Materials Letters 75 (2012) 33–35

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Biomimetic synthesis of silver nanoparticles by aqueous extract of

Syzygium aromaticum
K. Vijayaraghavan a,⁎, S.P. Kamala Nalini b, N. Udaya Prakash c, D. Madhankumar d
a
Centre for Nanotechnology, BIST, Bharath University, Selaiyur, Chennai 60073, Tamil Nadu, India
b
Department of Plant Biology & Plant Biotechnology, Sir Theagaraya College, Chennai 60021, Tamil Nadu, India
c
Research & Development Vel Tech Dr RR & Dr SR Technical University, Avadi, Chennai, Tamil Nadu, India
d
Marina Labs, Chennai 600093, Tamil Nadu, India

a r t i c l e i n f o a b s t r a c t

Article history: The present investigation deals with the synthesis of silver nanoparticles (AgNPs) by green synthesis that has
Received 4 November 2011 advantages over conventional methods involving chemical agents associated with environmental toxicity.
Accepted 19 January 2012 Green synthesis method involves the use of Syzygium aromaticum extract in the universal solvent namely
Available online 28 January 2012
water. The reaction process was simple and convenient to handle, and was monitored using ultraviolet–
visible spectroscopy (UV–vis). The results were promising and rapid in the production of silver nanopar-
Keywords:
Biomaterials
ticle with a surface plasmon resonance occurring at 430 nm. The formed nanoparticles ranged in dimen-
Syzygium aromaticum sion between 20 and 149 nm which was almost spherical in shape. EDAX confirmed that the formed
Clove nanoparticles are silver as the optical absorption peak was observed approximately at 3 keV, which is typ-
Nanoparticles ical for the absorption of metallic silver nanocrystallites.
Silver © 2012 Elsevier B.V. All rights reserved.
Green synthesis

1. Introduction most of the characteristic aroma. Eugenol has pronounced antiseptic

The current trend in the synthesis of metal nanoparticles depends
on the eco-friendly technique for production of well-characterized
nanoparticles, this has lead to the development of “green chemistry”.
The validity of the “green” nanoparticle synthesis depends on the na-
ture of the solvent, reducing and capping agent, coupled with minimal
wastage in terms of energy and raw materials, safety in nanomaterial
synthesis and reduced impact on environment. The nanoparticles may
either be synthesized intracellularly or extracellularly using bacteria,
yeast, fungi and plant materials which finds wide application [1]. Even
though there is growing interest in bioinspired synthesis of silver nano-
particles, a general understanding of growth is not yet known. For ex-
ample, dodecamer peptides produced various morphologies of silver
nanoparticles [2]. In pursuit of green synthesis, numerous biomimetic
approaches are being explored in the preparation of silver nanoparticle
using bacteria Pseudomonas stutzeri AG259 [3], Lactobacillus strains [4],
yeast [5] and Fusarium oxysporum [6]. Plant parts have been successfully
used for synthesis of silver nanoparticle from the leaves of Azadirachta
indica [7], lemongrass plant extract [8] and Syzygium aromaticum ex-
tract for gold nanoparticles synthesis [9]. Syzygium aromaticum is wide-
ly used as a spice, in cooking as a condiment and flavoring material. The
compound eugenol present in Syzygium aromaticum is responsible for
⁎ Corresponding author. Tel.: + 91 44 22299006.
E-mail address: vijaya025@yahoo.com (K. Vijayaraghavan).
and anesthetic properties. In the present study, we discuss the biosyn-
thesis of Ag nanoparticles using the commercially economic and abun-
dantly available Syzygium aromaticum as the biomaterial.
2. Materials and methods
2.1. Preparation of extract from Syzygium aromaticum bud powder
Syzygium aromaticum dried buds were purchased from a local
market, and were sieved to remove impurities and sun dried for
5 hrs to remove the residual moisture if any present on the buds.
The buds were powered in milling machine and then sieved in 10
mesh sieve to get finer particles. The finely sieved powder was used
for all further studies in the preparation of extract. 25 g of sieved
clove buds was extracted in 100 ml hot sterile distilled water. The
aqueous extract was filtered using sintered glass crucible.
2.2. Biosynthesis of nano-scale Ag particles using Syzygium aromaticum
extract
Silver nitrate was purchased from Sigma-Aldrich, USA. For the Ag
nanoparticle biosynthesis 500 μL of extract was used as a reducing
and capping agent in a 50 mL of 1 mM AgNO3 solution. The reaction
flask was covered with aluminium foil and subjected to constant mix-
ing in a rotary shaker at 120 rpm. The experiments were conducted in
room temperature at 28 °C. The color of the solution during the

0167-577X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.01.083
34 K. Vijayaraghavan et al. / Materials Letters 75 (2012) 33–35

course of the reaction gradually turned from colorless to brick red and
finally to dirty reddish brown in color at the end of 24 hrs. The pro-
gress of Ag nanoparticles formation during the biosynthesis was
monitored at regular intervals based on surface plasmon resonance
in a UV–visible spectrophotometer at 430 nm. Shape and size of the
formed nanoparticles was determined using scanning electron micro-
scope, while the energy dispersive X-ray analysis (EDAX) was per-
formed for providing the crystalline nature of the sample.

3. Results and discussion

Bioreduction of silver particle was measured using UV–vis spec-

troscopy based on the surface plasmon resonance leading to the in-
crease in color intensity. This is an indirect method of detecting the
nanoparticle formation, still valid to be an excellent indicator towards
nano-scale formation of metal particle. The raw clove extract
appeared dark brown in color. 500 μL of the extract was used as the
reductant and capping agent during the synthesis of silver nanoparti-
cle at an initial AgNO3 concentration of 1 mM in 50 mL of water. Dur-
ing the initial period of the reaction the solvent was colorless. Initial
appearance of pale red color occurred at the end of 5 min of reaction
time and thereafter its intensity increased further as the reaction time
progressed. The appearance of pale reddish tinge is the first indication
that the nanoparticle formation has been initiated. As the reaction pe-
riod increased the intensity of the red color increased up to 18 hrs.
Further increase in reaction time (24 hrs) resulted in change in sur-
face plasmon resonance (SRP) from reddish to dirty reddish brown,
which could be due to the growth of the nanoparticle. Sample was
drawn at the end of 24 hrs for the nano scale determination of syn-
thesized AgNPs. Nano scale formation of AgNPs was confirmed
based on its surface plasmon resonance, which was captured in UV–
vis spectrum as shown in Fig. 1. The observed results are in corrobo-
ration with the earlier researcher who stated that as the reductant
concentration increased the color intensity also increased [10]. Bio-
logical method of synthesis of silver nanoparticles exhibits strong ab-
sorption of electromagnetic waves in the visible range due to their
optical resonant property (SPR), which occurs due to its collective os-
cillation of conduction electrons in mutual with the incident light
[11]. The SPR is highly influenced by shape and size of the nanoparti-
cles [12].
UV–visible spectrum of silver nanoparticles upon the interaction
with CCl4 showed a plasmon excitation at 438 nm resulting in silver
nanoparticles of 60–80 nm diameters [13]. Biological synthesis of sil-
ver nanoparticle using Escherichia coli showed a wide spectrum
Fig. 2. Scanning electron microscope shows the presence of varying sized silver nano-
particle formed during the interaction with Syzygium aromaticum extract.
around 390 to 410 nm due to the aggregation of the silver nanoparti-
cles [14]. Sathishkumar et al., [10] stated that maximum absorbance
occurred at 435 nm due to the presence of silver particle. The peak
area increased with the increase in reaction time. The possible reason
for this type of behavior could be due to the reduction of silver ion by
the biomolecules in accordance with earlier researchers [15]. Shifting
of peak was due to the growth of particle, which could be visualized
by the change in color due to the surface palmonic emission. Clove
shares certain similarity in chemical compounds with C. zeylanicum
bark due to the presence of eugenol and caryophyllene, which con-
tribute to its distinct aroma [16].
Syzygium aromaticum extract is rich in eugenol which comprised
72–90% of the essential oil followed by other constituents such as ace-
tyl eugenol, beta-caryophyllene and vanillin, crategolic acid, tannins,
gallotannic acid, methyl salicylate, the flavonoids eugenin, kaemp-
ferol, rhamnetin, and eugenitin, triterpenoids like oleanolic acid, stig-
masterol and campesterol and several sesquiterpenes. It has been
proved that aliphatic and aromatic compounds contain a wide variety
of functional groups, e.g., cyano (―CN), mercapto (―SH), carboxylic
acid (―COOH) and amino (―NH2), known to have a high affinity
for functionalization of noble metal nanoparticles, and thus are useful
as surface-protective functional groups [17-20]. The reduction of sil-
ver nitrate by eugenol occurred due to the inductive effect of meth-
oxy and allyl groups, which are positioned at the ortho and para

Fig. 1. UV–visible spectrum of silver nanoparticles and its plasmon excitation upon the
interaction with Syzygium aromaticum extract. Fig. 3. EDAX confirms that the formed nanoparticles are silver.
 K. Vijayaraghavan et al. / Materials Letters 75 (2012) 33–35 35

Table 1 extract in environmentally friendly universal solvent namely water,

EDAX showing the purity of synthesized AgNP. which would open new ventures in the application of formed silver
Element Wt (%) At (%) nanoparticle. Future research based on synthesis of size specific nano-
particle based on the optimization of reaction condition would be an
ClK 00.92 02.75
AgL 99.08 97.25 interesting area.
Matrix Correction ZAF

Acknowledgments

positions of proton releasing ―OH group. This reaction leads to the We are grateful to Management of Bharath University, Sir Theagaraya
formation of resonating structure of the anionic form of eugenol College, Vel Tech Dr RR & Dr SR Technical University and Marina Labs. We
[21]. Earlier reports suggested that terpenoids present in the Gerani- acknowledge SAIF-IITM for the SEM analysis.
um and Cinnamomum camphora leaf were found to be involved in the
biosynthesis of Ag nanoparticle [7]. Polyols such as terpenoids, fla-
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