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Green synthesis of metal nanoparticles using

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Article in Green Chemistry · October 2011

DOI: 10.1039/C1GC15386B

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Green synthesis of metal nanoparticles using plants
Siavash Iravani*
Received 10th April 2011, Accepted 20th July 2011
DOI: 10.1039/c1gc15386b

In recent years, the development of efficient green chemistry methods for synthesis of metal
nanoparticles has become a major focus of researchers. They have investigated in order to find an
eco-friendly technique for production of well-characterized nanoparticles. One of the most
considered methods is production of metal nanoparticles using organisms. Among these organisms
plants seem to be the best candidates and they are suitable for large-scale biosynthesis of
nanoparticles. Nanoparticles produced by plants are more stable and the rate of synthesis is faster
than in the case of microorganisms. Moreover, the nanoparticles are more various in shape and size
in comparison with those produced by other organisms. The advantages of using plant and
plant-derived materials for biosynthesis of metal nanoparticles have interested researchers to
investigate mechanisms of metal ions uptake and bioreduction by plants, and to understand the
possible mechanism of metal nanoparticle formation in plants. In this review, most of the plants
used in metal nanoparticle synthesis are shown.

1. Introduction and single-walled carbon nanotube nanocapsules encapsulating

“Nanotechnology is the application of science to control matter
at the molecular level”.1 Tremendous growth in nanotechnology
has opened up novel fundamental and applied frontiers in
materials science and engineering, such as nanobiotechnology,2
bionanotechnology,3 quantum dots,4 surface-enhanced Raman
scattering (SERS),5 and applied microbiology. Developments
in the organization of nanoscale structures into predefined
superstructures ensure that nanotechnology will play a critical
role in many key technologies. It is gaining importance in
areas such as mechanics, optics, biomedical sciences, chemi-
cal industry, electronics, space industries, drug-gene delivery,
energy science, catalysis,6,7 optoelectronic devices,8,9 photo-
electrochemical applications,10 and nonlinear optical devices.11,12
For instance, nanometre-scale geranium quantum dots (less
than 10 nm) could be controllably formed for novel optoelec-
tronic device applications such as single electron transistors
(SETs) and light emitters.13 The ability to tune the optical ab-
sorption/emission properties of quantum dots (semiconductor
nanoparticles) by simple variation in nanoparticle size is partic-
ularly attractive in the facile band-gap engineering of materials14
and the growth of quantum dot lasers.15 Moreover, advances in
nanotechnology are creating a novel class of magnetic resonance
image contrast-enhancing agents such as small particles of
iron oxide, fullerenes encapsulating Gd3+ ions (gadofullerenes),
Biotechnology Department, Faculty of Pharmacy and Pharmaceutical
Sciences, Isfahan University of Medical Sciences, Isfahan, Iran.
E-mail: siavashira@gmail.com; Fax: +98 311 6251011; Tel: +98
9132651091
Gd3+ ion clusters (gadonanotubes).16
Nanoparticles are of great interest due to their extremely
small size and large surface to volume ratio, which lead to
both chemical and physical differences in their properties
(e.g. mechanical properties, biological and sterical properties,
catalytic activity, thermal and electrical conductivity, optical
absorption and melting point) compared to bulk of the same
chemical composition.17–19 Therefore, design and production of
materials with novel applications can be achieved by controlling
shape and size at nanometre scale. Nanoparticles exhibit size and
shape-dependent properties which are of interest for applications
ranging from biosensing and catalysts to optics, antimicrobial
activity, computer transistors, electrometers, chemical sensors,
and wireless electronic logic and memory schemes. These
particles also have many applications in different fields such
as medical imaging, nanocomposites, filters, drug delivery,
and hyperthermia of tumors.20–23 There are many important
applications for metal nanoparticles in medicine and pharmacy.
Gold and silver nanoparticles are the most common ones used
for biomedical applications and in emerging interdisciplinary
field of nanobiotechnology. For instance, oligonucleotide-
capped gold nanoparticles have been used for polynucleotide
or protein detection using various detection/characterization
methods, including atomic force microscopy, gel electrophoresis,
scanometric assay, surface plasmon resonance imaging, am-
plified voltammetric detection, chronocoulometry, and Raman
spectroscopy.24,25 Furthermore, gold nanoparticles have been
employed in immunoassay,26 protein assay,27 cancer nanotech-
nology (especially detection of cancer cells),28 and capillary
electrophoresis.29 In the field of medicine, gold nanoparticles

2638 | Green Chem., 2011, 13, 2638–2650 This journal is © The Royal Society of Chemistry 2011
are used for different proposes. They can be used as markers
for biological screening test. After cellular uptake, they can
act as precise and powerful heaters (thermal scalpels) to kill
cancer.30,31 Moreover, gold nanoparticles are capable of inducing
apoptosis in B cell-chronic lymphocytic leukemia (chronic
lymphoid leukemia).32 Silver nanoparticles have drawn the
attention of researchers because of their extensive applications
in areas such as integrated circuits,33 sensors,34 biolabelling,34
filters,34 antimicrobial deodorant fibres,35 cell electrodes,36 and
antimicrobials.103,104 Antimicrobial properties of silver nanopar-
ticles caused the use of these nanometals in different fields
of medicine, various industries, animal husbandry, packaging,
accessories, cosmetics, health and military. Silver nanoparticles
show potential antimicrobial effects against infectious organ-
isms such as Escherichia coli, Bacillus subtilis, Vibria cholera,
Pseudomonas aeruginosa, Syphillis typhus, and Staphylococcus
aureus.37,38
Nanoparticles have been produced physically and chemically
for a long time, but recent developments show the critical
role of microorganisms and biological systems in production
of metal nanoparticles (Fig. 1 and 2). The use of organisms
in this area is rapidly developing due to their growing success
and ease of formation of nanoparticles. Moreover, biosynthesis
of metal nanoparticles is an environmentally friendly method
(green chemistry) without use of harsh, toxic and expensive
chemicals.39–42 For instance, production of silver nanoparticles
by chemical reduction (e.g., hydrazine hydrate, sodium boro-
hydride, DMF, and ethylene glycol) may lead to absorption of
harsh chemicals on the surfaces of nanoparticles raising the
toxicity issue.
The organisms used in nanoparticle synthesis vary from sim-
ple prokaryotic bacterial cells to complex eukaryotes.43 Actually,
the ability of organisms in production of metal nanoparticles
has opened a new exciting approach toward the development
of these natural nano-factories. The important aspects which
Fig. 1 Some important manufacturing methods used in nanoparticle synthesis.
This journal is © The Royal Society of Chemistry 2011
might be considered in the process of producing highly stable
and well-characterized nanoparticles are as follows:
1. Selection of the best organisms: In order to choose the
best candidates for metal nanoparticle production, researchers
have focused on the important intrinsic properties of the
organisms such as enzyme activities and biochemical pathways.
For example, plants which have great potential in heavy metal
accumulation and detoxification are the best candidates for
nanoparticle synthesis.
2. Optimal conditions for cell growth and enzyme activity:
Optimization of the growth conditions is very important. The
nutrients, inoculum size, light, temperature, pH, mixing speed,
and buffer strength should be optimized. The presence of the
substrates or related compounds in subtoxic levels from the
beginning of the growth would increase the activity of the
enzymes.
3. Optimal reaction conditions: In order to use the organisms
for synthesis of metal nanoparticle in industrial scale, the yield
and the production rate are important issues to be considered.
Therefore, we need to optimize the bioreduction conditions in
the reaction mixture.39,43 The substrate concentration, the bio-
catalyst concentration, the electron donor and its concentration,
pH, exposure time, temperature, buffer strength, mixing speed,
and light need to be controlled and optimized. For example,
it was demonstrated that reaction time and dodecanethiol (as
the capping ligand) were important parameters in controlling
size and morphology of the gold nanoparticles produced by
reaction of the AuCl4 - ions with Bacillus megatherium biomass.44
Moreover, researchers have used some complementary factors
such as visible light or microwave irradiation, and boiling which
could affect the size, morphology, and rate of reaction.
Optimization of these crucial factors could control morpholo-
gies and other properties of nanoparticles. This exciting improve-
ment toward the use of eco-friendly methods for production of
nanoparticles with desired morphological characteristics and
Green Chem., 2011, 13, 2638–2650 | 2639
 Fig. 2 Some important synthetic methods for synthesis of gold, silver, palladium, zinc oxide, copper, magnetite, and indium oxide nanoparticles.
sizes might facilitate researcher’s abilities to overcome many
limitations of this field.
Biosynthesis of metal nanoparticles by plants is currently un-
der exploitation. The biological synthesis of metal nanoparticles
(especially gold and silver nanoparticles) using plants (inacti-
vated plant tissue, plant extracts and living plant) has received
more attention as a suitable alternative to chemical procedures
and physical methods. Synthesis of metal nanoparticles using
plant extracts is very cost effective, and therefore can be used
as an economic and valuable alternative for the large-scale
production of metal nanoparticles. Extracts from plants may act
both as reducing and capping agents in nanoparticle synthesis.
The bioreduction of metal nanoparticles by combinations of
biomolecules found in plant extracts (e.g. enzymes, proteins,
amino acids, vitamins, polysaccharides, and organic acids such
as citrates) is environmentally benign, yet chemically complex.
Because of the important and critical roles of plants in bio-based
protocols for metal nanoparticle production, the green synthesis
of metal nanoparticles using plants has been discussed in this
review.
2. Plant biomass and/or living plant
Plants have shown great potential in heavy metal accumulation
and detoxification.45 Several studies widely reported detoxifica-
tion and hyper-accumulation of toxic metals by plants, such as
Arabidopsis halleri and Thlaspi caerulescens.46,47 Different kinds
of plants such as Acanthopanax sciadophylloides, Maytenus
2640 | Green Chem., 2011, 13, 2638–2650
founieri, Brassica juncea, Ilex crenata, Sesbania drummondii,
and Clethra barbinervis have potential capacity for phytore-
mediation of heavy metals.45–48 Trace elements (heavy metals
and metalloids) are important environmental pollutants, and
are toxic even at very low concentrations. The use of plant
biomass for metal removal from aqueous solutions (known as
biosorption) gained attention because it has shown to be very
promising for the removal of contaminants from effluents in
an eco-friendly approach. The natural phenomenon of heavy
metal tolerance of plants has interested researchers to investi-
gate the related biological mechanisms as well as physiology
and genetics of metal tolerance in hyperaccumulator plants
(Fig. 3).
Researchers pay attention to use of plants with potential in
phytomining and phytoremediation of heavy metals in order
to phytosynthesise metallic nanoparticles. Gardea-Torresdey
et al. have reported for the first time the formation of gold
and silver nanoparticles inside living plants.49,50 They have
demonstrated the synthesis of gold and silver nanoparticles
within live Medicago sativa (alfalfa) plants by gold and silver ion
uptake, respectively, from solid media. The alfalfa plants were
grown in an AuCl4 - -rich environment. The information about
uptake and formation of these nanoparticles was confirmed
by X-ray absorption spectroscopy (XAS) and transmission
electron microscopy (TEM). The gold nanoparticles were in
crystalline state. Additionally, icosahedral particles (~4 nm)
and face centered cubic (fcc) twinned particles (6–10 nm) were
observed. In a related report, agricultural biomass was used to
This journal is © The Royal Society of Chemistry 2011

Fig. 3 Important mechanisms of heavy metal tolerance in plants.
reduce Cr(VI) to Cr(III) ions, indicating that biological methods
could be very efficient in decontaminating polluted waters and
soil polluted with heavy metal ions.51 Morphologies of gold
particles obtained by reacting gold(III) with alfalfa biomass
include irregular shaped, fcc tetrahedral and hexagonal platelet
particles which were larger than decahedral and icosahedral
multiple twinned particles.52
Magnetite nanoparticles attracted great attention for many
important technological and biomedical applications such as
drug delivery, cancer hyperthermia, optical and nanoelectronic
devices, magnetic separation, and magnetic resonance imaging
enhancement.53 Various chemical and physical methods have
been reported in order to synthesise magnetite nanoparticles,
but some of the chemical procedures involved in the synthesis
of these nanoparticles use toxic solvents which could poten-
tially generate unsafe and hazardous byproducts, and often
involve high energy consumption.54–56 New methods for growing
nanoparticles are exploring the use of biological systems. It was
reported that iron oxide nanoparticles could be synthesized
by using alfalfa biomass.57 pH 10 yielded smaller particles
with greater proportion of the Fe2 O3 , and the size could be
controlled in the range of 1–4 nm. When pH decreased (pH 5),
larger nanoparticles were produced. In another study, Au-
Fe3 O4 composite nanoparticles were prepared with a combined
chemical and biological reducing process (semi-biosynthesis
method). Magnetic cores were primarily produced using a
fabrication method consisting of coprecipitation of Fe2+ and
Fe3+ . An ethanol extract of Eucalyptus camaldulensis was used
for the reduction of Au+3 on the surface of the magnetite
nanoparticles and for the functionalization of the Au-Fe3 O4
nano-composite particles.58
Armendariz et al.59 reported for the first time the formation of
rod-shaped nanoparticles by biomaterials. They characterized
the gold nanoparticles formed by wheat biomass exposed to
a 0.3 mM potassium tetracholoaurate solution at pH values
of 2–6 at room temperature. It was concluded that wheat
biomass was able to reduce Au(III) to Au (0) forming fcc
tetrahedral, hexagonal, decahedral, icosahedral multitwinned,
irregular, and rod-shaped nanoparticles. In another study, pH
This journal is © The Royal Society of Chemistry 2011
dependent synthesis of rod-shaped Au nanoparticles using Avena
sativa (oat) has shown that biomass might carry more positive
functional groups such as positive amino groups, sulfhydryl
groups and carboxylic groups which allowed the Au(III) ions
to get more closure to binding sites and approved the reduction
of Au(III) to Au(0).60,61 A 0.1 mM solution of Au(III) was reacted
with powdered oat biomass at pH values of 2–6 for one hour.
As in the case of wheat, oat biomass produced fcc tetrahedral,
hexagonal, decahedral, icosahedral multitwinned, irregular, and
rod-shaped nanoparticles. It was reported that most of the
nanoparticles synthesized by using alfalfa, wheat, and oat at
pH 2 had an irregular shape. However, it seems that pH has a
major impact on the size of the produced nanoparticles rather
than on the shape of them.
Sterilized geranium leaves (P. graveolens) when exposed to
chloroaurate ions separately resulted in rapid reduction of the
metal ions and formation of stable gold nanoparticles of variable
size. The reduction of the AuCl4 - ions was nearly complete
after 60 min of reaction and the particles (20–40 nm) were
predominantly decahedral and icosahedral in shape.62
Not only silver nanoparticles (55 to 80 nm) could be produced,
but also triangular or spherical gold nanoparticles could be
easily formed by reaction of the novel sundried biomass
of Cinnamomum camphora leaf with aqueous silver or gold
precursors at ambient temperature.42 Size dispersity of quasi-
spherical silver nanoparticles as well as triangular or spherical
shapes of gold nanoparticles could be facilely controlled by
simple variation of the amount of biomass reacting with
aqueous solution of AgNO3 or HAuCl4 . When Huang et al.
switched the amount of the dried biomass from 0.1 to 0.5 g
subjected to the same chloroauric acid, the particles shifted
from nanotriangles to spherical particles. The utilization of
sundried C. camphora leaf for biosynthesis of the nanoparticles
has some defects. For example, the drying process of the leaf in
the sun was time-consuming. The polyol components and the
water soluble heterocyclic components were mainly found to
be responsible for the reduction of silver or chloroaurate ions
and the stabilization of the nanoparticles, respectively. Huang
et al.63 investigated biological production of silver nanoparticles
by lixivium of sundried C. camphora leaf in continuous-flow
tubular microreactors. They introduced polyols in the lixivium
as possible reducing agents.
Harris et al.64 have investigated the limits (substrate metal
concentration and time exposure) of uptake of metallic silver
by two common metallophytes, Brassica juncea and Medicago
sativa. They demonstrated that B. juncea and M. sativa could be
used in phytosynthesis (a broad application of phytoextraction)
of metallic silver nanoparticles. B. juncea, when exposed to
an aqueous substrate containing 1000 ppm silver nitrate for
72 h, accumulated up to 12.4 wt% silver. M. sativa accumulated
up to 13.6 wt% silver when exposed to an aqueous substrate
containing 10 000 ppm silver nitrate for 24 h. In the case
of M. sativa, an increase in metal uptake was observed with
a corresponding increase in the exposure time and substrate
concentration. In both cases, TEM analysis showed the presence
of roughly spherical silver nanoparticles, with a mean size of
50 nm. In another study, after a 9-week growth in gold, silver,
and copper-enriched soil, seeds of B. juncea grow into a plant
containing Au–Ag–Cu alloy nanoparticles.65
Green Chem., 2011, 13, 2638–2650 | 2641
 Sesbania drummondii is a medium-sized perennial shrub
in the legume family Fabaceae. S. drummondii (leguminous
shrub) seedlings could uptake high amounts of gold(III) ions,
resulting in intracellular formation of monodispersed spherical
gold nanoparticles (6–20 nm) inside plant cells or tissues.66
The catalytic function of the nanoparticle-rich biomass was
substantiated by the reduction of aqueous 4-nitrophenol (haz-
ardous and toxic pollutant). Attractively, nanoparticle-bearing
biomatrix of S. drummondii reduced aqueous 4-nitrophenol (4-
hydroxynitrobenzene).
3. Plant extracts
Current research in biosynthesis of nanometals using plant
extracts has opened a new era in fast and nontoxic methods for
production of nanoparticles. Many researchers have reported
the biosynthesis of metal nanoparticles by plant leaf extracts
and their potential applications.40,41,62,67–72 Sastry et al. have
studied bioreduction of gold and silver ions by leaf broth of
Pelargonium graveolens62,67 and Azadirachta indica.71 Moreover,
they have explored the formation mechanism of triangular gold
nanoprisms by Cymbopogon flexuosus (lemongrass) extracts,
the nano-triangles seemed to grow by a process involving
rapid bioreduction, assembly and room-temperature sintering of
‘liquid-like’ spherical gold nanoparticles.40 Also rapid synthesis
of stable gold nanotriangles using Tamarindus indica (tamarind)
leaf extract as reducing agent could be achieved.72 The shape
of metal nanoparticles considerably changed their optical and
electronic properties.73 They have demonstrated synthesis of gold
and silver nanoparticles with variety of shapes (spherical and
triangular) and sizes using Aloe vera plant extracts, as well.68 It
was explained that only biomolecules of molecular weights less
than 3 kDa caused reduction of chloroaurate ions, leading to the
formation of gold nanotriangles. Nevertheless, the bioreduction
of silver ions proceeded merely in the presence of ammonia.
The aqueous solution of gold ions when exposed to Coriandrum
sativum leaf extract was reduced and resulted in the extracellular
biosynthesis of gold nanoparticles with spherical, triangle,
truncated triangle and decahedral morphologies ranging from
6.75 nm to 57.91 nm. These nanoparticles were stable in solution
over a period of one month at room temperature.74
Shankar et al.71 have reported the biosynthesis of pure metallic
nanoparticles of silver and gold by the reduction of aqueous
Ag+ and AuCl4 - ions and also the synthesis of bimetallic
core-shell nanoparticles of gold and silver by simultaneous
reduction of aqueous Ag+ and AuCl4 - ions with the broth of
neem leaves (A. indica). They observed that the metal particles
were stable in solution even 4 weeks after their synthesis.
Moreover, stabilizing the nanoparticles was possibly facilitated
by reducing sugars and/or terpenoids present in the neem leaf
broth. The silver nanoparticles formed were predominantly
spherical and polydisperse with diameters in the range 5 to
35 nm. Gold nanoparticles synthesized using neem leaf broth
appeared to have a propensity to form thin, planar structures
rather than just spherical particles. The planar particles formed
were predominantly triangular with a very small percentage of
hexagonal shaped particles.71
Geranium leaf (P. graveolens) broth, when exposed to aqueous
silver nitrate solution, resulted in extracellular enzymatic synthe-
2642 | Green Chem., 2011, 13, 2638–2650
sis of stable crystalline silver nanoparticles.67 The bioreduction
of the metal ions was fairly rapid, occurred readily in solution,
and resulted in a high density of stable silver nanoparticles in
the size range 16–40 nm. The produced nanoparticles appeared
to be assembled into open, quasilinear superstructures and were
predominantly spherical in shape. It was believed that proteins,
terpenoids and other bio-organic compounds in the geranium
leaf broth participated in the bioreduction of silver ions and
in the stabilization of the nanoparticles thus formed by surface
capping. Shankar et al.62 reported the possibility of terpenoids
from geranium leaf in the silver nanoparticle synthesis. Polyols
such as terpenoids, polysaccharides, and flavones in the C.
camphora leaf were believed to be the main cause of the
reduction of silver and chloroaurate ions.42 Moreover, green
synthesis of nanosilver particles using methanol extract of
Eucalyptus hybrida (safeda) leaf was reported. Flavanoid and
terpenoid constituents which present in E. hybrid leaf extract
are responsible for stabilization of produced silver nanoparticles
(50–150 nm).75 Cinnamon zeylanicum bark extract could be used
in biosynthesis of cubic and hexagonal silver nanocrystals (31–
40 nm).76 The particle size distribution varied with variation
in the dosage of C. zeylanicum bark extract. The number of
particles increased with increasing dosage due to the variation
in the amount of reductive biomolecules. Small nanoparticles
were formed at high pH. The shape of silver nanoparticles at
high pH was more spherical in nature rather than ellipsoidal.
Moreover, bactericidal effect of produced nano-crystalline silver
particles was tested against E. coli strain. As a result, the various
tested concentrations of 2, 5, 10, 25, and 50 mg L-1 produced
inhibition of 10.9, 32.4, 55.8, 82, and 98.8%, respectively. The
minimum inhibitory concentration was found to be 50 mg L-1 . C.
zeylanicum bark is rich in terpenoids (linalool, methyl chavicol,
and eugenol) and in chemicals (such as cinnamaldehyde, ethyl
cinnamate, and b-caryophyllene) which contribute to its special
aroma. Furthermore, proteins are also present in the bark. It
was believed that water-soluble organics present in C. zeylanicum
bark were the reasons of the bioreduction of silver ions to nano-
sized Ag particles. Moreover, proteins from C. zeylanicum bark
capped the produced nanoparticles either through free amine
groups or cysteine residues, and thus stabilized them.76
Complimentary investigations have explained that Capsicum
annuum L. extract contains proteins with amine groups, which
played a reducing and controlling role during the formation of
silver nanoparticles in the solutions.77 Li et al.78 have shown
rapid precipitation of a-Se/protein in room temperature using
proteins extracted from C. annuum L. They also demonstrated
that proteins and vitamin C presented in C. annuum L. extract
were responsible for the synthesis of a-Se nanoparticles. The
proteins also stabilized nanoparticles via precipitation on their
surfaces and formation of a-Se/protein composites. The size and
shell thickness of the a-Se/protein composites were increased in
high concentrations of C. annuum L. extract, but decreased at
low pH values.
The reaction of aqueous silver ions with Desmodium trifolium
extract resulted in extracellular production of silver nanoparti-
cles at room temperature.79 The authors of this article believed
that H+ ions produced along with NAD during glycolysis were
responsible for formation of nanosilver particles as well as
water soluble antioxidative agents (e.g. ascorbic acids). These
This journal is © The Royal Society of Chemistry 2011
antioxidative agents were especially participating in reduction
of silver ions. Jha et al.80 used biotechnological method for
production of silver nanoparticles. They demonstrated that
Cycas leaf extract could be used in order to produce stable silver
nanoparticles. X-Ray data indicated that silver nanoparticles
had fcc unit cell structure. Phytochemicals such as polyphenols,
glutathiones, metallothioneins (a family of cysteine-rich, low
molecular weight proteins), and ascorbates probably were
responsible for formation of the nanoparticles. Glutathione
was implicated to play an important role in plants exposed to
metal stress, and metallothioneins have the capacity to bind
both xenobiotic (e.g. cadmium, silver, mercury, and arsenic)
and physiological (e.g. zinc, selenium, and copper) heavy metals
through the thiol group of their cysteine residues. Antioxidant
action of phenolic compounds (these compounds consist of
catechin, taxifolin, procyanidins of various chain lengths formed
by catechin and epicatechin units, and phenolic acids) is due
to their high tendency to chelate metals. Phenolic compounds
possess hydroxyl and carboxyl groups, may inactivate iron
ions by chelating and additionally suppressing the superoxide-
driven Fenton reaction, which is believed to be the most
important source of reactive oxygen species (ROS). There-
fore, plants with high content of phenolic compounds (e.g.
Pinus species) are one of the best candidates for nanoparticle
synthesis.
High density of extremely stable silver nanoparticles (16–40
nm) were rapidly synthesized by challenging silver ions with
Datura metel (a plant of family Solanaceae) leaf extract.81
Leaf extracts of this plant contain biomolecules such as al-
kaloids, proteins/enzymes, amino acid, alcoholic compound,
and polysaccharides which could be used as reluctant to react
with silver ions and scaffolds to direct the formation of silver
nanoparticles in solution. Quinol (alcoholic compound) and
chlorophyll pigment were responsible for reduction of silver
ions and stabilization of produced nanoparticles. The use of
pure natural constituents to reduce and stabilize the metal
nanoparticles is under investigation. Kasthuri et al.82 have
shown the ability of apiin compound extracted from henna
leaves to produce anisotropic gold and quasi-spherical silver
nanoparticles. Secondary hydroxyl and carbonyl groups of apiin
compound were responsible for the bioreduction of metal salts.
In order to control the size and shape of nanoparticles, they used
different amounts of apiin compound (as the reducing agent).
The nanoparticles were stable in water for 3 months, which could
be attributed to surface binding of apiin compound with the
reduced materials. In another study, geraniol as a volatile com-
pound obtained from P. graveolens was used for biosynthesis of
silver nanoparticles (1–10 nm). The cytotoxicity of the produced
silver nanoparticles was evaluated in vitro against Fibrosarcoma
Wehi 164 at different concentration (1–5 g ml-1 ).83 As a result,
the presence of 5 g ml-1 of silver nanoparticles significantly
inhibited the cell line’s growth (up to 60%). Therefore, it seems
that silver nanoparticles have inhibitory effects against the
proliferation of cancer cells. Bayberry tannin (a natural plant
polyphenol) was used for the one-step synthesis of Au@Pd core–
shell nanoparticles in aqueous solution at room temperature.
Bayberry tannin is able to preferentially reduce Au3+ ions to
Au nanoparticles when placed in contact with an Au3+ /Pd2+
mixture, and subsequently the formed gold nanoparticles served
This journal is © The Royal Society of Chemistry 2011
as in situ seeds for the growth of a Pd shell, resulting in the
formation of Au@Pd nanoparticles.84
Song et al.85 have elucidated that Pinus desiflora, Diospyros
kaki, Ginko biloba, Magnolia kobus and Platanus orientalis
leaves broth synthesized stable silver nanoparticles with average
particle size ranging from 15 to 500 nm, extracellularly. In
the case of M. kobus and D. kaki (persimmon) leaf broth,
synthesis rate and final conversion to silver nanoparticles
became faster when reaction temperature increased. But the
average particle sizes produced by D. kaki leaf broth decreased
from 50 nm to 16 nm when temperature increased from 25 ◦ C
to 95 ◦ C. They also illustrated that only 11 min was required
for more than 90% conversion at the reaction temperature
of 95 ◦ C using M. kobus leaf broth.85 Bimetallic Au/Ag
nanoparticles were formed with some cubic structures, by the
interactions between the bound bio-organic capping molecules
and gold and silver nanoparticles.86 In another study, it was
reported that M. kobus and D. kaki were capable of eco-
friendly extracellular production of metallic gold nanoparticles
(5–300 nm) with different triangular, pentagonal, hexagonal,
and spherical shapes within a few minutes (for up to 90%
conversion at a reaction temperature of 95 ◦ C).87 It was suggested
that the rate of synthesis of the nanoparticles was related to the
reaction and incubation temperature, and increased temperature
levels allowed nanoparticle growth at a faster rate. Moreover, by
increasing the temperatures and leaf broth concentrations, size
of nanoparticles became smaller. Fourier transformed infrared
spectroscopy (FTIR) analysis has shown that gold nanoparticles
produced by M. kobus extract were surrounded by proteins
and metabolites (such as terpenoids having functional groups
of amines, aldehydes, carboxylic acid, and alcohols). It was
also reported that the use of low concentration of phyllanthin
extract reacting with HAuCl4 led to production of hexagonal or
triangular gold nanoparticles, but spherical nanoparticles could
be formed by addition of higher concentration of the extract.87
Vilchis-Nestor et al.88 have used green tea (Camellia sinensis)
extract to produce gold nanoparticles and silver nanostructures
in aqueous solution at ambient conditions. They also investi-
gated control of size, morphology, and optical properties of
the nanostructures and reported initial concentrations of metal
ions and tea extract as controlling factors. It was investigated
that when the amount of C. sinensis extract was increased, the
resulted nanoparticles were slightly bigger and more spherical.
The authors of this study believed that phenolic acid-type
biomolecules present in C. sinensis extract were responsible for
production and stabilization of silver and gold nanoparticles.
Caffeine and theophylline present in tea extracts might be
responsible for catalysis and synthesis of nanoparticles. In
another study, black tea leaf extracts were used in production
of Au and Ag nanoparticles.89 The nanoparticles are stable and
have different shapes, such as spheres, trapezoids, prisms, and
rods. Findings of this study have demonstrated that polyphenols
and flavonoids were responsible for synthesis of nanoparticles.
Mode et al.90 reported production of spherical silver nanopar-
ticles (60–80 nm) using callus extract of Carica papaya. Proteins
and other ligands seemed to be responsible for the synthesis
and stabilization of silver nanoparticles. Furthermore, fcc silver
nanoparticles (10–20 nm) were synthesized by using the latex
of Jatropha curcas as reducing and capping agent.91 It was
Green Chem., 2011, 13, 2638–2650 | 2643
demonstrated that leaf extracts from the aquatic medicinal plant,
Nelumbo nucifera (Nymphaeaceae), could be able to reduce silver
ions and produce silver nanoparticles (with an average size of
45 nm) in different shapes.92 Biosynthesized silver nanoparticles
showed larvicidal activity against malaria (Anopheles subpictus)
and filariasis (Culex quinquefasciatus) vectors. Silver and gold
nanoparticles were synthesized biologically by using Sorbus
aucuparia leaf extract within 15 min. Produced nanoparticles
were found to be stable for more than 3 months. The authors
of this study believed that sorbate ion in the leave extract of
S. aucuparia encapsulated the nanoparticles and this matter
was responsible for maintenance of the stability.93 The effect
of leaf extract quantity, substrate concentration, temperature,
and contact time were also evaluated to optimize the process of
producing nanoparticles. With increase in the concentration of
metal ions from 10-4 to 10-2 M, increase in particle size was also
found.
Biosynthesis of silver and gold nanoparticles using fruit
extracts has been investigated by some authors. For example,
Emblica officinalis fruit extract produced highly stable Ag and
Au nanoparticles extracellularly.41 Pear fruit extract could be
used in order to room-temperature biosynthesis of triangular
and hexagonal gold nanoparticles (200–500 nm).94 Pear extract
contains essential phytochemicals consisting of organic acids,
peptides, proteins, and amino acids. In addition, it contains
saccharides which provide synergetic reduction power for the
bioreduction of chloroaurate ions into gold nanoparticles.
The pear fruit extract when exposed to chloroaurate ions
in an alkaline condition resulted in gold nanoparticles with
plate-like morphologies in a highly productive state. The gold
nanoparticles formed under normal conditions also exhibited
plate-like morphologies with a low productivity. In addition,
green synthesis of silver and gold nanoparticles with spherical
and triangular shapes by fruit extract of Tanacetum vulgare
has been reported.95 Ag and Au nanoparticles were 16 and
11 nm in size. Carbonyl group was involved in synthesis of these
nanoparticles. The effect of pH on zeta potential of the produced
nanoparticles has been investigated. Zeta potential values reveal
details about the surface charge and stability of the syn-
thesized metal nanoparticles.95 Actually, stability of produced
metal nanoparticles are evaluated with zeta potentiometer and
corresponding surface plasmon spectra.96,97 Ag nanoparticles
demonstrated lower zeta potential value at strongly acidic pH,
but when the pH increased higher zeta potential values were
obtained. Furthermore, larger particle size could be achieved by
decreasing the pH. It has been indicated that larger quantities
of T. vulgare extract leads to an increase in peak absorbance
in UV/Vis spectrum. Moreover, decrease in particle size of Ag
and Au nanoparticles has been reported due to an increase in
extract amount.95 The possibility of controlling the properties
of nanoparticles by changing the composition of the reaction
mixture has resulted in the use of different amount of biomass
or cell extract and substrate concentration in order to formation
of nanoparticles with desired shape and size. It appears that
the particle size decreased with an increase in the leaf broth
concentration or decrease in the concentration of metal ions.
Moreover, the rate of formation of metal nanoparticles was
found to be slower at lowest concentration.93,96,98,99 Bankar et al.99
reported banana peel (Musa paradisiaca) extract as a new source
2644 | Green Chem., 2011, 13, 2638–2650
for synthesis of silver nanoparticles. The banana peels were
washed and boiled in distilled water for 30 min at 90 ◦ C. It is
well known that the temperature at which the reaction mixtures
are incubated affects the process of metal reduction. When the
temperature is increased, the reactants are consumed rapidly
eventually leading to the production of smaller nanoparticles.
The produced silver nanoparticles displayed antifungal activity
against C. albicans and C. lipolytica, and antibacterial activity
against E. coli, Shigella sp., Klebsiella sp. and E. aerogenes.
The antimicrobial activity of the banana peel extract-mediated
silver nanoparticles was comparable to that synthesized by the
trisodium citrate method.
Nanoparticles of silver were prepared by using Bryophyllum
sp., Cyperus sp., and Hydrilla sp. plant extracts.100 X-Ray analysis
demonstrated that silver nanoparticles (2–5 nm) have fcc unit cell
structure. The reduction of silver ions was due to water-soluble
phytochemicals such as flavones, quinones, and organic acid
(e.g., oxalic, malic, tartaric, and protocatecheuic acid) present
in plant tissues. It was demonstrated that silver nanoparticles
might have resulted due to different aforementioned metabolites
or fluxes and other oxido-reductively labile metabolites such
as ascorbates or catechol/protocatecheuic acid.100 In the case
of Chenopodium album (an obnoxious weed), organic acids
were also responsible for nanoparticle biosynthesis. The plant
leaf has a high level of oxalic acid as well as lignin which
can act as reducing agents. C. album leaf extract was used
for the single-pot bio-inspired synthesis of spherical silver and
gold nanoparticles.96 Quasi-spherical shapes were observed for
produced nanoparticles within range of 10–30 nm.
Deshpande et al.101 have investigated the rapid and extracel-
lular formation of gold nanocrystals by using dried clove buds
(Syzygium aromaticum) solution within a few minutes. The XRD
(X-ray diffraction) and EDAX (energy dispersive X-ray analysis)
demonstrated that the particles were crystalline in nature. The
probable biochemical pathway of biosynthesis was studied using
FTIR. Water-soluble flavonoids of clove buds were responsible
for bioreduction and stabilization of nanoparticles (colloidal
solution was stable more than 6 weeks). Kumar et al.102 reported
that only high polar soluble constituents of Syzygium cumini
were responsible for synthesis of silver nanoparticles. It was also
demonstrated that the amount of polyphenols and biochemical
constituents could be one of the important parameters affecting
the size and distribution of silver nanoparticles.
The various synthetic and natural polymers such as
poly(ethylene glycol), poly-(N-vinyl-2-pyrrolidone), starch, hep-
arin, poly-cationic chitosan (1-4-linked 2-amino-2-deoxy-b-D-
glucose), sodium alginate (a polysaccharide gum derived from
the cell walls of brown algae), and gum acacia have been
reported as reducing and stabilizing agents for the biosynthesis
of gold and silver nanoparticles. Kora et al.98 reported that
monodispersed and spherical silver nanoparticles (3 nm) were
biosynthesized by using gum kondagogu (non-toxic polysaccha-
ride derived as an exudate from the bark of Cochlospermum
gossypium). It was suggested that carboxylate and hydroxyl
groups were involved in complexation and bioreduction of
silver ions into nanoparticles. This method is compatible with
green chemistry principles as the gum serves a matrix for both
bioreduction and stabilization of the synthesized nanoparticles.
Due to the availability of low cost plant derived biopolymer, this
This journal is © The Royal Society of Chemistry 2011
method could be implemented for the large scale production of
highly stable monodispersed nanoparticles. The formed silver
nanoparticles with an average size of 4.5 nm were used for
checking the antibacterial activity. As a result, the nanoparticles
had significant antibacterial effects against gram negative (E.
coli and P. aeruginosa) and positive (S. aureus) bacteria.
Acalypha indica (Euphorbiaceae) leaf extracts have pro-
duced silver nanoparticles (20–30 nm) within 30 min.103 These
nanoparticles had excellent antimicrobial activity against water
borne pathogens E. coli and V. cholera (minimum inhibitory
concentration (MIC) = 10 mg ml-1 ). Furthermore, spherical
silver nanoparticles (40–50 nm) were produced using leaf extract
of Euphorbia hirta.104 These nanoparticles had potential and
effective antibacterial property against Bacillus cereus and S.
aureus. In another study, silver nanoparticles (with an average
size of 57 nm) were produced when 10 ml of Moringa oleifera
leaf extract was mixed to 90 ml of 1 mM aqueous of AgNO3 and
was heated at 60–80 ◦ C for 20 min. The formed nanoparticles
had considerable antimicrobial activity against pathogenic mi-
croorganisms, including S. aureus, Candida tropicalis, K. pneu-
moniae, and C. krusei.105 It has been reported that cotton fibers
loaded with biosynthesized silver nanoparticles (~20 nm) using
natural extracts of Eucalyptus citriodora (neelagiri) and Ficus
bengalensis (marri) had excellent antibacterial activity against
gram-negative E. coli bacteria. These fibers have potential for
utilization in burn/wound dressings as well as in the fabrication
of antibacterial textiles and finishings.106 Garcinia mangostana
(mangosteen) leaf extract could be used as reducing agent in
order to synthesize silver nanoparticles. The aqueous silver ions
when exposed to leaf extract were reduced and resulted in silver
nanoparticles with an average size of 35 nm. These nanoparticles
had high effective antimicrobial activity against E. coli and S.
aureus.107 It was reported that Ocimum sanctum (tulsi) leaf ex-
tract could reduce silver ions into crystalline silver nanoparticles
(4–30 nm) within 8 min of reaction time. These nanoparticles
were stable due to the presence of proteins which may act as
capping agent. O. sanctum leaves contain ascorbic acid which
may play a role in bioreduction of silver ions into metallic
nanoparticles. Biosynthesized silver nanoparticles have shown
strong antimicrobial activity against both gram-negative (E. coli)
and gram-positive (S. aureus) microorganisms.108 Furthermore,
biosynthesis of silver nanoparticles by Cacumen platycladi
extract was investigated. Reducing sugars and flavonoids in the
extract were mainly responsible for the bioreduction of the silver
ions, and their reductive capability promoted at 90 ◦ C, leading to
the formation of silver nanoparticles (18.4 ± 4.6 nm) with narrow
size distribution. The nanoparticles had significant antibacterial
activity against E. coli and S. aureus.109
Ultrafine palladium (Pd) nanoparticles have application both
in heterogeneous and homogeneous catalysis, due to their high
surface-to-volume ratio and high surface energy.110 The common
synthetic methods for synthesis of palladium nanoparticles
involve chemical reduction of Pd(II) by alcohol,111 polyethylene
glycol,112 NaBH4 /ascorbic acid113 or CNCH2 COOK,114 ther-
mally induced reduction of Pd(Fod)2 in o-xylene,115 reduction
of Pd(OAc)2 by dimethylamine-borane in supercritical carbon
dioxide (CO2 ),116 and sonochemical reduction of Pd(NO3 )2 .117
Sathishkumar et al.118 have investigated phyto-crystallization of
palladium through a reduction process using C. zeylanicum bark
This journal is © The Royal Society of Chemistry 2011
extract. As a result, nano-crystalline palladium particles (15–
20 nm) were successfully synthesized. It was demonstrated that
reaction conditions such as pH, temperature, and biomaterial
dosage had no major effects on the shape and size of produced
nanoparticles. In another study, nano-crystalline palladium
particles (10–15 nm) have been synthesized using Curcuma longa
tuber extract as biomaterial. pH and temperature had no major
effect on size and shape of the nanoparticles. It was found
that the zeta potential of formed palladium nanoparticles was
negative and it increased with increase in pH. It has been also
reported that palladium nanoparticles could be synthesized by
using coffee and tea extract. The produced nanoparticles were
in the size range of 20–60 nm and crystallized in face centered
cubic symmetry.119 It was reported that crude water extract of
Gardenia jasminoides Ellis could be used for bioreduction of
palladium chloride. Identified antioxidants, including genipo-
side, chlorogenic acid, crocins and crocetin were reducing and
stabilizing agents for synthesizing palladium nanoparticles (3–
5 nm) in water crude extract. The particle size and disparity
of nanoparticles were temperature dependent, and the best
dispersity was revealed at 70 ◦ C.120
Indium oxide (In2 O3 ) is an important n-type semiconductor
which has interesting properties such as high transparency to
visible light, strong interaction between certain poisonous gas
molecules and its surface, and high electrical conductance.121,122
Indium oxide is an intersecting material for a wide range of
applications such as solar cells, organic light emitting diodes,
architectural glasses, panel displays, and field emission.123–125
Indium oxide nanoparticles have been intensively studied to
be used as promising materials for gas sensor applications.126
In addition to chemical synthetic methods, these nanoparticles
could be biologically synthesized using A. vera (Aloe barbadensis
Miller) plant extracted solution. In2 O3 nanoparticles (5–50 nm)
have been produced by using indium acetylacetonate and A.
vera plant extracted solution.126 The nanoparticles are formed
after calcination of the dried precursor of indium oxide in air at
400–600 ◦ C. The morphology and size of indium oxide materials
were affected by the temperature of calcination.
Copper (Cu) nanoparticles were biosynthesized using magno-
lia leaf extract. When aqueous solutions of CuSO4 ·5H2 O treated
with the leaf extract, stable copper nanoparticles (40–100 nm)
were formed. Foams coated with biologically synthesized copper
nanoparticles showed higher antibacterial activity against E.
coli cells.127 In another study, extracellular production of copper
nanoparticles was carried out using stem latex of a medicinally
important plant, Euphorbia nivulia. The produced nanoparticles
were stabilized and subsequently capped by peptides and
terpenoids present within the latex. The copper nanoparticles
are toxic to adenocarcinomic human alveolar basal epithelial
cells (A549 cells) in a dose-dependent manner. It was concluded
that the non-toxic aqueous formulation of latex capped copper
nanoparticles could be directly used for administration/in vivo
delivery of nanoparticles for cancer therapy.128
Zinc oxide (ZnO) is an attractive semiconductor material
for photonic and nano-electronic applications.129 In addition
to various chemical and physical synthetic approaches (e.g.,
sol-gel, vapor phase oxidation, micro-emulsion, thermal vapor
transport and condensation, sono-chemical, precipitation, hy-
drothermal, and polyol methods), ZnO nanoparticles could be
Green Chem., 2011, 13, 2638–2650 | 2645
Table 1 Important examples of nanoparticle biosynthesis using plants

Plant origin Nanoparticle Size (nm) Morphology References

68
Aloe vera gold & silver — spherical, triangular
126
Aloe vera (Aloe barbadensis Miller) indium oxide 5–50 spherical
103
Acalypha indica silver 20–30 spherical
82
Apiin extracted from henna leaves silver 39 spherical, triangular
82
Apiin extracted from henna leaves gold 7.5–65 quasi-spherical
61
Avena sativa (oat) gold 5–20 (pH 3 & 4), rod-shaped
25–85 (pH 2)
71
Azadirachta indica (neem) gold, silver & 5–35 & 50–100 spherical, triangular, hexagonal
silver-gold alloys
89
Black tea leaf extracts gold & silver 20 spherical, prism
133
Brassica juncea (mustard) silver 2–35 spherical
100
Bryophyllum sp. silver 2–5 fcc unit cell structure
66
Camellia sinensis (green tea) gold 40 spherical, triangular, irregular
90
Carica papaya silver 60–80 spherical
96
Chenopodiumalbum gold & silver 10–30 quasi-spherical
42
Cinnamomum camphora gold & silver 55–80 triangular, spherical (Au) and
quasi-spherical (Ag)
134
Cinnamomum camphora palladium 3.2–6 —
76
Cinnamon zeylanicum (cinnamon) silver 31–40 cubic, hexagonal
118
Cinnamon zeylanicum (cinnamon) palladium 15–20 crystalline
Citrus limon (lemon) silver <50 spherical, spheroidal 135
98
Cochlospermum gossypium silver 3 spherical
74
Coriandrum sativum (coriander) gold 6.75–57.91 spherical, triangular, truncated
triangular, decahedral
40
Cymbopogon flexuosus (lemongrass) gold 200–500 spherical, triangular
100
Cyperus sp. silver 2–5 fcc unit cell structure
80
Cycas sp. (cycas) silver 2–6 spherical
81
Datura metel silver 16–40 spherical, ellipsoidal
79
Desmodium triflorum silver 5–20 spherical
86
Diospyros kaki (persimmon) bimetallic gold/silver 50–500 cubic
136
Eclipta sp. silver 2–6 spherical
41
Emblica officinalis (indian gooseberry) gold & silver (10–20) & (15–25) —
137
Enhydra fluctuans silver 100–400 spherical
138
Eucalyptus camaldulensis (river red gum) gold 1.25–17.5 crystalline, spherical
Eucalyptus citriodora (neelagiri) silver ~20 spherical 106
75
Eucalyptus hybrida (safeda) silver 50–150 crystalline, spherical
104
Euphorbia hirta silver 40–50 spherical
Ficus bengalensis (marri) silver ~20 spherical 106
107
Garcinia mangostana (mangosteen) silver 35 spherical
120
Gardenia jasminoides Ellis palladium 3–5 —
139
Gliricidia sepium silver 10–50 spherical
140
Hibiscus rosa sinensis gold & silver 14 spherical, prism
141
Honey silver 4 spherical
100
Hydrilla sp. silver 2–5 fcc unit cell structure
137
Ipomoea aquatica silver 100–400 spherical & cubic
91
Jatropha curcas (latex) silver 10–20 fcc unit cell structure
142
Jatropha curcas (seed extract) silver 15–50 spherical
137
Ludwigia adscendens (ludwigia) silver 100–400 spherical
143
Medicago sativa (alfalfa) titanium-nickel alloys 1–4 fcc-like geometry for smallest
clusters and complex arrays for
biggest ones
49,50,52
Medicago sativa (alfalfa) gold 2–40 irregular, tetrahedral,
hexagonal platelet, decahedral,
icosahedral
57
Medicago sativa (alfalfa) iron oxide 2–10 crystalline
97
Mentha piperita (peppermint) silver 5–30 spherical
144
Mentha piperita (peppermint) silver 90 spherical
144
Mentha piperita (peppermint) gold 150 spherical
105
Moringa oleifera silver 57 spherical
145
Murraya koenigii silver 10 crystalline, spherical
145
Murraya koenigii gold 20 spherical, triangular
99
Musa paradisiaca (banana peel extract) silver — crystalline, irregular
92
Nelumbo nucifera (lotus) silver 25–80 spherical, triangular, truncated
triangular, decahedral
Ocimum sanctum (tulsi; root extract) silver 10 ± 2 & 5 ± 1.5 nm spherical 146
147
Ocimum sanctum (tulsi; leaf extract) gold 30 crystalline, hexagonal,
triangular
147
Ocimum sanctum (tulsi; leaf extract) silver 10–20 spherical
Parthenium hysterophorus (parthenium; silver ~ 50 irregular 148

leaf extract)
94
Pear fruit extract gold 200–500 triangular, hexagonal

2646 | Green Chem., 2011, 13, 2638–2650 This journal is © The Royal Society of Chemistry 2011
Table 1 (Contd.)

Plant origin Nanoparticle Size (nm) Morphology References

62
Pelargonium graveolens (geranium) gold 20–40 decahedral, icosahedral
67
Pelargonium graveolens (geranium) silver 16–40 crystalline
138
Pelargonium roseum (rose geranium) gold 2.5–27.5 crystalline
130
Physalis alkekengi zinc oxide 72.5 crystalline
149
Psidium guajava (guava) gold 25–30 mostly spherical
150
Scutellaria barbata D. Don (Barbated gold 5–30 spherical & triangular
skullcup)
131
Sedum alfredii Hance zinc oxide 53.7 hexagonal wurtzite &
pseudo-spherical
66
Sesbania drummondii (leguminous shrub) gold 6–20 spherical
93
Sorbus aucuparia (rowan) silver & gold 16–18 spherical, triangular, hexagonal
101
Syzygium aromaticum (clove) gold 5–100 crystalline, irregular, spherical,
elliptical
102
Syzygium cumini (jambul) silver 29–92 spherical
72
Tamarindus indica (tamarind) gold 20–40 triangular
95
Tanacetum vulgare (tansy fruit) gold & silver 11, 16 triangular, spherical
151
Terminalia catappa (almond) gold 10–35 spherical
152
Trichoderma koningii gold 30–40 triangular

synthesized by bio-based approach.130 It was reported that crys-
talline zinc oxide nanoparticles (72.5 nm) were synthesized using
Physalis alkekengi L. The TEM images demonstrated that the
produced nanoparticles were polydispersed and not uniformly
distributed.130 Furthermore, the synthesis of hexagonal wurtzite
ZnO nanoparticles from Zn-hyper-accumulator (Sedum alfredii
Hance) plants has been reported. The formed nanoparticles
were agglomerated, and single ZnO nanoparticles were pseudo-
spherical in shape with a mean size of 53.7 nm.131 It seems
that these hyper-accumulator plants are the best candidates for
biosynthesis of heavy metal nanoparticles (e.g., Ag, Cu, Cd, Co,
Zn and Ni).
Table 1 summarizes the important examples of nanoparticle
biosynthesis using plants. Moreover, some important features of
the nanoparticles including size and morphology are mentioned.
4. Extraction of biologically produced metal
nanoparticles
The extraction of metal nanoparticles from either living or non-
living plants for further applications is not well investigated,
but studies are moving toward solving such these problems and
finding best ways for extraction and purification of produced
nanoparticles. Armendariz et al.61 have extracted produced gold
nanoparticles from inactivated tissues of wheat and oat biomass.
The extraction process involved the use of cetyltrimethylammo-
nium bromide (CTAB) and citrate combined with sonication
to transfer the nanoparticles from the biomass into aqueous
solution. The results of this study have shown that the citrate
extractions were more successful than the CTAB extractions.
Moreover, TEM analysis of the extraction solutions indicated
that the smaller radius of the gold nanoparticles extracted at
first and then larger nanoparticles were being extracted.
In order to extract the produced nanoparticles from the cells,
some of the researchers used physicochemical methods including
freeze-thawing, heating processes, and osmotic shock. It seems
that these processes may interfere with the structure of nanopar-
ticles, and some events such as aggregation, precipitation, and
sedimentation could happen. These may change the shape and
size of nanoparticles and interfere with the suitable properties
of nanomaterials. On the other hand, enzymatic lysis of the
plant cells (e.g., cocktail of enzymes isolated from Trichoderma
longibrachiatum) containing intracellular nanoparticles could be
used, but this method is expensive and it could not be used
in up-scalable and industrial production of nanoparticles.132
In addition, a rigid cell wall around the plant cells makes
nanoparticle extraction difficult. It seems that surfactants and
organic solvents might be good candidates for both extraction
and stabilization of nanoparticles. It should be noted that in the
case of extracellular production of nanoparticles, centrifugation
could be used for extraction and purification of nanoparticles,
but aggregation might happen.
5. Conclusions
Various chemical, physical and biological synthetic methods
have been used in production of metal nanoparticles. Most of
these methods are still in the development stage and the problems
experienced are stability and aggregation of nanoparticles,
control of crystal growth, morphology, size and size distribution.
Moreover, separation of produced nanoparticles for further
applications is still an important issue.
It was shown that the metal nanoparticles produced by plants
are more stable in comparison with those produced by other
organisms. Plants (especially plant extracts) are able to reduce
metal ions faster than fungi or bacteria. Furthermore, in order
to use an easy and safe green method in scale-up and industrial
production of well-dispersed metal nanoparticles, plant extracts
are certainly better than plant biomass or living plants.
Researchers have focused their attention on understanding
the biological mechanisms and enzymatic processes of nanopar-
ticle biosynthesis as well as detection and characterization of
biomolecules involved in the synthesis of metallic nanoparticles.
Many biomolecules in plants such as proteins/enzymes, amino
acids, polysaccharides, alkaloids, alcoholic compounds, and
vitamins could be involved in bioreduction, formation and
stabilization of metal nanoparticles. Reduction potential of ions
and reducing capacity of plants which depend on the presence

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 2638–2650 | 2647
of polyphenols, enzymes, and other chelating agents present in
plants have critical effects on the amounts of nanoparticle pro-
duction. It should be mentioned that the future of investigations
might move toward the optimization of reaction conditions and
engineering the recombinant organisms for production of high
amounts of proteins, enzymes, and biomolecules involved in
biosynthesis and stabilization of nanoparticles. Understanding
the biochemical processes/pathways involved in plant heavy
metal detoxification, accumulation, and resistance will help
to improve nanoparticle production. Genetic modification of
plants with improved metal tolerance and accumulation capac-
ities is the future approach to increase the productivity of these
organisms in nanoparticle synthesis.
Acknowledgements
This review was part of the project of Faculty of Pharmacy
and Pharmaceutical Sciences, Isfahan University of Medical
Sciences.
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