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Efficient in-Planta biosynthesis and isolation of gold nanopartilces (AuNPs) View project
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Cumin seed was investigated for synthesis of gold nanoparticles. Polydispersed particles were
obtained at pH 3 and 30 C, and the effect of temperature and pH on synthesis of gold nanoparticles
was analyzed. TEM images showed that amount of platelets formed were predominant at lower
temperature where as more number of monodispersed spherical particle of size 1–10 nm were
perceived at high temperatures. The gold nanoparticles particles formed at higher pH were stable,
uniform and spherical in shape. XPS analysis showed the presence of pure gold nanoparticles.
Keywords: Gold Nanoparticle, Cumin Seed, XPS.
1. INTRODUCTION of temperature
Delivered by Ingenta to: and pH, followed by investigation on the
chemical of
Indian Association for the Cultivation state of the (IACS)
Science nanoparticles formed, using X-ray
Gold nanoparticles (AuNPs) have attracted significant photoelectron spectroscopy (XPS).
RESEARCH ARTICLE
IP : 202.54.54.240
attention owing to its wide range of applications from
Tue, 29 Mar 2011 08:26:11
catalysis to diagnostics. Numerous chemical synthetic
routes have been used for synthesis of AuNPs. Due to the 2. EXPERIMENTAL DETAILS
employment of harmful chemicals, the usage of chemically
2.1. Preparation of Cumin Seed
synthesized nanoparticles to biological applications is lim-
Powder Extract (CSE)
ited. This snag has lead biological synthesis routes to gain
considerable attention in the recent past.1 Even though Cumin seeds purchased from a local market were washed
number of reports are available on nanoparticle synthesis to remove any impurities and powdered in a mixer, and
by microbes, usage of plants to synthesize has continued sieved through a 20-mesh sieve, to obtain uniform size
to flourish in order to materialize their use in large scale particles. 2.5 g of the sieved powder was added to 100 mL
production, since they are non pathogenic, easily avail- sterile distilled water in a 500 mL Erlenmeyer flask and
able and easy to use.2 Although plants such as Coriander boiled for 2 min. This was then allowed to cool to room
leaf, Alfalfa, Aloe vera, Neem, Cinnamomum camphora, temperature and filtered using sterile Wattman No. 1 filter
Emblica offincianalis, lemon grass and tamarind have been paper to obtain CSE.
reported as potent biological materials for synthesis of
AuNPs, the available resources are yet to be completely 2.2. Biosynthesis of Gold Nanoparticles
explored.3 Toting up to these plants we have used Cumin
seed for biosynthesis of AuNPs. Cumin is an herbaceous Chloroauric acid was purchased from Sigma-Aldrich,
plant grown in Mediterranean climate and is known for its USA. AuNPs were synthesized from CSE by adding
stimulant, antispasmodic and carminative properties. 50 mL of 1 mM AuCl− 4 solution to 5 mL of freshly pre-
Cumin’s distinctive flavor and strong, warm aroma are pared CSE in a 250 mL Erlenmeyer flask and incubated in
due to its essential oil content.4 shaker at 160 rpm at 30 C for 24 h. Followed by visual
Present study describes for the first time use of observations, after 24 h the biogenic nanoparticles were
cumin seed powder for synthesis of gold nanoparticle collected by centrifuging the samples at 10000 rpm for
and nanoplatelets. We have also scrutinized the effect 15 min. The effects of pH and temperature on biosynthe-
sis were performed at various initial pH ranging from 1–9
∗
Author to whom correspondence should be addressed. and temperature ranging from 0 to 100 C.
Absorbance
0.30
670 double beam spectrophotometer using 0.1 mL of the
0.25
sample, diluted to 2 mL with sterile de-ionised water.
0.20
The synthesized AuNPs suspension was centrifuged and
0.15
the sample was subjected to TEM analysis. TEM sam-
0.10
ples of biogenic AuNPs were prepared by placing a drop 400 500 600 700 800
Wavelength (nm)
of the suspension on carbon-coated copper grids and the
films on the TEM grids were allowed to stand for 2 min,
after which the surplus solution was removed using a
blotting paper and the grid was allowed to dry prior
to measurement. TEM observations were performed on
a HITACHI-JP/H7600 instrument (Japan) operated at an
accelerating voltage of 100 kV. The residual metal ion
concentration after bioreduction was analysed using ICP
(Agilent 7500). X-ray photoelectron spectroscopy (XPS) Fig. 1. TEM image of AuNPs produced after 24 h using 2.5 mL of
analysis, for determining the chemical state of the biogenic CSE at 30 C and pH 3.
AuNPs was performed on AXIS-NOVA (Kratos Inc) with
monochromatic Al K (1486.6 eV) X-ray as source, base vibration component (longitudinal component of SPR
pressure 85 × 10−9 Torr, pass energy 160 eV (wide scan), band).5 6 Similarly, the UV-Vis-NIR spectrum illustrates
20 eV (narrow scan), dwell time-100 ms and no surface the increase in intensity of the out of plane (transverse)
treatment. SPR band. A broad SPR band from 800 to 1200 nm indi-
cates the formation of anisotropic nanoparticles, as incuba-
3. RESULTS AND DISCUSSION tion temperature increased to 20 C.7 Drastic changes were
observed as the incubation temperature increased to 100 C
3.1. Biosynthesis of Gold Nanoparticles Delivered by Ingenta (Fig. 2). to:
The UV-Vis-NIR data represents the shift of the
in plane SPR band towards lower wavelength and this is
Addition of CSE to 10−3 Indian Association
M aqueous HAuCl− for the Cultivation of Science
4 solution, assigned to the
(IACS)
decrease in the edge length of triangu-
RESEARCH ARTICLE
Control 0 °C pH 1 pH 5
20 °C 40 °C pH 9
Absorbance
pH 3
pH 5
pH 1
pH 7 pH 9
80 °C
100 °C
Delivered by Ingenta to:
ture. Nanotriangles have a wide range of applications from
Indian Association for the Cultivation
40 °C of Science
use on cantilevers (IACS)
to drug delivery.10 Since at lower tem-
RESEARCH ARTICLE
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: 202.54.54.240
°C perature, more number of nanoplatelets was formed; XPS
0 °C Tue,6029
°C
Mar 2011 08:26:11
studies were performed for biogenic AuNPs obtained at
400 600 800 1000 1200 20 C to quantify the elemental composition and electronic
Wavelength (nm) configuration. Wide scan spectrum of AuNPs reveals the
Fig. 2. Effects of temperature on AuNPs biosynthesis. presence of C, O, Au elements. The existence of these
peaks is due to the use of biomaterial and no other peaks
at pH 1 whereas a wide range of spherical nanoparti- are observed from the spectrum which reveals highly pure
cles and anisotropic nanoparticles were formed at pH 3 AuNPs. The inset Figure 4 (i) represents Au4f doublet nar-
(with a prominent broad SPR band in the NIR region) row scan spectrum AuNPs. The binding energies observed
(Fig. 3). at 85.15 and 88.8 eV represent 4f 7/2 and 4f 5/2 energy
In contrast to lower pH, it is observed that with increase states of Au particles, respectively. The obtained binding
in pH, the intensity of SPR band in the NIR region
decreases. The noted changes in the UV-Vis-NIR spec- 2000
Intensity (a.u)
energies are higher than that of bulk gold particles (84 eV) 4. CONCLUSION
but are closer to the binding energies of AuI (84.9 eV).
On the other hand, Zhang and Sham11 reported that the In summary, the study reveals that AuNPs thus obtained
electron donated from the surface of gold atoms to thio- are pure; and stable in nature over a period of 1 month at
late lead to the high binding energy shift of the material room temperature. Nanoplatelets can be produced at 20 C
and spherical AuNPs can be synthesized at 100 C. Poly-
Au0 (4f) energy state. A plausible reason for the shift in
dispersed AuNPs can be obtained at pH 3 and room tem-
binding energy of CSE-synthesized AuNPs may be due
perature. These biogenic AuNPs are water soluble and this
the capping of AuNPs by the polyols present in the CSE.
property widens their scope in various applications. XPS
Electron donated from the gold atom to the capping agent
studies show the pure and crystalline nature of biogenic
or the un-reacted precursor may have lead to a high bind-
nanoparticles.
ing energy shift.
The peak positions, shapes, and peak to peak distance
Acknowledgment: This work was supported by NRF
(3.65 eV) observed for the prepared material are consis-
(2009-0083194) and KEITI Grants funded by the Korean
tent with the identical spectrum of the gold oxidation state Government.
Au0 . XPS study shows the pure and crystalline form of
CSE-synthesized AuNPs. Shankar et al.10 stated that the
reduction of chloroaurate ion may have been caused by References and Notes
the reducing sugars present in lemon grass extract and that 1. Y. Nangia, N. Wangoo, S. Sharma, J.-S. Wu, V. Dravid, G. S.
the formation of nanoplatelets may be due to the the inter- Shekhawat, and C. R. Suri, Appl. Phys. Lett. 94, 233901 (2009).
action between AuNPs and aldehydes/ketones. It has also 2. M. Sathishkumar, K. Sneha, S. W. Won, C.-W. Cho, S. Kim, and
been suggested that enzymatic reduction of metal nanopar- Y.-S. Yun, Coll. Surf. B. 73, 332 (2009).
3. K. Badri Narayanan and N. Sakthivel, Mater. Lett. 62, 4588 (2008).
ticle can occur in the presence of NADH-reductase and 4. S. A. Willatgamuwa, K. Patel, G. Saraswathi, and K. Srinivasan,
nitroreductases enzymes.5 Previous studies have revealed Nutritional Res. 18, 131 (1998).
that various polyols such as terpenes, flavonoids and other 5. J. Y. Song, H.-K. Jang, and B. S. Kim, Process Biochem. 44, 133
polysaccharides may act as reducing and capping agent in (2009).
nanoparticle biosynthesis. However, the exact mechanism 6. A. Rai, A. Singh, A. Ahmad, and M. Sastry, Langmuir 22, 736
IP : 202.54.54.240
and can prove to be a low cost, efficient, green approach 8. R. Sajanlal and T. Pradeep, Adv. Mater. 20, 980 (2008).
Tue, 29 Mar
for synthesis of spherical and non spherical nanoparticles.
20119. 08:26:11
A. Shipway, M. Lahav, R. Gabai, and I. Willner, Langmuir 16, 8789
(2000).
Nevertheless, the use of plant extracts for biological syn- 10. S. S. Shankar, A. Rai, B. Ankamwar, A. Singh, A. Ahmad, and
thesis of nanoparticles can be a definite retreat for conven- M. Shastry, Nature Mater. 3, 482 (2004).
tional methods of nanoparticles fabrication. 11. P. Zhang and T. K. Sham, Phys. Rev. Lett. 90, 245502 (2003).