Review
The greener synthesis of nanoparticles
Oxana V. Kharissova1, H.V. Rasika Dias2, Boris I. Kharisov3, Betsabee Olvera Pérez3,
and Victor M. Jiménez Pérez3
1
Universidad Autónoma de Nuevo León, Facultad de Ciencias Fı́sico-Matemáticas, CIIDIT, Ciudad Universitaria, Monterrey,
NL 66450, Mexico
2
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019, USA
3
Universidad Autónoma de Nuevo León, Facultad de Ciencias Quı́micas, CIIDIT, Ciudad Universitaria, Monterrey, NL 66450,
Mexico
In this review, we examine ‘greener’ routes to nanopar-
ticles of zerovalent metals, metal oxides, and salts with
an emphasis on recent developments. Products from
nature or those derived from natural products, such as
extracts of various plants or parts of plants, tea, coffee,
banana, simple amino acids, as well as wine, table sugar
and glucose, have been used as reductants and as cap-
ping agents during synthesis. Polyphenols found in plant
material often play a key role in these processes. The
techniques involved are simple, environmentally friend-
ly, and generally one-pot processes. Tea extracts with
high polyphenol content act as both chelating/reducing
and capping agents for nanoparticles. We discuss the
key materials used in the field: silver, gold, iron, metal
alloys, oxides, and salts.
Green chemistry and nanotechnology
The ‘greener’ environmentally friendly processes in chem-
istry and chemical technology are becoming increasingly
popular and are much needed as a result of worldwide
problems associated with environmental contamination.
Within the last 2 years, several ‘green chemistry’ books
have been published describing green processes in general
[1–4] and their specialized aspects, including ultrasound,
microwaves, and other methods in synthesis [5,6], green
analytical chemistry [7], green tribology [8], polymers and
green polymerization [9,10], green engineering and
manufacturing [11,12], food [13], textiles [14], hydrogen
and syngas production and uses [15,16], wastewater treat-
ment [17], particle technology [18], biofuels, biomass and
biocomposites [19–21], and other ‘green chemistry’ areas
[22,23]. The 12 principles of green chemistry [24] have now
become a classic guide for chemists and chemical technol-
ogists worldwide in developing less hazardous chemical
syntheses.
Although UV irradiation, aerosol technologies, lithog-
raphy, laser ablation, ultrasonic fields, and photochemical
reduction techniques have been used successfully to pro-
duce nanoparticles, they remain expensive and involve the
use of hazardous chemicals. Therefore, there is a signifi-
cant interest in the development of environmentally
friendly and sustainable methods [25]. At the same time,
despite intensive developments of the nanotechnology, the
adverse effects of nanomaterials are still relatively
unknown. The synthesis of such materials using
Keywords: ‘green’ synthesis; plant extracts; tea extract; nanoparticles
240 0167-7799/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.tibtech.2013.01.003 Trends in Biotechnology, April 2013, Vol. 31, No. 4
environmentally friendly and biocompatible reagents
could lower the toxicity of the resulting materials and
the environmental impact of the byproducts [26,27]. To
reach this goal, non-toxic solvents (preferably water),
closed reactors, ‘green’ techniques without contacting re-
action media and air (ultrasound, microwave, hydrother-
mal, magnetic, biological methods, among others), and low
temperatures, can be used. In this short review which
focuses on the most recent developments, we describe
the methods which we consider as relatively greener routes
to nanoparticles and nanomaterials involving extracts of
plants [28] and other natural products.
Green production of nanoparticles
The techniques for obtaining nanoparticles using natu-
rally occurring reagents such as vitamins, sugars, plant
extracts, biodegradable polymers, and microorganisms
as reductants and capping agents could be considered
attractive for nanotechnology. These syntheses have led
to the fabrication of limited number of inorganic
nanoparticles (mainly metal nanoparticles, although
several metal oxides and salts are also reported). Among
the reagents mentioned above, plant based materials
seem to be the best candidates and they are suitable
for large-scale ‘biosynthesis’ of nanoparticles [29]. Plant
parts such as leaf, root, latex, seed, and stem are being
used for metal nanoparticle synthesis. The key active
agent in some of these syntheses are believed to be
polyphenols, present for example, in tea, wine and win-
ery waste, red grape pomace. Greener synthesis of nano-
particles provides advancement over other methods as it
is simple, cost-effective, and relatively reproducible and
often results in more stable materials [30]. Microorgan-
isms can also be utilized to produce nanoparticles but the
rate of synthesis is slow and only limited number of sizes
and shapes are amenable compared to routes involving
plant based materials. At present, fungi are gaining
worldwide popularity as nano-factories for the green
synthesis of nanoparticles [31]. Overall, biological mate-
rials provide an environmentally friendly or greener
chemical method to produce invaluable materials be-
cause the biomaterial based routes eliminate the need
to use harsh or toxic chemicals [32]. Mechanisms of these
bioreductive transformations [33–35], as well as catalytic
properties of materials obtained via these routes [36–39]
have been discussed in a series of reports.
Review Trends in Biotechnology April 2013, Vol. 31, No. 4

Table 1. Synthesis of silver nanoparticles by greener methods (precursor AgNO3 in all cases)
Reducing agent
Aqueous extracts of the manna of
hedysarum plant and the soap-root
(Acanthe phylum bracteatum) plant
Extract of Argemone mexicana leaf
Culture supernatants of Aspergil
lusterreus
Leaf extract of Euphorbia hirta L.
Euphorbia milii
F. vulgare leaves
Basic amino acids, such as L-lysine
(Figure 1d) or L-arginine, as reducing
agents and soluble starch as a protecting
agent
Conditions, observations
13–20 min at 25–95 8C
4 h at room temperature
24 h at 28 8C; reduced nicotinamide
adenine dinucleotide (NADH) was found
to be an important reducing agent for the
biosynthesis, and the formation of
AgNPs; this could be an enzyme-
mediated extracellular reaction process
50–95 8C
Irradiation of a silver nitrate and solution
by light from a xenon lamp followed by
ultra-short laser pulses; the irradiation
times were 1, 3, and 5 min
Room temperature
The mixture was heated to 150 8C by
microwave under magnetic stirring
and was maintained at this temperature
for 10 s
Properties of formed Ag nanoparticles Refs
Average diameter of the prepared [96]
nanoparticles in solution was about 29–68 nm
Average size of the particles synthesized was [97]
20 nm, size range was 10–50 nm, with cubic
and hexagonal shape
Polydispersed spherical particles ranging in [98]
size from 1 to 20 nm
Relatively spherical shape with diameter range [99]
40–50 nm
Nanoparticles are present after the xenon lamp [100]
illumination, and after the laser irradiation the
silver nanoparticles sizes are reduced to the
range of 10–50 nm
127 nm [101]
26 nm (average size); this synthetic process can [40]
be readily applied to large-scale production, for
example, a reaction yielding 0.1 g of nearly
monodisperse silver nanoparticles can be
performed in a 80 ml microwave sealed vessel

Silver nanoparticles are the classic and the most pre-
ferred target of the above mentioned ‘green’ methods (Ta-
ble 1) [40–43]. This is related to the antibacterial
properties of zerovalent silver and easy reduction of sil-
ver(I) salts to form zerovalent silver. Gold nanoparticles
are also of a considerable interest, although to a much
lesser degree than Ag. Other metal and other inorganic
nanoparticles are represented by small number of reports.
We discuss various greener routes for the synthesis of
these nanoparticles below.
In general, as it will be seen below, ‘green’ methods are
not so widespread (although rapidly being developed) in
nanoscience and nanotechnology as classical wet-chemistry
routes for nanoparticles fabrication [44,45]. This relatively
hot topic possesses such important advantage as lesser or
almost zero contaminations for the environment. Waste
products are usually compatible with environmental
requirements (except microbial synthesis of nanoparticles,
where the waste material could be dangerous depending on
the type of microbe applied) because they are derived from
natural plant extracts. Precursor costs may vary, but gen-
erally they are low. On reviewing a series of reports of
authors from different countries, we observed that in gen-
eral commonly available and economical products for those
regions are used, for example, nut putamen (India) or cactus
extracts (Mexico). Obviously, the ‘greener’ methods do not
pretend to substitute all conventional techniques; however,
at least a small decrease in damage to nature can be reached.
Silver (Ag)
A large number of reports are dedicated to greener synthe-
sis of silver nanoparticles, therefore here we will examine
only the most representative examples. Silver nanoparti-
cles ranging from 5 to 10 nm in size have been synthesized
under microwave irradiation conditions using glutathione
(Figure 1a), an absolutely benign antioxidant that serves
as the reducing as well as the capping agent in aqueous
medium [46]. The process takes only 30–60 min and is
adaptable for the synthesis of palladium, platinum, and
gold nanoparticles. The formation of dendritic nanostruc-
tures on the transmission electron microscopy (TEM) grid
was observed when the reaction mixtures without complete
conversion of AgNO3 were loaded on the TEM grid prior to
the washing procedure. The copper and carbon present on
the TEM grid are responsible for catalyzing the reaction.
Synthesis of silver nanoparticles (1–10 nm) has also been
investigated using geraniol (Figure 1b) [47]. A concentration
of 1 mg/ml of these silver nanoparticles could inhibit cancer
cell line (Fibrosarcoma-Wehi 164) growth by less than 30%.
Sugars have been used with silver salts as a part of the
well-known Tollen’s test to produce silver mirrors. Sugars
have also been used in Ag nanoparticle fabrication. Synthe-
sis of biocompatible Ag nanoparticles (10–20 nm) employing
table sugar as a capping and a reducing agent is a relatively
economical, easily adaptable, and greener route [48]. A
remarkable antitumor potency of the resulting Ag nanopar-
ticles was seen against HT144 (malignant skin melanoma)
and H157 (squamous cell lung carcinoma) cells as compared
to the clinically used reference compounds vincristine and
methotrexate. Ag nanoparticles have also been synthesized
in a natural polymeric matrix, using silver nitrate, gelatin,
glucose, and sodium hydroxide as silver precursor, stabiliz-
er, reducing agent, and accelerator reagent, respectively
[49]. The resultant nanoparticles had faced centered cubic
(fcc) structures smaller than 20 nm in diameter. Gelatin was
used as the stabilizer and matrix during this synthesis. The
possible chemical equations (Equations 1 and 2) for prepar-
ing the Ag nanoparticles are as follows:
Agþ ðaqÞ þgel ! ½AgðgelÞþ ðaqÞ [1]
2½AgðgelÞþ ðaqÞ þ2OH þC5 H11 O5 -CHO ! 2Ag þ 2gelþ
H2 O þ C5 H11 O5 -COOH [2]

241
Review
(a) HO
O
HN
O
HS
HN
O OH
H2N
O
Glutathione
(c)
HO
O
OH
OH
Epicatechin
Figure 1. Chemical structures of some components of plant extracts.
Plant extracts have also been used for Ag nanoparticle
synthesis. The reactions have generally been carried out at
room temperature, although in some processes a heating
was applied, mainly below 100 8C. For example, silver
nanoparticles have been synthesized (at room temperature
and 60 8C) using Polyalthia longifolia leaf extract as a
reducing and capping agent along with D-sorbitol used
to increase the stability of the nanoparticles [50]. The
synthesized silver nanoparticles were more highly toxic
to Gram-positive bacteria than Gram-negative bacteria. In
addition, silver nanoparticles have been synthesized using
sulfated polysaccharide isolated from marine red algae
(Porphyra vietnamensis) [51]. The resulting silver nano-
particles showed surface plasmon resonance centered at
404 nm with average particle size measured to be 13 
3 nm. The involvement of the sulfate moiety of the poly-
saccharide for reduction of silver nitrate was revealed
spectroscopically.
Silver nanoparticles have been synthesized from aque-
ous silver nitrate (1 mM) using leaf broth of Ocimum
sanctum as reductant and stabilizer [52]. The resulting
silver nanoparticles ranged in size from 3 to 20 nm. Leaf
extract of Morinda citrifolia L. was assessed for the syn-
thesis of silver nanoscale particles at different tempera-
tures and reaction times [53]. High amounts of phenolic
compounds in the plant extract are likely to influence the
reduction process and stabilize nanoparticles preventing
242
Trends in Biotechnology April 2013, Vol. 31, No. 4
(b) CH3
OH
H3C CH3
Geraniol
OH (d)
O
H2N
OH
OH
H NH2
L-lysine
TRENDS in Biotechnology
agglomeration. Among many other plant extracts applied
for reduction of Ag+, we note aqueous extracts of Moringa
oleifera [54] and Vitex negundo L. [55].
Extracts from well-known commercial products like
coffee and tea were used in silver chemistry as well. Thus,
by reducing silver nitrate in solutions of tea extract or
epicatechin (Figure 1c) of varying concentrations, spherical
silver nanoparticles were formed that had controllable size
distributions depending on the concentration of tea extract
or epicatechin in the samples [56]. The nanoparticles were
in fact interacting with the keratinocytes. These nanopar-
ticles are potentially biocompatible and warrant further
evaluation in other biological systems. In another example,
the use of soap nuts [57] resulted in Ag nanoparticles that
showed more inhibitory activity on pathogenic Gram-posi-
tive than Gram-negative bacteria.
Among the engineering achievements in the production
of nanoparticles of silver and other metals, we especially
note the reactor designed for Ag nanoparticles obtained by
lixivium of sundried Cinnamomum camphora [58]. Here,
synthesis was carried out in a continuous-flow tubular
microreactor (Figure 2). According to the temperature
profiles, at the inlet of the microreactors at 90 8C, the high
fluid temperature induced the burst of silver nuclei by
homogeneous nucleation. Subsequently, the nuclei grew
gradually along the reactors into silver nanoparticles
from 5 to 40 nm. Polydisperse particles were formed by
Review
Rotang direcon of
electric sha
Peristalc
pump
Lixivium of
C. camphora leaf
Key:
Electric sha
Rotang and moving cylinder
Figure 2. Schematic of the experimental setup for continuous-flow biosynthesis of silver nanoparticles. Reproduced/adapted, with permission, from [58].
a combination of heterogeneous nucleation and Ostwald
ripening along the tubes at 60 8C.
Gold (Au) and its alloys
Gold nanoparticles can also be obtained by greener meth-
ods [59,60], but the number of reports is significantly fewer
compared to that of silver. The size of gold particles may
vary in a considerable range (from 20 to 300 nm in distinct
reports). For example, a variety of gold nanoparticles
(average size 300 nm; strictly speaking, some of these
are microparticles, according to a 100-nm accepted size
restriction of the nano-area) have been synthesized by
banana peel extract (BPE) as a simple, non-toxic,
eco-friendly green material [61]. The boiled, crushed,
acetone-precipitated, air-dried banana peel powder was
used to reduce chloroauric acid. The aggregation of the
nanoparticles into microcubes and microwire networks
towards the periphery of the air-dried samples was
observed. The involvement of carboxyl, amine, and hydrox-
yl groups during the synthetic process was indicated.
Nanocomposites of Au nanoparticles can also be obtained
using tea extracts. Tea leaf extracts in 1-methyl-2-pyrro-
lidinone (NMP) solution were used for fabrication of 20 nm
Au nanoparticles [62]. These nanoparticles were incorpo-
rated in NMP solution of polyaniline emeraldine base
(PANIEB) to cast the nanocomposite films. TEM analysis
confirmed the presence of gold nanoparticles in polyaniline
matrix. In addition, a facile and completely greener route
to Au nanoparticles by mixing the Au(III) ion-dissolved rice
wine and soda at pH 6.5 at a slightly elevated temperature
(25–55 8C) in the absence of extra protective agents was
reported [63]. Rice wine was used as a solvent and a
reducing agent; soda not only functioned as a protective
agent but also played the role of base catalyst. The resul-
tant solution was quite stable: no precipitation occurred
even after several months.
The effects of synthetic conditions on the morphology of
biologically-formed Au nanoparticles were examined.
Trends in Biotechnology April 2013, Vol. 31, No. 4
Glycerin bath
Aqueous
silver nitrate
Heater Silver hydrosol
Silicone tube ‘T’ juncon
Tubular reactor
TRENDS in Biotechnology
Thus, the effect of halide ions on the formation of biogeni-
cally prepared gold nanotriangles using the leaf extract of
lemongrass (Cymbopogon flexuosus) plant was studied
[64]. Iodide ions have a greater propensity to transform
flat gold nanotriangles into circular disk-like structures as
compared to other halide ions. Also, the presence of Cl
ions during the synthesis promotes the growth of nano-
triangles, whereas the presence of I ions distorts the
nanotriangle morphology and induces the formation of
aggregated spherical nanoparticles (Figure 3). By varying
the temperature of reaction condition, the shape, size, and
optical properties of anisotropic nanoparticles can be fine-
tuned. The ability to tailor the size/morphology of gold
nanoparticles and thus their optical properties by simple
variation in experimental conditions by a fully green chem-
istry approach could be important in applications such as
hyperthermia and architectural optical coatings.
Some gold alloys were also produced by greener routes.
Dextrose and the ethanol extract of black tea (Camellia
sinensis) were used as natural reducing agents for prepar-
ing Au–Ag alloy nanoparticles (molar ratio 3:1, although
the Au3+/Ag+ mixture was selected with a molar ratio of
1:1) under microwave irradiation [65]. The resulting alloy
nanoparticles were further purified with the agarose gel
Cl- l-
100 nm 100 nm
TRENDS in Biotechnology
Figure 3. Influence of halide ions on gold nanoparticle morphology. Reproduced/
adapted, with permission, from [64].
243
 Review
electrophoresis technique. Purified Ag–Au alloy nanopar-
ticles were spherical in the size range of 200 nm, and
possessed an average size of 92 nm. The final concentra-
tions of glucose and plant extract should be considered as
the main parameters affecting the Ag/Au ratio in the Ag–
Au alloy nanoparticles. In addition, a facile and eco-friend-
ly method for the preparation of Au–Pd bimetallic nano-
particles (7 nm) was developed based on simultaneous
bioreduction of Au(III) and Pd(II) precursors with Cacu-
men Platycladi leaf extract in aqueous environment [66]. It
was shown that the C=O and C–O groups in the plant
extract play a critical role in capping the nanoparticles.
Iron (Fe), its alloys, and oxides
Nanoscale iron particles, FexOy and FeOOH (in total 16
polymorphic forms) are of significant interest because of
their rapidly developing applications for disinfection of
water and remediation of heavy metals from soils
[67,68]. Therefore, methods using mainly tea extracts on
the polyphenol basis, as well other plant extracts, have
been utilized for obtaining Fe-containing nanoparticles
[69] and their further uses for the purposes above. Thus,
nanoscale zerovalent iron (NZVI) particles (Figure 4), pre-
pared using tea polyphenols [70], were assessed with
methyl tetrazolium [MTS, 3-(4,5-dimethylthiazol-2-yl)-5-
(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazoli-
um] and lactate dehydrogenase (LDH) toxicological assays.
Some of them were found to be nontoxic compared to the
control samples prepared using the conventional borohy-
dride reduction protocols.
In addition to ‘pure’ iron nanoparticles produced using
extracts of green tea leaves, the samples may contain
mainly iron oxide and iron oxohydroxide [71]. The nano-
particles were then utilized as a Fenton-like catalyst for
decolorization of aqueous solutions containing methylene
blue (MB) and methyl orange (MO) dyes. The results
indicated fast removal of the dyes with the kinetic data
3
Key:
A Palladium nanoparticles (PdNps), which are of interest
B because of their catalytic properties and affinity for hydro-
C
2
Absorbance (a.u.)
1 65 to 80 nm (S-PdNp-LA), and 75 to 100 nm (S-PdNp-
0 room temperature [78]. The reported method is general
300 400 500 600 700 800
Wavelength (nm)
TRENDS in Biotechnology
Figure 4. UV spectra of (a) Fe(NO3)3 control, (b) control tea extract, and (c) the
reaction product (Fe nanoparticles) obtained from Fe(NO3)3 and tea extract. The
inset shows the photographic image of the tea extract, the control Fe(NO3)3
solution, and after mixing them (from left to right vials). Reproduced/adapted, with
permission, from [70].
244
Trends in Biotechnology April 2013, Vol. 31, No. 4
of MB following a second order removal rate, whereas those
of MO were closer to a first order removal rate. Almost
complete removal of both dyes from water takes place over
a wide range of concentrations (10–200 mg/l). Superpara-
magnetic Fe3O4 nanoparticles [blocking temperature (TB)
of 150 K and saturation magnetization of 37.1 emu/g] were
synthesized via soya bean sprout (SBS) templates at room
temperature and normal atmospheric pressure [72].
Spherical Fe3O4 nanoparticles with an average diameter
of 8 nm simultaneously formed on the epidermal surface
and the interior stem wall of SBS, which were responsible
for size and morphologic control during the whole forma-
tion of nanoparticles. In addition, NixCu0.25Zn0.75–xFe2O4
(x = 0.25, 0.35, 0.5) polycrystalline nanopowders (15–
40 nm) with spinel structure were prepared by a simple
solution method using metal nitrates and Aloe vera plant
extract solution [73]. The samples exhibited ferromagnetic
behavior. Finally, iron alloys are also available by these
methods. Thus, membranes containing reactive nanopar-
ticles (Fe and Fe/Pd) immobilized in a polymer film [poly-
acrylic acid (PAA)-coated polyvinylidene fluoride (PVDF)
membrane] were prepared with the use of tea extract [74].
The membrane-supported nanoparticles were used for the
degradation of a common and highly important pollutant,
trichloroethylene (TCE).
Other metals
Copper (Cu)
Other metals and their compounds are represented by a
considerably fewer number of reports. Highly stable
dispersions of nanosized copper particles with an aver-
age particle size less than 2 nm have been synthesized
using a straightforward and cost-effective method,
utilizing nontoxic L-ascorbic acid as both a reducing agent
and capping agent precursor in aqueous medium [75].
Also, greener fabrication of nanoparticles of copper
and other metals using various fruit extracts and other
products of natural origin (such as red wine) was
patented [76].
Palladium (Pd)
gen, have been phyto-synthesized under moderate pH and
room temperature using Solanum trilobatum [77] and
conjugated with lipoic acid (S-PdNp-LA) and vitamins
(S-PdNp-Vitamin-LA). S-PdNp are polydisperse and of
different morphologies ranging from 60 to 70 nm (S-PdNp),
Vitamin-LA) in size. Bulk quantities of nanocrystals
(20–60 nm) of Pd, as well as other noble metals such as
Ag, have been obtained using coffee and tea extracts at
and may be extended to other noble metals such as Au and
Pt. One-pot biogenic fabrication of palladium nanoparticles
(small size from 3.2 to 6.0 nm) was also carried out by a
simple procedure using broth of Cinnamomum camphora
leaf without extra surfactant, capping agent, and/or tem-
plate [79]. The size of PdNPs could be easily controlled by
variation of the initial concentration of Pd(II) ions. Like-
wise, the reaction between broth of C. camphora leaf and
Review
the Pd(II) species might occur according to the following
equation (Equation 3):
nPdðIIÞ þ 2R-ðOHÞn ! nPdð0Þ þ 2nR ¼ O þ 2nHþ [3]
Finally, palladium nanoparticles (15 nm) were synthesized
using a Glycine max (soybean) leaf extract-mediated bio-
synthesis process [80]. Protein-rich soybean leaf extract
acts as an effective reducing agent for palladium ions. Also,
these biosynthesized palladium nanoparticles can be used
in catalysis, specifically for the degradation of azo dyes.
Platinum (Pt)
The leaf extract of Diopyros kaki has been used as a
reducing agent in the eco-friendly extracellular synthesis
of platinum nanoparticles (2–12 nm, depending on the
reaction temperature and concentrations of the leaf broth
and PtCl62) from an aqueous H2PtCl6.6H2O solution [81].
A greater than 90% conversion of platinum ions to nano-
particles was achieved with a reaction temperature of
95 8C and a leaf broth concentration of >10%. Platinum
nanoparticle synthesis using Diopyros kaki may not be an
enzyme-mediated process. Other related methods for plat-
inum nanoparticle formation are reviewed in [82].
Metal oxides and metal salts
Titanium(IV) oxide (TiO2)
In addition to the above-mentioned iron oxide nanoparti-
cles, other metal oxide nanoparticles like TiO2 (one of the
most important compounds in nanotechnology) have also
been obtained by greener methods. Titanium(IV) oxide
nanoparticles (100–150 nm) have been prepared from tita-
nium isopropoxide solution using nyctanthes leaf extract
[83]. Alternatively, TiO2 nanoparticles (25–100 nm) have
been prepared by using 0.3% aqueous extract prepared
from latex of Jatropha curcas L. [84]. Curcain (enzyme) and
cyclic peptides [namely curcacycline A (an octapeptide) and
curcacycline B (a nonapeptide)] have been identified as
possible reducing and capping agents present in the latex
of J. curcas L. There are two broad categories of nanopar-
ticles – the first have diameters from 25 to 50 nm and are
mostly spherical in shape; the second have larger and
uneven shapes.
Zinc(II) oxide (ZnO)
Highly stable and spherical zinc oxide nanoparticles (25–
40 nm) are produced by using zinc nitrate and Aloe barba-
densis Miller leaf extract [85]. As a result, greater than 95%
conversion to nanoparticles was achieved using aloe leaf
broth concentration greater than 25%. It was shown that
the zinc oxide nanoparticles were poly dispersed. The
particle size could be controlled by varying the concentra-
tions of leaf broth solution. Alternatively, ZnO nanoparti-
cles (30–60 nm) were synthesized via the sol–gel method in
gelatin media [86], where long-chain gelatin compounds
were utilized to terminate the growth of ZnO nanoparticles
and to stabilize them. It was concluded by authors that
gelatin is an interesting material that can be used as a
stabilizer in the sol–gel technique for preparing small ZnO-
NPs. In addition, formation of ZnO (and also gold, silver,
copper, and gold–silver–copper alloy) in living plants is
discussed in an extremely interesting recent review [87].
Trends in Biotechnology April 2013, Vol. 31, No. 4
Copper oxides (Cu2O and CuO)
Cu2O nanoparticles were prepared by reduction of Barfoed’s
solution, using agriculture wastes of Arachis hypogaea L.
(Fabaceae) leaf extracts containing reducing sugars, which
act as reducing agent at room temperature [88]. The alde-
hyde group present in reducing sugar plays an excellent role
in the formation of cuprous oxide nanoparticles in the solu-
tion. The cuprous oxide nanoparticles had antibacterial
effects on Gram-negative Escherichia coli. The morphology
of divalent copper oxide in 15–30 nm nanoparticles can be
controlled by tuning the amount of Aloe vera extract [89].
This eco-friendly approach for synthesis is suitable for large-
scale commercial production and health-related applica-
tions of CuO nanoparticles.
Indium(III) oxide (In2O3)
In addition, cubic In2O3 nanoparticles (5–50 nm) were
synthesized by a simple, cost-effective and environmental-
ly friendly route using indium acetylacetonate and Aloe
vera plant extract solution followed by a calcinations step
in air at 400–600 8C for 2 h [90]. Alternatively, In2O3
hollow spheres were ‘one-pot’ synthesized by hydrothermal
reaction of glucose and InCl3 mixtures at 180 8C for 12 h,
followed by calcination in air at 600 8C for 1 h [91]. These
spheres were sensitive to six flammable organic vapors
including alcohol, acetone, 93# gasoline, formaldehyde,
chloroform, and acetonitrile.
Lead(II) sulfide (PbS)
Finally, the intracellular synthesis of stable cubic lead
sulfide nanoparticles by a marine yeast, Rhodosporidium
diobovatum, has been reported [92]. The particles were
found to be composed of lead and sulfur in a 1:2 ratio
indicating that PbS nanoparticles were capped by a sul-
fur-rich peptide. It was revealed that 55% of lead in the
medium was accumulated in the exponential phase, where-
as a further 35% was accumulated in the stationary phase,
thus providing 90% overall recovery of PbS nanoparticles.
Concluding remarks and future perspectives
Fabrication of metal, metal oxides, and salt nanoparticles
using natural substances is a very promising area in nano-
technology, which came to prominence only a few years ago.
Useful materials can be produced easily even in reasonable
scale because the biomaterial-based routes eliminate the
need to use harsh or toxic chemicals. Waste products are
relatively innocuous and easier to dispose of because they
are mostly composed of leftover natural plant extracts. The
majority of greener synthetic efforts reported thus far are
dedicated to obtaining silver nanoparticles, perhaps due to
their ease of preparation, importance in disinfection science,
and utility in several applications. Several other metals (Au,
Fe, Pt, Pd, Cu), their alloys, oxides, and salts have also been
obtained by ‘greener’ methods.
In these greener routes, products from nature or derived
from plant materials such as extracts of various plants, tea,
coffee, banana, simple amino acids, as well as wine, table
sugar, and glucose, have been utilized as reductants and
capping agents. A considerable number of efforts are de-
voted to tea extracts, which, owing to a number of poly-
phenols present, can act as both chelating/reducing and
245
Review
capping agents for the nanoparticles. Therefore, the result-
ing particles are protected from further reactions and
aggregation, which increases their stability and longevity.
Greener methods involving plant materials that have been
used in nanoparticle synthesis are generally single-pot
reactions, without the use of additional surfactants, cap-
ping agents, and/or templates. Frequently, the technique
developed for a given metal and metal oxide nanoparticle
could also be applied for other metals.
We note that the bulk of these investigations have been
carried out at research laboratories in small scale (which is
normal) whereas there are no reports on pilot plant or
industrial-scale fabrication of nanomaterials using natural
products. We believe that there are good opportunities for
developing large-scale greener processes, where nanopar-
ticles have important applications. For example, iron nano-
particles derived from cheap widespread natural
precursors for remediation of heavy metals or disinfection
of water could be an attractive option in nanotechnological
environmental applications. Systematic studies are also
needed for uncovering some of the reaction mechanisms
and to reach more firm conclusions. For example, there are
several theories on Ag+ reduction to Ag0 and the disinfec-
tion action of silver nanoparticles [93–95]. Overall, the use
of natural products for greener synthesis of nanoparticles/
nanomaterials is an emerging and exciting area of nano-
technology and may have a significant direct impact on
further advances in biotechnology.
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