcus pyogens, Pseudomonas
aeruginosa, Escherichia coli, Bacillus
subtilis and Staphylococcus aureus
Klebsiella pneumoniae, Bacillus
subtilis, Pseudomonas aeruginosa and
Salmonella paratyphi
E. coli
P. aeruginosa, S. aureus, A. flavus
and Aspergillus niger
E. coli and P. aeruginosa
Escherichia coli; Pseudomonas
aeruginosa; Aspergillus flavus
S. typhi, E. coli, S. aureus and B.
substilus
P. aeruginosa, P. mirabilis, E. coli,
Shigella flexaneri, S. somenei and
Klebsiella pneumonia
Method
References
[93]
[94]
[95]
Kirby-Bauer
[96]
[97]
[98]
Disc diffusion
[99]
Disc diffusion
Disc diffusion for
bacteria and food
poisoning for fungi
[100]
[101]
[102]
Disc diffusion
[103]
Literature Review
Green Synthesis of Silver nanoparticles using plant extract is a very simple and costeffective way that satisfies the demand of research community and eliminates the possibility
of environment hazards simultaneously. Till date several groups had reported the synthesis of
silver nanoparticles using plant extract which are listed in Table 2. such as bioreduction of
silver ions to yield metal nanoparticles with the help of living plants, geranium, Neem leaf,
Aloevera plant extracts, Emblicaofficinalis (amla, Indian Gooseberry. The green synthesis of
silver nps using Capsicum annuum leaf extract has been reported. These biogenic silver
nanoparticles show high antimicrobial activity against gram-positive and gram-negative
bacteria. Table 3.
In a recent report, these nanoparticles have been synthesized on irradiation using an aqueous
mixture of Ficuscarica leaf extract.[104] The silver nanoparticles were formed after three hour
of incubation at 370C using aqueous solution of 5mM silver nitrate. Cymbopogan citratus
(DC) stapf (commonly known as lemon grass) a native aromatic herb from India and also
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cultivated in other tropical and subtropical countries showed strong antibacterial effect
against P. aeruginosa, P. mirabilis, E. coli, Shigella flexaneri, S. Somenei and Klebsiella
pneumonia.[105] Many plants such as Pelargonium graveolens[106], Medicagosativa[107],
Azadirachta indica[108], Lemongrass[109], Aloevera[110], Cinnamomum Camphora[111], Emblica
officinalis[112], Capsicum annuum[113], Diospyros kaki[114], Caricapapaya[115], Coriandrum
sp.[116], Boswellia ovalifoliolata[117], Tridax procumbens, Jatropha curcas, Solanum
melongena, Datura metel, Citrus aurantium[118] and many weeds[129,120] have shown the
potential of reducing silver nitrate to give formation of AgNPs.
The bio-synthesis of silver nanoparticles from a silver nitrate solution using two medicinal
plant extract namely Ocimum tenuiflorum(Ag NP1) and Catharanthus roseus(Ag NP2)
has been reported by Dulen Saikia.[121] The plant leaf extracts were prepared by mixing 5 g
of dried leaves in 100 ml of deionized water in an Erlenmeyer flask, boiled for 30 minutes at
desired temperature and then filtered through a Whatman 42 no. filter paper. In a typical
reaction, 9 mL of the leaf extracts was added to the desired amount of aqueous AgNO 3
solution (110 -3 mol dm-3, 210 -3 mol dm-3, 310-3 mol dm-3, 410-3 mol dm-3 and 510 -3 mol
dm-3 AgNO3) and the reaction mixture was left at room temperature for the reduction process
to take place. When the leaf extract was mixed in the aqueous solution of the silver ion
complex, it started to change colour (within 30 minutes) from brown to reddish brown.
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Figure 6: Colour change of AgNO3 solution with the change in concentration of AgNO3
solution (1mM to 5mM) containing Ocimum tenuiflorum leaf extract; (b) Colour
change of AgNO3 solution with the change of concentration of AgNO3 solution (1mM to
5mM) containing Catharanthus roseus leaf extracts; (c) UV-Vis absorption spectra of
AgNP1 using different concentrations of aqueous AgNO3 solution; (1) 110-3 mol dm-3,
(2) 210-3 mol dm-3, (3) 310-3 mol dm-3, (4) 410-3 mol dm-3, (5) 510-3 mol dm-3; (d) UVVis absorption spectra of AgNP2 using different concentrations of aqueous AgNO3
solution; (1) 110-3 mol dm-3, (2) 210-3 mol dm-3, (3) 310-3 mol dm-3, (4) 410-3 mol dm3
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Figure 9: Optical image. (A) Gradual colour change for the formation of AgNPs by 7%
of O. sanctum leaf extract at different time intervals. (B) AgNPs formation with O.
sanctum leaf extract at different concentrations (10%, 7%, 5% and 3%) measured at 60
min.
Figure 10: (a) UV-visible spectra for different concentrations of O. sanctum Linn. leaf
extract (PLE) with 103M AgNO3 measured at 60 min. (b) UV-visible spectra of 7%
aqueous leaf extract (PLE) of three different plants (Curve A) Ocimum sanctum Linn.
(Curve B) Citrus limon L (Curve C) Justicia adhatoda L with 103 M AgNO3
measured at 60 min.
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Figure 11: (a) TEM image of biosynthesized silver nanoparticles using O. sanctum leaf
extract at 100 nm scale (b) Effect of the treatment of actively growing cells. With AgNPs
(dispersed in the aqueous leaf extract) formed by 7% leaf extracts of O. Sanctum on
growth pattern of Staphylococcus aureus [() for untreated and () for treated]
and Pseudomonas aeruginosa [() for untreated and () for treated]. All
values are means of three sets of experimental data.
In one more study, the Green Synthesis of Silver nanoparticles by Mulberry Leaves Extract
has been reported by Akl M. Awwad1, Nid M. Salem[123] by utilizing the reduced property
of mulberry leaves extract and silver nitrate to synthesize a silver nanoparticles (Ag NPs) at
room temperature and characterized by using UV-visible absorption spectroscopy, scanning
electron microscopy (SEM) and X-ray diffraction (XRD). Further, silver nanoparticles
showed effective antibacterial activity toward Staphylococcusaureus and Shigella sp.
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Figure 12: (a) Effect of contact time on AgNPs synthesised by mulberry leaves extract
(b) FT-IR spectra of Mulberry leaves powder.
Figure 13: (a) XRD pattern of AgNPS synthesized by mulberry leaves extract (b) SEM
image of silver nanoparticles.
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Figure14: Activity of silver nanoparticles against: (a) Staphylococcus aureus and (b)
Shigella sp.
DISCUSSION
It was found that the average size of silver nanoparticles was 20 2.8 nm that was calculated
by using Debye-Scherer equation. The presence of structural peaks in XRD patterns and
average crystalline size around 20nm clearly illustrates the crystalline nature of AgNPs.
The SEM image of silver nanoparticles, showed cubical and relatively uniform shape of
nanoparticle formation with diameter range 20-40 nm. The larger silver particles may be due
to the aggregation of the smaller ones.
In this study, Banerjee et al.[124], proposed a Leaf extract mediated green synthesis of silver
nanoparticles from widely available Indian plants: Musa balbisiana (banana), Azadirachta
indica (neem) and Ocimum tenuiflorum (black tulsi) and their synthesis, characterization,
antimicrobial property and toxicity analysis. This study investigates an efficient and
sustainable route of AgNP preparation from 1mM aqueous AgNO3 using leaf extracts of
three indian plants. The Ag NPs were characterized by UV-visible spectrophotometer,
particle size analyzer (DLS), scanning electron microscopy (SEM), transmission electron
microscopy (TEM) and energy-dispersive spectroscopy (EDS), Fourier transform infrared
spectrometer (FTIR) to determine the nature of the capping agents in each of these leaf
extracts. Ag NPs showed significantly higher antimicrobial activities against Escherichia coli
(E. coli) and Bacillus sp. in comparison to both AgNO3 and raw plant extracts. Additionally,
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a toxicity evaluation of these Ag NPs containing solutions was carried out on seeds of Moong
Bean (Vigna radiata) and Chickpea (Cicer arietinum). Results depicts the treatment of seeds
with Ag NPs solutions exhibited better rates of germination and oxidative stress enzyme
activity (nearing control levels), though detailed mechanism of uptake and translocation are
yet to be analyzed.
Figure 15: UVVis absorption spectrum of silver nanoparticles. From (A) banana, (B)
neem and (C) Tulsi leaf extracts.
Figure 16: Graphs obtained from FTIR analysis of AgNPs. Curve: (A)- Banana, (B)Neem and (C)- Tulsi leaf extracts respectively.
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Figure 18: TEM images of silver nanoparticles formed by the reaction of 1 mM silver
nitrate and 5% leaf extract of (A) banana. (B) neem and (C) tulsi leaves respectively.
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CONCLUSION
As metal nanoparticles seems to fascinate for the future diverse industry due to their enrich
chemical, electrical and physical properties. Metal nanoparticles are synthesized
predominantly by wet chemical methods, where the chemical used are toxic and flammable.
So there is need of eco friendly nanoparticles synthesis approach. Green nanotechnology
accomplish this need by synthesize the metal nanoparticles without using any toxic chemical
as a reducing agent. Plant extract mediated biological synthesis of nanoparticles is known as
Green Synthesis or Green Nanotechnology and these nanoparticles are known as biogenic
nanoparticles. Green synthesis provides benefits over chemical and physical method as it is
cost effective. eco friendly, more stable and there is no need any high energy, pressure,
temperature and toxic chemicals.
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