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Short Views on Insect Biochemistry and Molecular Biology Vol.(2), October 2014

2014

Section VI
Insect Molecular Biology

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Vol. (2) 473 496, 2014

Chapter 21

Green protocol for synthesis of metal nanoparticles to control insect pests

K. Murugan1*, R. Chandrasekar2, C. Panneerselvam1, A. Naresh Kumar1,


P. Madhiyazhagan1, P. Mahesh Kumar1, Jiang-Shiou Hwang3, Jiang Wei4

1
Department of Zoology, Bharathiar University, Coimbatore-641046, India.
Department of Biochemistry & Molecular Biophysics, Kansas State University,
Manhattan, KS 66506, USA.
3
Institute of Marine Biology, National Taiwan Ocean University, Keelung 20224, Taiwan
4
Department of Microbiology, College of Biological Sciences, China Agricultural University,
Beijing 100094, China.
2

Abstract

Biosynthesis of metallic nanoparticles is a novel research area of nanotechnology which has


economic and environmental friendly advantages over conventional chemical and physical
methods of synthesis. Biological methods were used to synthesize metal nanoparticles of
specific shape and size by enhancing the properties of nanoparticles in a safer route.
Biosynthesis of nanoparticles may be triggered by several compounds such as carbonyl groups,
terpenoids, phenolics, flavonones, amines, amides, proteins, pigments, alkaloids and other
reducing agents present in the biological compounds. Silver (Ag) and gold (Au) nanoparticles
have been the particular focus of plant-based synthesis. The plant extract based synthesis can
provide nanoparticles of a controlled size and morphology. Owing to the rich biodiversity of
plants in India, their potential use towards the synthesis of these nobel metal nanoparticles is yet
to be explored. The aim of this review is to provide the potential to use of nanoparticle surfaces
to kill insects and vectors with specifically vectors to human pathogens.

Key words: Silver, Gold, Phytosynthesis, Anopheles stephensi, Culex quinquefasciatus, Aedes aegypti,
*For Correspondence (email:

kmvvkg@gmail.com)

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Overview
1. Introduction
1.1. Vector-Borne Disease
1.1.1. Malaria
1.1.2. Dengue
1.1.3. Lymphatic filariasis
2. Nanotechnology
3. Types of nanoparticles
4. Characterization of nanoparticles
5. Biological synthesis of silver nanoparticles
6. Biosynthesis of metal nanoparticles by plants
6.1. Silver Nanoparticles
6.2. Gold Nanoparticles
7. Larvicidal activity of metal nanoparticles on human pest
8. Conclusion
9. References

1. Introduction
Vector mosquitoes are capable of transmitting potential pathogens to human
beings, and they are responsible for several infectious diseases like malaria, filariasis,
Japanese encephalitis, yellow fever, dengue, and Chikungunya (1). They have,
therefore, become a challenging problem to public health worldwide, and it has a
serious social and economical impact especially in tropical and subtropical countries
(2). Mosquito-borne diseases are endemic over 100 countries, causing mortality of
nearly two million people every year, and at least one million children die of such
diseases each year, leaving as many as 2,100 million people at risk around the world
(3, 4, 5). There is an urgent need to check the proliferation of the population of vector
mosquitoes in order to reduce vector-borne diseases by appropriate control methods
(6). Vector control is an essential and effective means for controlling transmission of
vector-borne diseases, especially in areas where resistance in parasite to drugs is
growing. Unlike insecticides, bio-control agents are host specific, safer to the
environment, find easy application in the field, are cost-effective in production, lack
infectivity and pathogenicity in mammals including man and has little evidence of
resistance development in target mosquito species. Many populations of mosquito
vectors of diseases have developed resistance to synthetic organic insecticides, used
mostly during the last half of the 20th century. Thus interest in alternate strategies as
well as in integrated control grew increased (7, 8, 9). Since single method of control is
ineffective to produce the desired results, emphasis should be laid on the
comprehensive mosquito control strategies including the use of insecticides,
bio-control agents and environmental management. In this chapter we highlighted
about the biosynthesis of silver and gold nanoparticles for the management of human
pest.This prompts intensive research and studies to give more insights for development
of effective method/s for vector control.
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1.1. Vector-Borne Disease


1.1.1. Malaria
Malaria is the most prevalent among the insect-borne diseases. Every year, it kills
between one and two million people with as many as 300500 million people being
infected. It is estimated that nearly half of the world population is at risk with fatality
rates being extremely high among young children below 5 years of age. Malaria is a
classical example of a disease that affects the productivity of individuals, families, and
the whole society. It is common in the poorer and less-developed countries of the
world. Africa faces its greatest impact and the other hard-hit tropical areas include East
Asia, China, and India (10, 11). Currently, resistant varieties of the malarial parasite are
commonly observed in almost all parts of the world where malaria is endemic (12).The
increased drug resistance continues to be a major issue, with ongoing problems related
to drug quality, availability and cost to treat the disease (13). So, the transmission of
malaria is best reduced by the control of vector mosquito. Among 53 Anopheline
species present in India, nine are vectors of malaria. Anopheles stephensi is responsible
for transmission of malaria in urban regions of India (14). In India, malaria is still the
most important cause of morbidity and mortality with approximately two to three
million new cases arising every year (15).
1.1.2. Dengue
Dengue is a vector-borne disease of tropical and subtropical human populations,
which occurs predominantly in urban areas. Dengue is transmitted by Aedes
mosquitoes that breed in container habitats. The main vector Aedes aegypti is a
cosmotropical species that proliferate in water containers in and around houses.
Secondary vectors include Aedes albopictus , an important vector in Southeast Asia
and that has spread to the America, Western Africa, and the Mediterranean rim; Aedes
mediovittatus in the Caribbean; and Aedes polynesiensis and Aedes scutellaris in the
western Pacific region. Aedes aegypti breeds in many types of household containers,
such as water storage jars, drums, tanks, and plant or flower containers (16, 17, 18).
The World Health Organization (W.H.O) estimates that around 2.5 billion people are at
risk of dengue. Infections have dramatically increased in recent decades due to
increased urbanization, trade, and travel. No effective drug or vaccine is available so
far. The only solution is to prevent the disease-carrying mosquito from breeding and
biting humans. Dengue is the most important mosquito spread viral disease and a major
international public health concern. It is a self limiting disease found in tropical and
subtropical regions around the world, predominantly in urban and semi-urban areas.
DF or DHF is caused by dengue virus which belongs to genus Flavivirus, family
Flavivirus and includes serotypes 1, 2, 3, and 4 (Den-1, Den-2, Den-3 and Den-4) (19).

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1.1.3. Lymphatic filariasis


Lymphatic filariasis is a mosquito-borne disease caused by mosquito-transmitted
filarial nematodes, including Wuchereria bancrofti and Brugia malayi. The infected
people carry the nocturnally periodic W. bancrofti, which has Culex quinquefasciatus
as the main mosquito vector. C. quinquefasciatus is a vector of lymphatic filariasis,
which is a widely distributed tropical disease with around 120 million people infected
worldwide and 44 million people have common chronic manifestation (20).
C. quinquefasciatus is a predominant house-resting mosquito in many tropical
countries. It is important as a vector of filariasis in some countries as well as a nuisance
mosquito. Mosquitoes breed in polluted waters such as blocked drains, damaged septic
tanks, or soak age pools close to human habitations. According to WHO, about 90
million people worldwide are infected with W. bancrofti, the lymphatic dwelling
parasite, and ten times more people are at the risk of being infected. In India alone, 25
million people harbor micro- filaria and 19 million people suffers from filarial disease
mani- festations (21, 22).

2. Nanotechnology
Nanotechnology operates at the first level of organization of atoms and molecules
for both living and anthropogenic systems. This is where the properties and functions
of all systems are defined. Such fundamental control promises a broad and a
revolutionary technology platform for industry, biomedicine, environmental
engineering, safety and security, food, water resources, energy conversion, and
countless other areas.
Nanoscience is, at its simplest, the study of the fundamental principles of
molecules and structures with at least one dimension roughly between 1 and 100
nanometers. These structures are known, perhaps uncreatively, as nanostructures.
Nanotechnology is the application of these nanostructures into useful nanoscale
devices. That isnt a very fulfilling definition, and it is certainly not one that seems to
explain the hoopla. To explain that, its important to understand that the nanoscale isnt
just small, its a special kind of small. Nanoscience has been established recently as a
new interdisciplinary science. It can be defined as a whole knowledge of the
fundamental properties of nano-size objects (23, 24, 25). The term nano is adapted
from the Greek word meaning dwarf. When used as a prefix, it implies 109.
A nanometer (nm) is one billionth of a meter, or roughly the length of three atoms side
by side. A DNA molecule is 2.5 nm wide, a protein approximately 50 nm, and a flu
virus about 100 nm. A human hair is approximately 10,000 nm thick. A nanoparticle is
a microscopic particle with at least one dimension less than 100 nm.
The results of Nanoscience are realized in nanotechnology as new materials and
functional facilities. At the present time nanochemistry becomes one of the main
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growing directions of nanoscience (25). Frequently, nanometer-sized metallic


particles show unique and considerably changed physical, chemical and biological
properties compared to their macro scaled counterparts, due to their high
surface-to-volume ratio. Thus, these nanoparticles have been the subject of
substantial research in recent years (26).
Synthesis of noble metal nanoparticles for applications such as catalysis,
electronics, optics, environmental, and biotechnology is an area of constant interest
(27, 28, 29, 30, 31). Gold, silver, and copper have been used mostly for the synthesis of
stable dispersions of nanoparticles, which are useful in areas such as photography,
catalysis, biological labeling, photonics, optoelectronics and surface-enhanced Raman
scattering (SERS) detection (32, 33). Additionally, metal nanoparticles have a surface
plasmon resonance absorption in the UVVisible region. The surface plasmon band
arises from the coherent existence of free electrons in the conduction band due to the
small particle size (34, 35, 36).The band shift is dependent on the particle size,
chemical surrounding, adsorbed species on the surface, and dielectric constant (36).
A unique characteristic of these synthesized metal particles is that a change in the
absorbance or wavelength gives a measure of the particle size, shape, and interparticle
properties (36, 37).
Owing to the greater surface area of nanoparticles per mass unit, they are expected
to be more biologically active than larger sized particles of the same chemical
composition. Nanoparticles of noble metals, such as gold, silver, and platinum, are
widely applied in products that directly come in contact with the human body, such as
shampoos, soaps, detergent, shoes, cosmetic products, and toothpaste, besides medical
and pharmaceutical applications. Gold nanoparticles (AuNPs) have unique optical and
electronic properties, which are different from gold bulk and are related to their size
and shape (38, 39, 40). Red colloidal gold has been used as medicine for revitalization
in China and India (41). Gold nanoparticles have found use in diagnostic and drug
delivery applications (42). Silver nanoparticles are of interest because of the unique
properties (e.g., size and shape depending optical, electrical, and magnetic properties)
which can be incorporated into antimicrobial applications, biosensor materials,
composite fibers, cryogenic superconducting materials, cosmetic products, and
electronic components. Several physical and chemical methods have been used for
synthesizing and stabilizing silver nanoparticles (43). The most popular chemical
approaches, including chemical reduction using a variety of organic and inorganic
reducing agents, electrochemical techniques, physicochemical reduction, and
radiolysis are widely used for the synthesis of silver nanoparticles. Recently,
nanoparticle synthesis has been among the most interesting scientific areas of inquiry,
and there is growing attention to produce nanoparticles using environmental friendly
methods (green chemistry). Green synthesis approaches include mixed-valence
polyoxometalates, polysaccharides, tollens, biological, and irradiation method which
have advantages over conventional methods involving chemical agents associated with
environmental toxicity.
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3. Types of nanoparticles
Nanoparticles are classified into major types viz. organic and inorganic
nanoparticles. Carbon nanoparticles are grouped as organic nanoparticles. Magnetic
nanoparticles, noble metal nanoparticles (platinum, gold and silver) and
semiconductor nanoparticles (titanium dioxide and zinc oxide) are grouped as
inorganic nanoparticles. Inorganic nanoparticles are increasingly used in drug
delivery applications due to their distinctive features such as ease of use, good
functionality, biocompatibility, ability to target specific cell and controlled release of
drugs.

4. Characterization of nanoparticles

Fig.1. Ultra-violet light absorbance of synthesized silver nanoparticles in 1mM AgNO3 in 5%


Annona squamosa leaf broth at different reaction times. Reproduced with permission from Naresh
Kumar et al.(128).

Nanoparticles are generally characterized by their size, shape, surface area,


dispersity (44) and homogeneity of these properties is important in many applications.
The common techniques of characterizing nanoparticles are as follows: UVvisible
spectrophotometry, scanning electron microscopy (SEM), transmission electron
microscopy (TEM), Fourier transforms infrared spectroscopy (FTIR), powder X-ray
diffraction (XRD) and energy dispersive spectroscopy (EDS) (45, 46, 47). UVvis
spectroscopy is an important technique to obtain the formation and stabilization of
aqueous metal nanoparticles. It is generally recognized that UVVis spectroscopy
could be used to examine size and shape-controlled nanoparticles in aqueous
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suspensions (48). The visible absorption spectrum obtained from UVvis spectro
-photometer showed a slight red shift in the wavelength for the nanoparticles
synthesized with Zingiber officinale extract compared to the nanoparticles prepared
with citrate as a capping agent (49) which is around 523nm. The UV-vis spectrum of
silver nanoparticles produced by Penicillium citrinum exhibited an absorption band at
around 400- 420 nm which is a typical plasmon band, suggesting the formation of
silver nanoparticles. It is reported that the absorption band at 265 nm is due to
electronic excitation in tryptophan and tyrosine residues in protein (50, 51). The UV
absorption spectrum of silver nanoparticles as a function of reaction time is shown in
Fig. 1. There was maximum absorption between 438 and 442nm with average
maximum absorption at 4401.6 nm. The surface plasmon peak of silver nanoparticles
at 440nm steadily increased with reaction time and became saturated at 120 min,
indicating complete reduction of the silver nitrate.

Fig.2. Scanning electron micrograph of synthesized silvernanoparticles using leaf broth of


An. squamosa. Reproduced with permission from Naresh Kumar et al.(128).

It is well known that when liquids that contain fine particles were evaporated on
a flat surface, the particles accumulate along the outer edge and form typical
structures (52). The SEM visualization enables to measure the size and shape of the
AgNPs formed. The images of the SEM results are shown in the Fig. 2. The silver
nanoparticles synthesized were spherical in shape and showed a large distribution of
sizes in the range of 2530 nm. Similar approaches for nanoparticle synthesis using
plants like Azadirachta indica, Glycine max, Cinnamon zeylanicum, Camellia sinensis,
Medicago sativa, Brassica juncea, Carica papaya, Cinnamon camphora, etc. have also
been reported to synthesize nanoparticles having wide range of size of 870 nm and all
of them also produced polydispersed nanoparticles (47, 53, 54, 55, 56, 57, 58, 59).
SEM analysis showed the particle size between 25 and 110 nm as well as the cubic
structure of the nanoparticles (60).
The morphology and size of the green synthesized Ag NPs were studied by TEM.
Most of the nanoparticles were aggregated with only a few of them scattered, as
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observed under TEM. To measure the maximum size, diagonal lengths of the
individual particles are considered. It was noticeable that the edges of the particles
were lighter than the centers, suggesting that biomolecules, such as proteins in ASPE
have capped the silver NPs and were adhered to their surfaces (61). Fig. 3 shows the
TEM images of the gold nanoparticles formed predominantly with diameter ranging
from 20 to 50 nm. Similarly, TEM images of silver nanoparticles from Emblica
officinaris were also predominantly spherical with an average size of 16.8 nm ranging
from 7.5 to 25 nm (62).

Fig.3. TEM images and corresponding size distribution of gold nanoparticles obtained by reduction
of HAuCL4 with Cymbopogan citratus. Reproduced with permission from Naresh Kumar et al.(136 ).

The energy dispersive X-ray analysis (EDAX) revealed the strongest signal in
the silver region and confirmed the formation of AgNPs. Metallic silver nanocrystals
generally show typical optical absorption peak approximately at 3 keV due to surface
plasmon resonance (63). There were also observed spectral signals for carbon and
oxygen indicated that the extracellular organic moieties were adsorbed on the surface
or in the vicinity of the metallic nanoparticles. However, Zr comes from the artifact
during sample preparation. The EDX profile showed a strong elemental signal along
with weaker oxygen, which may have originated from the biomolecules bound to the
surface of the nanoparticles (64). The presence of the elemental silver can be seen in
the graph presented by the EDX analysis, which indicated the reduction of silver ions
to silver (Fig. 4). The EDX profile shows a strong silver signal along with weaker
oxygen, which taken to study the crystalline nature of the gold nanoparticles.

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Fig.4. EDX spectrum of biosynthesized silver nanoparticles using leaf broth of An. Squamosal.
Reproduced with permission from Naresh Kumar et al. (128).

A reliable, precise and very reproducible method to quantify the relative phase
abundances in silver nanoparticle is X-ray diffraction (XRD) method. X-ray diffraction
is used to characterize crystallographic structure, grain size, and preferred orientation
in polycrystalline or powder solid samples. This is a preferred method of analysis for
characterization of unknown crystalline materials. Compounds are identified by
comparing diffraction data against a database of known materials.This analysis is a
powerful method for the determination of quantitative phase amounts in multiple phase
mixtures (65).The results of Sathyavathi et al., was in good agreement with the results
of present study with the diffraction peaks at 44.50, 52.20 and 76.7 corresponding to
the (111), (200) and (220) facets of the face centred cubic crystal structure (66).There
were intense silver nanoparticle (AgNP) diffraction peaks at 38.10, 44.44 , 64.47 ,
77.53 , and 81.62 2h, corresponding to facets 111, 200, 220, 311, and 222 of the
face-centered cubic crystal structure (Fig. 5).
FTIR is most useful for identifying chemicals that are either organic or inorganic.
It can be utilized to quantitate some components of an unknown mixture. The
composition of polymer materials can be readily determined by measuring their
infrared spectra using a Fourier transform infrared (FT-IR) spectrometer (67). The
FTIR spectroscopic study confirmed that the carbonyl group form amino acid residues

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Fig.5. X-ray diffraction pattern of synthesized silver nanoparticles in 1Mm AgNO3 in


An. Squamosa leaf broth. Reproduced with permission from Naresh Kumar et al.(128).

and proteins has the strong ability to bind metal indicating that the proteins could
possibly form a layer covering the metal nanoparticles (i.e., capping of silver
nanoparticles) to prevent agglomeration and thereby stabilize the medium. This
suggests that the biological molecules could possibly perform dual functions of
reduction and stabilization of silver nanoparticles in the aqueous medium. The total
disappearance of secondary metabolites was observed in FTIR spectroscopy after the
bioreduction of silver nanoparticles. When the metal nanoparticles form in solution,
they must be stabilized against the Van der Waals forces of attraction which may
otherwise cause coagulation. Physisorbed surfactant and polymers may cause steric or
electrostatic barriers or purely electrostatic barriers around the particle surface and may
thereby provide stabilization (36). FTIR peaks that were corresponding to aromatic
rings, geminal methyls, and ether linkages indicate the presence of flavones and
terpenoids responsible for the stabilization of the AgNPs synthesized by the Sesuvium
portulacastrum leaf extract (68). The peaks at 1,6201,636 cm1 represent carbonyl
groups from polyphenols such as catechin gallate, epicatechin gallate, epigallocatechin, epigallocatechin gallate, gallocatechin gallate and theaflavin; the results
suggest that molecules attached with AgNPs have free and bound amide groups. These
amide groups may also be in the aromatic rings. This concludes that the compounds
attached with the AgNPs could be polyphenols with an aromatic ring and bound amide
region. The bands at 1,594, 1,498 and 1,360 cm1 are due to C=C [(in-ring)
aromatic], NH2, N=O and CC [(in-ring) aromatic]. Moreover, the intense
absorption spectra of the nanoparticle at about 1,639 cm1 may results from stretching
vibration of C=C (58). The fate of nanoparticles mainly depends on the
characterization which reveals the size, shape and nature of the nanoparticles. The
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FTIR spectra of aqueous silver nanoparticles prepared from the N. oleander leaf extract
(Fig. 6) showed transmittance peaks at 509.12 (CH bend alkenes), 1077.05 (CO
stretch alcohols), 1600.63 (NH bend amines), 2736.49 and 2479.04 (OH stretch
carboxylic acids), and 3415.31 (NH stretching due to amine group).

Fig.6. FTIR spectrums of silver nanoparticles synthesized by Nerium oleander leaf extract.
Reproduced with permission from Roni, et al.(94).

5. Biological synthesis of silver nanoparticles


Production of nanoparticles can be achieved through different methods. Chemical
approaches are the most popular methods for the production of nanoparticles.
However, some chemical methods cannot avoid the use of toxic chemicals in the
synthesis protocol. Since noble metal nanoparticles such as gold, silver and platinum
nanoparticles are widely applied to human contacting areas, there is a growing need to
develop environmental friendly processes of nanoparticles synthesis that avoid toxic
chemicals use. Biological methods of nanoparticles synthesis using microorganism
(69,70,71), enzyme (72) and plant or plant extract (73) have been suggested as possible
eco-friendly alternative to chemical and physical methods. Using plant for
nanoparticles synthesis can be advantageous over other biological processes by
eliminating the elaborate process of maintaining cell cultures (73). It can also be
suitably scaled up for large-scale synthesis of nanoparticles.

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6. Biosynthesis of metal nanoparticles by plants


Plants are the predominant photosynthetic autotrophs at the first level and
producers in the food chain with high biomass production in terrestrial environment.
They capture almost 75% of light energy from sun and convert into chemical energy of
glucose. The use of plants and plant products as sustainable and renewable resources in
the synthesis of nanoparticles is more advantageous over prokaryotic microbes, which
needs expensive methodologies for maintaining microbial cultures and downstream
processing.The recent reports on phytosynthesis of nobel metal nanoparticles have
been summarized in Tables 1, 2 and are discussed below.
6.1. Silver Nanoparticles
Jain et al., reported the synthesis of highly stable and Cubic, hexagonal silver
nanoparticles (15 nm) by exposing the aqueous Carica papaya L fruit extract to silver
nitrate solution (74). Ashok kumar et al.(62) and Mallikarjuna et al.(76) reported the
synthesis of silver nanoparticles from the leaf extracts of Parthenium Hysterophorus
and Ocimum plants, respectively (75, 76). Prasad et al. (77) performed an interesting
experiment using the young leaf extracts of Nicotiana tobaccum and the resultant
nanoparticle was 8nm in size. Rajakumar et al.(78) demonstrated the rapid synthesis of
silver nanoparticles using the leaf extract of Eclipta prostrata and they obtained the
same with an average size of 45nm, which was spherical in shape with a small
percentage of elongated particles and found that the synthesized nanoparticles were
highly toxic against different mosquito vectors of Malaria and Filariasis (78).
Annamalai et al.(79) reported rapid synthesis of stable silver nanoparticles of
spherical and cubic shapes with 32-53 nm in size using Phyllanthus amarus leaf
extract. Silver nanoparticles of 39.60 nm were successfully synthesized using the
Lantana camera leaf extract (80). Extracellular synthesis of silver nanoparticles has
been reported using Agaricus bisporus (white button mushrooms) with a spherical
shape and an average size of 8.5nm (81). The use of extract of Foeniculum vulgare
young leaves in the extracellular biosynthesis of silver nanoparticles with an average
of 18-83nm (82). Zargar et al.(83) has checked the compatibility of the matured leaf
extracts of Vitex negundo L. towards the formation of silver nanoparticles and
reported that the extract could produce silver nanoparticles of spherical shape with
18.2 8.9 nm sizes. Satyavani et al. (84) highlighted the possibility of tissue
culture-derived callus extract from Citrullus colocynthis (L.) for the synthesis of silver
nanoparticles. The resulted nanoparticle has a spherical shape and size of 31nm.
Similarly, other researchers also reported the formation of silver nanoparticles using
rhizome extract of Dioscorea batatas, which gave a circular and flower shaped
nanoparticles (85).

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Table 1. Phytosynthesis of Silver Nanoparticles

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Table 2. Phytosynthesis of Gold Nanoparticles

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Arshad Farooqui et al.(86) reported the formation of spherical silver


nanoparticles using leaf extract of Clerodendrum inerme. Similarly, Dubey et al.,
stated that the synthesized silver nanoparticles with cubical, uniform shape and an
average size of 50-150nm using the leaf extract of Eucalyptus hybrida (Safeda) (87),
while Geethalakshmi et al.(88) used extracts of Trianthema decandra and it was
found that cubical, hexagonal shape and 15nm size. Similarly, Safaepour et al., also
obtained silver nanoparticles of 6nm using the leaf extract of Pelargonium graveolens
(89), while Nagajyoti et al.(90) reported the synthesis of silver nanoparticles using the
leaf extract of the Saururus chinenis plant and the obtained nanoparticles were in the
range of 38-54nm in size (90). Recently, bioinspired synthesis of highly stabilized
silver nanoparticles using Paederia foetida (91) as well as Euphorbia hirta (92) was
reported. They reported the size of AgNPs in the range of 24nm and 30-60nm
respectively. Synthesized silver nanoparticles with an average size of 15-30 nm using
leaf extract of Pedilanthus tithymaloides and proven their activity against malaria
parasite (93).
Roni et al.(94) reported the rapid synthesis of silver nanoparticles using the leaf
extract of Nerium oleander and found that the synthesized nanoparticles were highly
toxic against the malaria vector, Anopheles stephensi (94). The obtained nanoparticles
were spherical- and cubic-shaped with an average size of 20-35nm. Similarly, Suganya
et al.(95) reported rapid synthesis of silver nanoparticles of spherical- and cubic-shapes
using Murraya koenigii leaf extract which was effective against Anopheles stephensi
and Aedes aegypti (95). Sahu et al.(96) reported the synthesis and characterization of
silver nanoparticles using Cynodon dactylon leaves and assessment of their
antibacterial activity. The obtained nanoparticles were 8-10nm in size with spherical
shape (96).
Microwave-assisted rapid extracellular synthesis of stable silver nanoparticles
from guava (Psidium guajava) leaf extract (97) was reported and the resulted
nanoparticles were spherical in shape with 265 nm in size. Gnanadesigan et al.(98)
demonstrated the antibacterial potential of synthesized silver nanoparticles with
spherical shape and about 71-110nm using Avicennia marina mangrove plant (98).
Similarly, Song et al.(99) studied and reported the antibacterial latex foams coated with
biologically synthesized silver nanoparticles using Magnolia kobus leaf extract, which
was 25nm in size (99). Coleus aromaticus leaf extract mediated synthesis of silver
nanoparticles and its bactericidal activity was performed (100), while Awwad
et al.(101) studied the antibacterial activity of green synthesized AgNPs using carob
leaf extract and the obtained AgNPs were 5-40nm with spherical in shape (101).
The phytosynthesis of AgNPs using aqueous extract of Portulaca Oleracea and
the reported nanoparticles are less than 60nm (102). In order to study the antibacterial
activity of biosynthesized AgNPs using Bryophyllum pinnatum and they have got the
same with spherical shape of 70-90nm in size, which shown a very good antibacterial
activity as they expected (103). Similarly, Firdhouse et al.(104) studied and reported
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the novel approach to synthesize AgNPs using the leaf ethanol extract of Pisonia
grandis which was spherical in shape and the size was in the range of less than 150nm
in size (104). Recently, the synthesized silver nanoparticles with an average size of
32-53nm by using phyllanthus niruri to study the antimicrobial activity and cytotoxic
effects (105). Larvicidal activity of synthesized silver nanoparticles of spherical in
shape with 32-200nm using Plumeria rubra plant latex against Aedes aegypti and
Anopheles stephensi (106) was also reported.
6.2. Gold Nanoparticles
Annamalai et al., reported the formation of gold nanoparticles using the leaf
extract of Phyllanthus amarus (107). Similarly, other studies of Gan et al., reported the
synthesis of gold nanoparticles using the plant leaf extract of Mangifera indica leaf,
Acanthella elongate and pulp extract of Sugar beet to produce the capability of gold
nanoparticles of spherical and irregular shapes with 20-17nm, 7-20nm and 20-160nm
respectively (108). Thirumurugan et al., reported the formation of gold nanoparticles
from the leaves of Azadirachta indica with particle size of 2-100nm (109). The
extracellular synthesis of gold nanoparticles using the fruit extract of Emblica
officinalis has been attempted by Ankamwar et al., and they have reported that the
synthesized nanoparticles have an average size of 15-25nm (110). Krishnamurthy et al.
(111) assayed the seed extracts of Cuminum cyminum for the reduction of plant seed
extract with AuNPs. The results indicated that all the tested leaf extracts have the
ability to produce gold nanoparticles with spherical shaped, 1-10nm nanoparticles
(111). The green synthesis of gold nanoparticles using the leaf extract of Trigonella
foneumgraecum with 15-25nm spherical shaped AuNPs (112). Gold nanoparticles of
various sizes were also attained by using dried leaf extract of Aloe vera (113).
Similarly, the formation of highly stable gold nanoparticles (6.75-57.91 nm) when the
aqueous leaf extract of Coriander was exposed (114). In another report, sphericalshaped gold nanoparticles were synthesized using flower extract of Nyctanthes
arbortristis and leaf extract of Ocimum sanctum. Very recently, Dubey et al.(87)
reported the synthesis of gold nanoparticles with Spherical, triangular and hexagonal
shapes and about 18nm size using leaves of Sorbus aucuparia. In addition, syntheses of
Quasi-spherical and spherical gold nanoparticles have been reported on the reduction
of AuCl4 by the leaf extract and root extract of Chenopodium album and Panax
ginseng C.A. Meyer. Through this study they have synthesized nanoparticles with a
size of 10-30nm and 16.2-3.0 nm respectively (115). The green synthesis of AuNPs
using Panax ginseng C.A.Meyer root extract and the resultant nanoparticle were
spherical in shape with an average size of 16.2-3.0nm in size.
In the study of Coleus amboinicus Lour leaf extract-assisted phytosynthesis of
Au nanoparticles (116, 117) and the generation of Spherical, triangle, truncated
triangle, hexagonal and decahedral shaped Au nanoparticles of 4.6-55.1nm (118). The
formation of triangles and hexagon in patterned Au nanowire were demonstrated (119)
with peeled extract of Musa pradisiaca. These nanowires were in the range of
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10-20m. Synthesis of gold nanoparticles of various size range of 5500 nm were


obtained from the leaf extract of Diopyrus kaki (120). Noruzi et al.(121) reported the
biosynthesis of Au nanoparticles of 10nm with spherical, triangular and hexagonal
shapes using the petal extracts of Rosa hybrid (121). In addition, synthesis of Au
nanoparticles was achieved by using the leaf extract of Eucalyptus camaldulensis and
the nanoparticles were in crystalline form with an average size of 5.5-7.5nm (122).
The biosynthesis of AuNPs using the leaf extract of Stevia rebaudiana and the
resulted nanoparticles were octahedral in shape with an average size of 8-20nm (123).
Rapid synthesis of Au nanoparticles has also been reported by Smitha et al.(124) using
the Cinnamomum zeylanicum leaf extract and the obtained nanoparticles were
spherical, prism of average 25nm in size (124). Similarly, Ghodake et al., also obtained
triangular and hexagonal AuNPs, having a size range of 200-500nm using the pear fruit
extract (125). The synthesis of circular, triangular, hexagonal shaped gold
nanoparticles of 10-45nm size using the leaf extract of Memecylon edule (126).
Recently, Ghule et al.(127) synthesized Au nanoparticles of triangular size using bean
extract of Cicer arietinum (127).

7. Larvicidal activity of metal nanoparticles on human pest


A biological method was used to synthesize stable silver nanoparticles using
Annona squamosa that were tested as mosquito larvicides against A. aegypti,
A. stephensi, and C. quinquefasciatus with the median lethal concentrations (LC50) of
silver nanoparticles that killed fourth instars of A. aegypti, C. quinquefasciatus, and
A. stephensi were 0.30, 0.41, and 2.12 ppm, respectively (128). AgNPs synthesized
using Euphorbia hirta plant leaf extract against malarial vector A. stephensi was
determined, the highest larval mortality was found in the synthesized AgNPs against
the first to fourth instar larvae and pupae of values LC50 (10.14, 16.82, 21.51, and 27.89
ppm, respectively), LC90 (31.98, 50.38, 60.09, and 69.94 ppm, respectively), and the
LC50 and LC90values of pupae were determined as 34.52 and 79.76 ppm, respectively
(92). Larvicidal activity of synthesized silver nanoparticles using Eclipta prostrate
against C. quinquefasciatus (LC50=27.49 and 4.56 mg/l; LC90=70.38 and 13.14 mg/l)
and against A. subpictus (LC50=27.85 and 5.14 mg/l; LC 90 =71.45 and 25.68 mg/l),
respectively (78). AgNPs synthesized with Rhizophora mucronata leaf extract against
the larvae of A. aegypti and C. quinquefasciatus and the LC50 values of the
synthesized AgNPs were identified as 0.585, 2.615 mg/L and LC90 values as 0.891
and 6.291 mg/L (98). The larvicidal activity of synthesized AgNPs using Cocos
nucifera coir against A. stephensi and C. quinquefasciatus with LC50 and LC90 values
of synthesized AgNPs instars of A. stephensi (LC50=87.244.75mg/L; LC90=230.90
17.10mg/L), and against the larvae of C. quinquefasciatus (LC50=49.892.42 mg/L;
LC90 = 84.856.50 mg/L) respectively, showed that the fourth instars were
significantly more susceptible (df = 8.49 and 13.86) for 72 h of exposure (129).
Suman et al., studied the GCMS analysis of bioactive components and synthesis of
silver nanoparticle using Ammannia baccifera aerial extract and its larvicidal activity
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against malaria and filariasis vectors. The synthesized silver nanoparticles shown
significant toxic effects against the larvae of A. subpictus with an LC50 = 29.54 ppm
and against the larvae of C. quinquefasciatus LC50 = 22.32 ppm (130).
The larvicidal activity of synthesized silver nanoparticles (Ag NPs) utilizing
aqueous bark extract of Ficus racemosa was tested against fourth instar larvae of
filariasis vector, Culex quinquefasciatus and Japanese encephalitis vectors, Culex
gelidus. The maximum efficacy was observed in crude aqueous extract of F. racemosa
against the larvae of Cx. quinquefasciatus and Cx. gelidus (LC50=67.72 and 63.70
mg/L; r2=0.995 and 0.985) and the synthesized Ag NPs (LC50=12.00 and 11.21 mg/L;
r2=0.997 and 0.990), respectively (131). Encapsulated citronella oil nano-emulsion is
prepared by high-pressure homogenization of 2.5% surfactant and 100% glycerol, to
create stable droplets that increase the retention of the oil and slow release. The release
rate depends upon the protection time; consequently a decrease in release rate can
prolong mosquito protection time (132). Nanoparticles loaded with garlic essential oil
are efficacious against Tribolium castaneum Herbst (133). Pithecellobium dulce
mediated extra-cellular green synthesis of silver nanoparticles shown effective
larvicidal activity against Culex quinquefasciatus (LC50 = 21.56 mg/L and r2 = 0.995)
due to high surface to volume ratio (134) Larvicidal studies were carried out against
Culex quinquefasciatus and the results were compared with bulk permethrin. The LC50
of nanopermethrin to Cx. quinquefasciatus was 0.117 mg/L. The LC50 of bulk
permethrin to Cx. Quinquefasciatus was 0.715 mg/L. Nanopermethrin may be a good
choice as a potent and selective larvicide for Cx. Quinquefasciatus (135).

8. Conclusion
From the review we conclude that the botanicals can be used as an effective
capping as well as reducing agent for the synthesis of metal nanoparticles.
Nanoparticles synthesized by green protocol are stable for more than months. Further
research is needed to improve the efficiency of production of metal nanoparticles
using botanicals as a reducing and stabilizing agents and to increase the biological
activity of the product against agriculture and human pests to levels commensurate
with commercially available microbial insecticides. We also seek to develop the
methods and techniques necessary for green synthesis of nanoparticles using
microorganisms, such as bacteria, fungi, algae etc. for insect pest control.

Acknowledgement
The authors acknowledge Prof. Donald R.Barnard, USDA-ARS-CMAVE, USA
for comments that improved the manuscript.

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84. Satyavani, K., Gurudeeban, S., Ramanathan, T., Balasubramanian, T. (2011) Biomedical potential of silver
nanoparticles synthesized from calli cells of Citrullus colocynthis (L.) Schrad J. Nanobiotechnol. 9:43.
85. Nagajyothi, P.C., Lee, K.D (2011) Synthesis of plant-mediated silver nanoparticles using Dioscorea batatas rhizome
extract and evaluation of their antimicrobial activities. J. Nanomaterials 7 pp.
86. Arshad Farooqui, M.D., Chauhan, P.S., Krishnamoorthy, P., Shaik, J. (2010) Extraction of silver nanoparticles from
the leaf extracts of Clerodendrum Inerme. Dig. J. Nanomater Biostruct. 5(1):43-49.
87. Dubey, M., Bhadauria, S., Kushwah, B.S. (2009) Green Synthesis of nanosilver particles from extract of Eucalyptus
Hybrida (Safeda) Leaf. Dig. J. Nanomater Biostruct. 4(3):537-543.
88. Geethalakshmi, R., Sarada, D.V.L. (2010) Synthesis of plant-mediated silver nanoparticles using Trianthema
decandra extract and evaluation of their anti microbial activities. Int. J. Engg. Sci. and Technol. 2(5) 970-975.
89. Safaepour, M., Shahverdi, A.R., Shahverdi, H.R., Khorramizadeh, M.R., Gohari, A.R. (2009) Green synthesis of
small silver nanoparticles using geraniol and its cytotoxicity against Fibrosarcoma Wehi 164. Avicenna J. Med.
Biotech. 1(2):111-115.
90. Nagajyoti, P.C., Prasad, T.N.V.K.V., Sreekanth, T.V.M., Lee, K.D. (2011) Bio-Fabrication of silver nanoparticles
using leaf extract of Saururus Chinenis. Dig. J. Nanomater. Biostruct. 6(1) 121-133.
91. Lavanya, M., Veenavardhini, S.V., Gim, G.H., Kathiravan, M.N., Kim, S.W. (2013) Synthesis, Characterization and
Evaluation of Antimicrobial Efficacy of Silver Nanoparticles using Paederia foetida L. leaf extract. Int. Res. Biol. Sci.
2(3): 28-34.
92. Agalya Priyadarshini, S., Murugan, K., Panneerselvam, C., Ponarulselvam, S., Hwang, J-S., Nicoletti, M. (2012)
Biolarvicidal and pupicidal potential of silver nanoparticles synthesized using Euphorbia hirta against Anopheles
stephensi Liston (Diptera: Culicidae). Parasitol. Res. (2012) 111:9971006.
93. Sundaravadivelan, C., Nalini Padmanabhan, M., Sivaprasath, P., Kishmu, L. (2013) Biosynthesized silver
nanoparticles from Pedilanthus tithymaloides leaf extract with anti-developmental activity against larval instars of
Aedes aegypti L. (Diptera, Culicidae). Parasitol. Res. 112:303311.
94. Roni, M., Murugan K., Panneerselvam, C., Subramaniam, J., Hwang, J.S. (2013) Evaluation of leaf aqueous extract
and synthesized silver nanoparticles using Nerium oleander against Anopheles stephensi (Diptera: Culicidae)
Parasitol. Res. 112:981990.
95. Suganya, A., Murugan K., Kovendan, K., Mahesh Kumar, P., Hwang, J.S. (2013) Green synthesis of silver
nanoparticles using Murraya koenigii leaf extract against Anopheles stephensi and Aedes aegypti. Parasitol. Res.
112:13851397.
96. Sahu, N., Soni, D., Chandrashekhar, B., Sarangi, B.K., Satpute, D., Pandey, R.A. (2013) Synthesis and
characterization of silver nanoparticles using Cynodon dactylon leaves and assessment of their antibacterial activity.
Bioprocess Biosyst. Eng. 36(7):999-1004.

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Invited Review

97. Raghunandan, D., Mahesh, B.D., Basavaraja, S., Balaji, S.D., Manjunath, S.Y.,Venkataraman, A. (2011)
Microwave-assisted rapid extracellular synthesis of stable bio-functionalized silver nanoparticles from guava
(Psidium guajava) leaf extract. J. Nanopart. Res. 13:20212028.
98. Gnanadesigan, M., Anand, M., Ravikumar, S., Maruthupandy, M., Syed Ali, M., Vijayakumar, V., Kumaraguru, A.K.
(2012) Antibacterial potential of biosynthesised silver nanoparticles using Avicennia marina mangrove plant. Appl.
Nanosci. 2:143-147.
99. Song, J.Y., Kwon, E.Y., Kim, B.S. (2012) Antibacterial latex foams coated with biologically synthesized silver
nanoparticles using Magnolia kobus leaf extract. Korean J. Chem. Eng. 29(12): 1771-1775.
100. Vanaja, M., Annadurai, G. (2013) Coleus aromaticus leaf extract mediated synthesis of silver nanoparticles and its
bactericidal activity. Appl. Nanosci. (2013) 3:217223.
101. Awwad, A.M., Salem, N.M., Abdeen, A.O. (2013) Green synthesis of silver nanoparticles using carob leaf extract and
its antibacterial activity. Int. J. Indus. Chem. 4:29.
102. Firdhouse, M.J., Lalitha, P. (2013) Green Synthesis of silver nanoparticles using the aqueous extract of Portulaca
oleracea (L.).Asian J. Pharma. and Clin. Res. 6(1):92-94.
103. Baishya, D., Sharma, N., Bora, R. (2012) Green synthesis of silver nanoparticle using Bryophyllum pinnatum (Lam.)
and monitoring their antibacterial activities. Arc. Appl. Sci. Res. 4(5):2098-2104.
104. Firdhouse, M.J., Lalitha, P., Sripathi, S.K. (2012) Novel synthesis of silver nanoparticles using leaf ethanol extract of
Pisonia grandis (R. Br). Der. Pharma. Chemica. 4(6):2320-2326.
105. Krishnamoorthy, P., and Jayalakshmi, T. (2012) Preparation, characterization and synthesis of silver nanoparticles by
using Phyllanthus niruri for the antimicrobial activity and cytotoxic effects. J. Chem. and Pharma. Res. 4(11):
4783-4794.
106. Patil, C.D., Patil, S.V., Borase, H.P., Salunke, B.K., Salunkhe, R.B. (2012) Larvicidal activity of silver nanoparticles
synthesized using Plumeria rubra plant latex against Aedes aegypti and Anopheles stephensi. Parasitol. Res. 110(5):
1815-22.
107. Annamalai, A., Babu, S.T., Jose, N.A., Sudha, D., Lyza,, C.V. (2011) Biosynthesis and Characterization of silver and
gold nanoparticles using aqueous leaf extraction of Phyllanthus amarus Schum. & Thonn. World Appl. Sci. J. 13 (8):
1833-1840
108. Gan, P.P., Yau, Li, S.F. (2012) Potential of plant as a biological factory to synthesize gold and silver nanoparticles
and their applications. Rev. Environ. Sci .Biotechnol. 11:169206.
109. Thirumurugan. A., Jiflin, G.J., Rajagomathi, G., Tomy, N.A., Ramachandran, S., Jaiganesh, R. (2010) Biotechnological synthesis of gold nanoparticles of Azadirachta indica leaf extract. Int. J. Biol. Tech. 1(1):75-77.
110. Ankamwar, B., Damle, C., Ahmad, A., Satry, M. (2005b) Biosynthesis of gold and silver nanoparticles using Emblica
officinalis fruit extract, their phase transfer and transmetallation in an organic solution. J. Nanosci. Nanotechnol. 5
(10):1665-1671.
111. Krishnamurthy, S., Sathishkumar, M., Lee, S.Y., Bae, M.A., Yun, Y.S. (2011) Biosynthesis of Au nanoparticles using
cumin seed powder extract. J. Nanosci. Nanotechnol. 11(2):18111814.
112. Aromal, S.A., Philip. D. (2012) Green synthesis of gold nanoparticles using Trigonella foenum-graceum and its
size-dependent catalytic activity. Spectrochim Acta Part A 97:15.
113. Chandran, S.P., Chaudhary, M., Pasricha, R., Ahmad, A., Sastry, M. (2006) Synthesis of gold nanotriangles and silver
nanoparticles using Aloe vera plant extract. Biotechnol. Prog. 22(2): 577583.
114. Narayanan, K.B., Sakthivel, N. (2008) Coriander leaf mediated biosynthesis of gold nanoparticles. Mater Lett. 62(30):
45884590.
115. Dubey, S.P., Lahtinen, M., Sarkka, H., Sillanpaa, M. (2010). Bioprospective of Sorbus aucuparia leaf extract in
development of silver and gold nanocolloids. Colloids Surf. B 80(1): 2633.
116. Dwivedi, A.D., Gopal, K. (2010) Biosynthesis of silver and gold nanoparticles using Chenopodium album leaf
extract. Colloids Surf. A 369 (13):2733.
117. Leonard, K., Ahmmad, B., Okamura, H., Kurawaki, J. (2011) In situ green synthesis of biocompatible ginseng capped
gold nanoparticles with remarkable stability. Colloids Surf. B 82(2):391396.
118. Narayanan, K.B., Sakthivel, N. (2010b) Phytosynthesis of gold nanoparticles using leaf extract of Coleus amboinicus
Lour. Mater Charact 61(11):12321238.
119. Bankar, A., Joshi, B., Ravi Kumar, A., Zinjarde, S. (2010) Banana peel extract mediated synthesis of gold
nanoparticles. Colloids Surf. B 80(1):4550.

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Invited Review

120. Song, J.Y., Jang, H.K., Kim, B.S. (2009) Biological synthesis of gold nanoparticles using Magnolia kobus and
Diopyros kaki leaf extracts. Process Biochem. 44 (10): 11331138.
121. Noruzi, M., Zare, D., Khoshnevisan, K., Davoodi, D. (2011) Rapid green synthesis of gold nanoparticles using Rosa
hybrid petal extract at room temperature. Spectrochim Acta Part A Mol. Biomol. Spectrosc. 79(5): 14611465.
122. Ramezani, N., Ehsanfar, Z., Shamsa, F., Amin, G., Shahverdi, H.R., Esfahani, H.R.M., Shamsaie, A., Bazaz, R.D.,
Shahverdi, A.R. (2008) Screening of medicinal plant methanol extracts for the synthesis of gold nanoparticles by their
reducing potential. Z. Naturforsch. 63:903908.
123. Mishra, A.N., Bhadauria S., Gaur, M.S., Pasricha, R., Kushwah, B.S. (2010) Synthesis of gold nanoparticles by
leaves of zero-calorie sweetener herb (Stevia rebaudiana) and their nanoscopic characterization by spectroscopy and
microscopy. Int. J. Green Nanotechnol. Phys. Chem. 1 (2):118124.
124. Smitha, S.L., Philip, D., Gopchandran, K.G. (2009) Green synthesis of gold nanoparticles using Cinnamomum
zeylanicum leaf broth. Spectrochim Acta Part A 74 (3):735739.
125. Ghodake, G.S., Deshpande, N.G., Lee, Y.P., Jin, E.S. (2010) Pear fruit extract-assisted room-temperature biosynthesis
of gold nanoplates. Colloids Surf. B 75(2):584589.
126. Elavazhagan, T., Arunachalam, K.D. (2011) Memecylon edule leaf extract mediated green synthesis of silver and gold
nanoparticles. Int. J. Nanomed. 6:12651278.
127. Ghule, K., Ghule, A.V., Liu, J.Y., Ling, Y.C. (2006) Microscale size triangular gold prisms synthesized using Bengal
gram beans (Cicer arietinum L.) extract and HAuCl4.3H2O: A green biogenic approach. J. Nanosci. Nanotechnol.
6(12): 37463751.
128. Naresh Kumar, A., Murugan, K., Rejeeth, C., Madhiyazhagan, P., Barnard, D.R. (2012) Green Synthesis of Silver
Nanoparticles for the Control of Mosquito Vectors of Malaria, Filariasis, and Dengue Vector-Borne Zoo Dis. 12(3):
262-268.
129. Roopan, S.M., Rohit, G.M., Rahuman, A.A., Kamaraj, C., Bharathi, A., Surendra, T.V. (2013) Low-cost and
eco-friendly phyto-synthesis of silver nanoparticles using Cocos nucifera coir extract and its larvicidal activity.
Industrial Crops and Products 43: 631635
130. Suman, T.Y., Elumalai, D., Kaleena, P.K., Radhika Rajasree, S.R. (2013) GCMS analysis of bioactive components
and synthesis of silver nanoparticle using Ammannia baccifera aerial extract and its larvicidal activity against malaria
and filariasis vectors. Industrial Crops and Products 47: 239245.
131. Velayutham, K., Rahuman, A.A., Rajakumar, G., Roopan, S.M., Elango, G., Kamaraj, C., Marimuthu, S., Santhoshkumar, T., Iyappan, M., Siva, C. (2013) Larvicidal activity of green synthesized silver nanoparticles using bark
aqueous extract of Ficus racemosa against Culex quinquefasciatus and Culex gelidus. Asian Pac. J. Trop. Med. 6 (2):
95-101.
132. Sukul, N.C., Singh, R.K., Sukul (Chunari), S., Sen, P., Bhattacharyya, A, Sukul A., Chakrabarty, R. (2009) Potentized
Drugs Enhance Growth of Pigeon pea. Environ. Ecol. 26(3): 1115-1118.
133. Yang, F.L., Li, X.G., Zhu, F., Lei, C.L. (2009) Structural Characterization of Nanoparticles Loaded with Garlic
Essential Oil and Their Insecticidal Activity against Tribolium castaneum (Herbst) (Coleoptera: Tenebrionidae). J.
Agric. Food Chem. 57(21): 10156-10162.
134. Raman, N., Sudharsan, S., Veerakumar, V., Pravin, N., Vithiya, K. (2012) Pithecellobium dulce mediated
extra-cellular green synthesis of larvicidal silver nanoparticles. Spectrochimica Acta Part A Molecular and
Biomolecular Spectroscopy 96: 1031-7.
135. Anjali, C.H., Sudheer Khan, S., Margulis-Goshen, K., Magdassi, S., Mukherjee, A., Chandrasekaran, N. (2010)
Formulation of water-dispersible nanopermethrin for larvicidal applications. Ecotoxicol Environ. Safety, 73(8):
1932-1936.
136. Naresh Kumar, A., Jeyalalitha, T., Murugan, K., Madhiyazhagan P. (2013) Bioefficacy of plant-mediated gold
nanoparticles and Anthocepholus cadamba on filarial vector, Culex quinquefasciatus (Insecta: Diptera: Culicidae).
Parasitol Res 112:10531063.
Article History: Received 15th June 2013; Revised 27th September 2013 and Accepted 10th April 2014; and
Published 30th October 2014.
Reviewed by: Donald R.Barnard, USDA-ARS-CMAVE, USA.

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Table Contents

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Page No.

Preface
Forward message
Contributors
Reviewers
Acknolwedgement

i
ii
iii
iv
v

Volume1
Section I: Insect Biochemical approaches

1. Introduction to Insect Molecular Biology.

Raman Chandrasekar, P.G., Brintha, Enoch Y.Park, Paolo Pelsoi, Fei Liu,
Marian Goldsmith, Anthony Ejiofor, B.R., Pittendrigh, Y.S., Han,
Fernando G. Noriega, Manickam Sugumaran, B.K., Tyagi, Zhong Zheng Gui,
Fang Zhu, Bharath Bhusan Patnaik, and P. Michailova

2.

Modulation of Botanicals on pests biochemistry.

57

Sahayaraj, K.

3.

Detoxication, stress and immune responses in insect antenna:


new insights from transcriptomics.

75

David Siaussat, Thomas Chertemps and Martine Maibeche

4.

Application of isotopically labeled compounds and tandem mass


spectrometry for studying metabolic pathways in mosquitoes.

99

Stacy Mazzalupo and PatriciaY.Scaraffia

5.

Field Response of Dendroctonus armandi Tsai & Li (Coleoptera:


Scolytinae) to Synthetic Semiochemicals in Shaanxi, China.

127

Shou-An Xie, Shu-Jie L.V., Hui-Chen, Raman Chandrasekar

xvii

Section II: Insect Growth

6. Insect Cuticular SclerotizationHardening Mechanisms and Enzymes.

149

Manickam Sugumaran

7. New Approaches to Study Juvenile Hormone Biosynthesis in Insects.

185

Crisalejandra Rivera-Perez, Marcela Nouzova and Fernando G. Noriega

8. The regulatory biosynthetic pathway of juvenile hormone.

217

Zhentao Sheng and Raman Chandrasekar


Section III:

Insect Immunity

9. The innate immune network in a hemimetabolous insect, the brown


planthopper, Nilaparvata lugens.

233

Yanyuan Bao, Raman Chandrasekar, Chuan-Xi Zhang

10. Immune Pathways in Anopheles gambiae.

253

Maria L. Simes and Raman Chandrasekar

11. Key biochemical markers in silkworms challenged with immuno-

271

elicitors and their association in genetic resistance for survival.

Somasundaram, P., Chandraskear, R., Kumar,K.A., and Manjula, A.


Section IV:

Insect Molecular Genetics

12. The recent progress of the W and Z chromosome studies of the

291

silkworm, Bombyx mori

Hiroaki Abe, Tsuguru Fujii and Raman Chandrasekar

13. Molecular characterization and DNA barcoding for identification of

317

agriculturally important insects.

Rakshit Ojha, Jalali, S.K., and Venkatesan, T.

14. Polytene chromosomes and their significance for Taxonomy,

331

Speciation and Genotoxicology

Paraskeva V. Michailova

15. Insect exuvium extracted DNA marker: a good complementary


molecular taxonomic characteristics with special reference
to mosquitoes.

355

Dhanenjeyan, K. J., Paramasivam, R., Thanmozhi, V., Chandrasekar,R., and Tyagi, B.K.
Index

363

xviii

Volume2
Section V:

Molecular Biology of Insect Pheromones

16. Understanding the functions of sex-peptide receptors?

373

Orly Hanin, Ada Rafaeli

17. Current views on the function and evolution of olfactory receptors

385

in Lepidoptera.

Arthur de Fouchier, Nicolas Montagn, Olivier Mirabeau, Emmanuelle Jacquin-Joly

18. Molecular architecture, phylogeny and biogeography of pheromone

409

biosynthesis and reception genes / proteins in Lepidoptera.

Jian-Cheng Chang, P. Malini, R. Srinivasan

Section VI:

Insect Molecular Biology

19. Application of Nanoparticles in sustainable Agriculture :

429

Its Current Status.

Atanu Bhattacharyya , Raman Chandrasekar, Asit Kumar Chandra,


Timothy T. Epidi and Prakasham, R.S.

20. Mosquito Ribonucleotide Reductase: A Site for Control.

449

Daphne Q.-D. Pham, Victor H. Perez, Lissette Velasquez, Dharty Bhakta,


Erica L. Berzin, Guoli Zhou, and Joy. J. Winzerling.

21. Green protocol for synthesis of metal nanoparticles


to control insect pests.

473

Murugan, K., Chandrasekar, R., Panneerselvam, C., Naresh Kumar, A.,


Madhiyazhagan, P., Mahesh Kumar, P., Jiang-Shiou Hwang, Jiang Wei

22. Aquaporins in Blood-Feeding Arthropods.

497

Lisa L. Drake, Hitoshi Tsujimoto, Immo A. Hansen

23. Mimetic analogs of three insect neuropeptide classes

509

for pest management.

Ronald J. Nachman

xix

Section VII:

Insect Pest Management through


Biochemical and Molecular approaches

24. Induced resistance in plants against insect pests and

533

counter-adaptation by insect pests.

Abdul Rashid War and Hari C Sharma

25. Insect Chemical communication - an important component of

549

novel approaches to insect pest management.

Usha Rani, P.

26. Mosquito control using biological larvicides: Current Scenario.

575

Subbiah Poopathi, C. Mani and R. Chandrasekar

27. Application of RNAi toward insecticide resistance management.

595

Fang Zhu, Yingjun Cui, Douglas B. Walsh, Laura C. Lavine

Section VIII:

Insect Bioinformatics

28. Entomo-informatics: A prelude to the concepts in Bioinformatics.

621

Habeeb, S.K.M. and Raman Chandrasekar

29. Molecular expression and structure-function relationships of

633

apolipophorin III in insects with special reference to innate immunity.

Bharat Bhusan Patnaik, Raman Chandrasekar, Yeon Soo Han

30. Computer-aided pesticide design: A short view

685

Jitrayut Jitonnom

Index

709

xx

ISBN No. 978-1-63315-205-2 (USA)

First Edition: Volume 1, 2 October 2014


Total No. Pages: 398 + 372 = 770

Edited by Raman Chandrasekar


B.K. Tyagi
Zhong Zheng Gui
Gerald R. Reeck
Copyright Reserved
Published by International Book Mission, Academic Publisher, South India.

Printed in the K-State Union, Copy and Printing services,


Kansas State University, Manhattan 66506, KS, USA.
This publication is considered to provide accurate and authoritative information with regards to the
subject matter has been obtained by its authors. The publisher has taken reasonable care in the
preparation of this book volume. However, the publisher and its authors shall in no event be liable for
any errors or omission arising out of use of this information and specifically disclaim any implied
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Application for such permission, with a statement of the purpose and extend for the reproduction,
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Book Mission Project # 2: Initiated on June 2010; Completed on March 2014 and Published on Oct. 2014.

Volume 1 & 2, October 2014

Short Views on Insect Biochemistry


and Molecular Biology

PREFACE
Entomology as a science of inter-depended branches like biochemistry, molecular entomology, insect
biotechnology; has made rapid progress in its attributes in the light of modern discoveries. This also
implies that there is an urgent need to manage the available resources scientifically for the good of man.
In the past five decades, entomology in the world/country has taken giant steps ahead. Continued
research has evolved better pest management through molecular approaches. The aim of the Short
Views on Insect Biochemistry and Molecular Biology book is to integrate perspectives across
biochemistry and molecular biology, physiology, immunology, molecular evolution, genetics,
developmental biology and reproduction of insects. This century is proclaimed as the Era of
Biotechnology and its consists of all types of Mol-Bio applications, which is an essential component for
a through understanding of the Insect Biology. This volume 1 & 2 (8 section with 30 chapters)
establishes a thorough understanding of physiological and biochemical functions of proteins, genes in
insects life processes; the topics dealt with in the individual chapters include chemistry of the insect
cuticle, hormone and growth regulators; biochemical defenses of insects; the biochemistry of the toxic
and detoxification action; modern molecular genetics and evolution; inter- and intra-specific chemical
communication and behavior; insect pheromone and molecular architecture, phylogeny and chemical
control of insect by using insect pheromones biotechnology; insect modern biology and novel plant
chemical and microbial insecticides for insect control, followed by a discussion of the various
mechanisms of resistance (both behavioral and physiological) and resistance management; modern insect
pest management through biochemical and molecular approaches; Mimetic analogs of insect
neuropeptide for pest management; entomo-informatics and computer-aided pesticide designing. In short
this book provides comprehensive reviews of recent research from various geographic areas around the
world and contributing authors area recognized experts (leading entomologist/scientist) in their
respective filed of molecular entomology. We will miss this collaboration now it has ended, but will feel
rewarded if this book is appreciated by our team/colleagues and remarkable mile stone in entomology
field.
This book emphasizes upon the need for and relevance of studying molecular aspects of entomology in
Universities, Agricultural Universities and other centers of molecular research. To encompass this
knowledge and, particularly disseminate it to the scientific community free of cost, was the major
inspiring force behind the launch of Short Views on Insect Biochemistry and Molecular Biology.

Editors

Raman Chandrasekar
Brij Kishore Tyagi

ii

iii

iv

vi

ShortViewson

InsectBiochemistryand
MolecularBiology
Editedby
Raman Chandrasekar, Ph.D.,
Kansas State University, USA.
B.K.Tyagi, Ph.D.,
Centre for Research in Medical Entomology (ICMR), India.
Zhong Zheng Gui, Ph.D.,
Jiangsu University of Science and Technology,
Sericultural Research Institute, Chinese Academy of
Agricultural Sciences, China.
Gerald R. Reeck, Ph.D.,
Kansas State University, USA.

vii

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Contributing Authors

Dr. B.K.Tyagi

Prof.Fernando G. Noriega

Centre for Research in Medical Entomology,


4Sarojini Street, Chinna Chokkikulam,
Madurai 625002 (TN), India

Department of Biological Sciences


HLS 227, Florida International University
11200 SW 8th St, Miami, FL 33199, USA.

Prof. Gui Zhongzheng

Dr. Zhentao Sheng

Sericultural Research Institute,


Chinese Academy of Agricultural
Sciences, Zhenjiang, 212018,
Jiangsu, P. R. China.

Chicogo University, Chicogo, USA.

Prof. K. Sahayaraj

Prof.Yanyuan Bao
Institute of Insect Science,
Zhejiang University, China.

Dept. of Advanced Zoology and Biotechnology,


St. Xavier's College
Palayamkottai 627 002, Tamil Nadu, India.

Prof. Chuan-Xi Zhang,

Prof. David Siaussat

Dr. Maria L. Simes

Universit Pierre et Marie Curie (Paris 6/UPMC),


UMR 1272A Physiologie de l'Insecte:
Signalisation et Communication (PISC),
7 Quai Saint Bernard, Batiment A - 4me tage bureau 410, 75252 Paris Cedex 05, France.

Prof. PatriciaY.Scaraffia
Department of Tropical Medicine,
Tulane University, New Orleans,
LA 70112, USA.

Prof. Shou-An Xie

Institute of Insect Science,


Zhejiang University, China.

UEI Parasitologia Mdica,


Centro de Malria e Outras Doenas Tropicais,
Instituto de Higiene e Medicina Tropical,
Rua da Junqueira 96, 1300 Lisboa,
Portugal.

Dr. P. Somasundaram
Central Sericultural Germplasm Resources Centre,
P.B.No.44, Thally Road,
Hosur-635109,
Tamilnadu, India.

College of Forestry,
Northwest A & F University
Yangling, Shaanxi 712100, China

Dr. Hiroaki Abe

Dr. Raman Chandrasekar

Dr. S.K. Jalali

Department of Biochemistry and Molecular


Biophysics, Kanas State University,
Manhattan, 66506, KS, USA.

Prof. Gerald R. Reeck


Department of Biochem. and Molecular
Biophyscis, Kansas State University, KS, USA.

Prof. Manickam Sugumaran


Department of Biology
University of Massachusetts Boston
100 Morrissey Blvd,
Boston, MA 02125, USA.

Tokyo University of Agriculture and Technology,


Japan.

National Bureau of Agriculturally Important


Insects, ICAR, India.

Prof. Paraskeva V. Michailova


Institute of Biodiversity and
Ecosystem Research,
1 Tzar Osvoboditel boulv
Bulgarian Academy of Sciences
Sofia 1000, Bulgaria.

Prof. Ada Rafaeli


Associate Director for Academic Affairs &
International Cooperation
Agricultural Research Organization,
The Volcani Center, P. O. Box 6,
Bet Dagan 50250, Iseral.

ix

Prof. Emmanuelle Jacquin-Joly

Dr. Fei Liu

UMR PISC Physiologie de l'insecte


INRA, Route de Saint-Cyr
78026 Versailles cedex, France..

Department of Biological Science & Technol.,


Shaanxi Xueqian Normal University,
Shaanxi, China.

Dr. R. Srinivasan

Prof. Marian Goldsmith

Entomologist and Head of Entomology Group


AVRDC-The World Vegetable Center
60 Yi Ming Liao, Shanhua
Tainan 74151, Taiwan.

Biological Sciences Department,


University of Rhode Island,
Kingston, RI 02881, USA

Prof. Atanu Bhattacharyya

Prof. Anthony Ejiofor

Vidyasagar College for Women,


Post Graduate Department of Environmental
Science,
University of Kolkata, India.

Department of Biological Sciences,


College of Agriculture, Human & Natural
Sciences, Tennessee State University,
3500 John A Merritt Blvd., Nashville,
Tennessee 37209, USA.

Prof. Daphne Q.-D. Pham

Dr. Bharath Bhusan Patnaik

Dept of Biological Sciences,


University of Wisconsin-Parkside,
900 Wood Road, Kensoha,
WI 53144, USA.

School of Biotechnology,
Trident Academy of Creative Technology
(TACT), Bhubaneswar 751013 Odisha, India.

Prof. Jitrayut Jitonnom

Prof. B.R. Pittendrigh

School of Science
University of Phayao, Thailand.

Department of Entomology,
University of Illinois, Urbana-Champaign, IL,
61801, USA
.

Prof. K. Murugan

Dr. Subbiah Poopathi

Department of Zoology, School of Life Sciences,


Bharathiar University,
Coimbatore - 641 046, India.

Prof. Immo A. Hansen


Department of Biology,
New Mexico State University,
Las Cruces, NM, USA.

Dr. Ronald J. Nachman


USDA-ARS,
Food Animal Protection Research Laboratory,
USA.

Dr. Hari C Sharma


International Crops Research Institute for the
Semi-Arid Tropics (ICRISAT), Patancheru502324,
Andhra Pradesh, India.

Prof. Paolo Pelsoi


State Key Laboratory for Biology Plant Diseases
and Insect Pests, Institute of Plant Protection,
Chinease Academy of Agricultural Sciences,
Bejing, China.

Unit of Microbiology and Immunology,


Vector Control Research Centre
(Indian Council of Medical Research),
Medical complex, Indira Nagar,
Puducherry 60 5006, India.

Dr. P.Usha Rani


Biology and Biotechnology Division
Indian Institute of Chemical Technology
(CSIR)Taranaka,
Hyderabad - 500 007 (AP), India.

Dr. Fang Zhu


Irrigated Agriculture Research and Extension
Center, Dept.of Entomology,
Washington State University,
Prosser, WA, USA.

Prof. S.K.M. Habeeb


Department of Bioinformatics,
Faculty of Engineering & Technology,
SRM University, Kattankulathur,
Chennai 603203, Tamilnadu, India.

Prof. Yeon Soo Han


Division of Plant Biotechnology,
College of Agriculture & Life Science,
Chonnam National University,
Gwangju 500-757, South Korea

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Reviewer & External supportive members

Prof. Michael Riehle, Department of Entomology, University of Arizona, USA.


Dr. Dawn L.Geiser, College of Agriculture and Life Sciences, University of Arizona, USA.
Prof. Young Jung Kwon, School of Applied Biosci., Kyungpook National University, South Korea.
Dr. Kaliappandar Nellaiappan, CuriRx Inc. USA.
Prof. Patricia Y. Scaraffia, Department of Tropical Medicine, Tulane University, USA.
Prof. Richard Newcomb, Plant & Food Research, University of Auckland, New Zealand.
Dr. S. Krishnaswamy, School of Biotechnology, Madurai Kamaraj University, South India.
Dr. Mary-Anne Hartley, University of Lausanne, Switzerland.
Dr. Igor F. Zhimulev, Institute of Molecular and Cellular Biology, Novosibirsk, Russia.
Dr. S. Subramanin, Indian Agricultural Research Institute. India.
Prof. Gustavo F. Martins, Departament de Biologia Geral, Universidade Federal de Vicosa, Brazil.
Prof. Helena Janols, Infektionsklinien, Skanes Universitetsisjukhus, Sweden.
Prof. Donald R.Barnard, USDA, Agricultural Research Service, CMAVE, USA.
Dr. Keith White, Faculty of Life Science, University of Manchester, UK.
Prof. Marten J.Edwards, Biology Department, Muhlenberg College, USA.
Prof. E. Warchalowska-Sliwa, Polish Academy of Sciences, Poland.
Dr. K. Balakrishnan, Department of Immunology, Madurai Kamaraj University, India.
Dr. J.Joe Hull, USAD-ARS, Arid Land Agricultural Research Centre, USA.
Dr. Neil Audsley, The Food & Environment Research Agency, UK.
Dr. Raman Chandrasekar, Kansas State University, USA.
Dr. B.K. Tyagi, Centre for Research in Medical Entomology (ICMR), Madurai, TN, India.
Prof. Zhongzheng Gui, Sericulture Research Institute, Chinese Academy of Agricultural Sci., China.
Dr. Fang Zhu, Irrigated Agril. Research and Extension Center, Washington State University, USA.
Prof. K. Murugan, Department of Zoology, Bharathiar University, Coimbatore, India.
Dr. Xiao-Wei Wang, Institute of Insect Science, Zhejiang University, China.
Dr. Haijun Xu, Institute of Insect Science, Zhejiang University, China.
Dr. Alisha Anderson, CSIRO Ecosystem Sciences, Australia.
Prof. Eric D.Dodds, Department of Chemistry, University of Nebraska-Lincoln, USA.
Prof. P. Mosae Selvakumar, Department of Chemistry, Karnaya University, Coimbatore, India.
Prof. A.K.Dikshit, Indian Agriculture Research Institute, New Delhi.
Prof. K.R.S. Sambasiva Rao, Dept. of Biotech. & Zoology, Acharya Nagarjuna University, India
Dr. R. Rangeshwaran, National Bureau of Agriculturally Important Insects, Banglore, India.
Dr. V. Selvanarayanan, Faculty of Agriculture, Annamalai University, Tamil Nadu, India.
Prof. Fernando G. Noriega, Florida International University, Miami, USA.
Prof. Ada Rafaeli, Department of Food Quality and Safety, A.R.O., Israel.
Prof. Daphne Q.-D. Pham, Dept. of Biological Sciences, University of Wisconsin-Parkside, USA.
Prof. Emmanuelle Jacquin-Joly, INRA, UMR 1272 Physiologie de lInsecte, Versailles, France.
Prof. Manickam Sugumaran, University of Massachusetts Boston, USA.
Prof. Nannan Liu, Auburn University, USA.
Prof. Michihiro Kobyashi, Nagoya University, Japan.
Prof. Enoch Y.Park, Innovative Joint Research Center, Shizuoka University, Japan.
Prof. Luiz Paulo Moura ANDRIOLI, Universidade de So Paulo, SP - Brazil
Prof. SHIMADA Toru, The University of Tokyo, Japan.
Prof. Erjun Ling, Institute of Plant Physiology and Ecology, China.

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Acknowledgements
Writing and publishing a book requires the assistance of individuals who are
creative, talented, and hard-working. All of these qualities were present in the
individuals assembled to produce this book volume. I would like to express my
heartfelt gratitude to my former teacher Prof. Seo Sook Jae, (GSNU, South Korea),
Prof. Subba Reddy Palli (University of Kentucky, USA), and other external mentors
Prof. Marian R. Goldsmith (University of Rhode Island, USA), Prof. Enoch Y. Park
(Shizuoka University, Japan), Prof. M. Kobayashi (Nagoya University, Japan), Prof.
CHU Jang Hann (National University of Singapore, Singapore), Prof. Thomas W.
Sappington (USDA-ARS, USA), Prof. Fernando G. Noriega (Florida International
University, USA), Dr. Srinivasan Ramasamy, AVRDC, The World Vegetable
Center, Taiwan), Dr. H.C. Sharam (ICRISAT, India), who inspiration and
supported me at many ways for the commencement of this International Book
Mission Program. The book mission program was initiated on May 2010,
completed on March 2014 and published on October 2014. I have no words to
express my feeling for all those who provided valuable contributions from USA,
South Korea, Japan, China, India, Thailand, Taiwan, Bulgaria, France, Iseral, and
Portugal (Contributors name list, see page no. v) and made the completion of this
book possible. We express our appreciation to the following people (Reviewer
name list, see page no. vii) who reviewed various part of the manuscript as it was
being developed and improved quality of each chapter. I thank the ICMR, New
Delhi, and Chinese Academy of Agricultural, China, and Kansas State University for
support from several aspects. Many others (scientists and publishers) have also
allowed us to use their materials in the various chapters, their color image have then
been converted to gray color/BW. Iam especially indebted to International Book
Mission Organization, Academic Publishing Services for the production of book. I
thank my Co-Editors for their continuous vigilance over the book project and for
always giving advance notice of the editing and proofreading schedules. I thank also
my Brintha, P.G., (my wife), who in all possible way, encouragement helped
transform our original efforts into an acceptable final form. I apologize to those
whose work could not be cited owing to space considerations limitation. Further, I
wish to recognize the moral support extended by colleagues and friends. I hope that
this volume will inspire interest on the diverse aspects of insect biochemistry and
molecular biology in aspiring and established scientists.
Raman Chandrasekar

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A Note from the Publisher


Dear Readers,
This edition represents the first number of the Short Views on Insect
Biochemistry and Molecular Biology book series published by International
Book Mission. It serves to show the public how important entomology field in
expanding basic knowledge or in the development of new technologies nowadays,
in virtually all fields of knowledge. We called for piece of work falling into two
volumes (Basic and Advance aspects).
Far from being complete, the 30 chapters clearly structured and simply explained
experts contributions may provide an overview about current and prominent
advances in insect biochemistry and molecular biology which will help students and
researchers to broaden their knowledge and to gain an understanding of both the
challenges and the opportunities behind each approach.
We look forward to receiving new proposals for the new edition 2015 - 2017.
International Book Mission
Academic Publisher
Manager

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Book Series

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