E-ISSN: 2278-3229

IJGHC, March 2014 - May-2014; Vol.3, No.2, 401-408.

International Journal of Green and Herbal Chemistry

An International Peer Review E-3 Journal of Sciences

Available online atwww.ijghc.com

Green Chemistry
Research Article CODEN (USA): IJGHAY

Eco-friendly Green Synthesis and Spectrophotometric Characterization of Silver Nanoparticles Synthesized using Some Common Indian Spices
Sankar Narayan Sinha* and Dipak Paul
Environmental Microbiology Research Laboratory, Department of Botany, University of Kalyani, Kalyani 741235, West Bengal, India
Received: 20 January 2014; Revised: 20 February 2014; Accepted: 1 March 2014

Abstract: Biosynthesis of nanoparticles is under exploration is due to wide biomedical applications and research interest in nanotechnology. In this study bio-reduction of silver nitrate (AgNO3 ) for the green synthesis of silver nanoparticles with the twelve spices extract has been carried out. The spices extract are mixed with silver nitrate solution, incubated and studied synthesis of nanoparticles using UVvisible spectrophotometer and also confirmed by the change of the colour of the nanoparticle solutions and concerned pH was also determined. The results showed that the spice extracts are very good bio-reductant for the synthesis of silver nanoparticles. Keywords: Eco-friendly synthesis, Green synthesis, Silver nanoparticles, Spices extract, Spectrophotometry

INTRODUCTION The field of nanotechnology is one of the most active areas of research in modern materials science. Nanoparticles exhibit totally new or improved properties based on specific characteristics like size, form and distribution1-3. Synthesis of silver nanoparticles has drawn considerable attention owing to their various properties like catalysis, magnetic and optical polarizability4, electrical conductivity5, antimicrobial activities6 and surface enhanced Raman scattering7. Various techniques are available for the synthesis of silver nanoparticles for example, reduction in solutions8, thermal decomposition of 401 IJGHC, March 2014 - May-2014; Section A; Vol.3, No.2, 401-408.

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silver compounds9, chemical and photochemical reactions in reverse micelles10 , radiation assisted11, electrochemical12, sonochemical13, microwave assisted process14 and via green chemistry route15-17. Green synthesis provides benefit over chemical and physical method because it is cost effective, ecofriendly, easily scaled up for mass-scale synthesis and there is no need to use temperature, high pressure, energy and toxic chemicals. Synthesis of nanoparticle using bacteria18, fungus19, algae20, enzymes21 and plants extracts22-24 have been suggested as possible eco-friendly alternatives to chemical and physical methods. Using plant parts for nanoparticle synthesis can be advantageous over other biological methods because it eliminates the elaborate process of maintaining cell cultures and can also be suitably scaled up for mass-scale synthesis of nanoparticles under natural environment25. It has been reported that medicinally important angiosperms have the greatest potential for the synthesis of metallic nanoparticles with respect to quality and quantity26, 27. The main phytochemical compounds responsible for the synthesis of nanoparticles are terpenoids, flavonoids, ketones, aldehyde, amides and other molecules with bioactivity. Herein, we investigated the biosynthesis of silver nanoparticles via green chemistry route, reducing the silver ions present in the silver nitrate solution by the aqueous extract of twelve common Indian spices. Reduction of silver nitrate to silver ions was confirmed by the colour change from colourless to brown. The formation of silver nanoparticles was also confirmed by spectrophotometric determination. MATERIALS AND METHODS Preparation of plant extracts: Twelve spices (Figure 1), such as Cuminum cyminum, Foeniculum vulgara, Nigella sativa, Trigonella foenum-graecum, Trachyspermum roxburghianum, Trachyspermum ammi, Elettaria cardamomum, Coriandrum sativum, Syzygium aromaticum, Cinnamomum verum, Cinnamomum tamala and Piper nigrum which was included in this study were collected from local market and it was thoroughly washed with distilled water and dried with water absorbent paper (wet filter paper).

Figure 1: Photographs of the spices used for silver nanoparticles synthesis. A. Cumin, B. Fennel, C. Black cumin, D. Fenugreek, E. Ajmod, F. Ajwain, G. Coriander, H. Cardamom, I. Clove, J. Cinnamon, K. Indian bay leaf, L. Black pepper 402 IJGHC, March 2014 - May-2014; Section A; Vol.3, No.2, 401-408.

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After that, grind the spices to make fine powder using mortar and pestle. About 10 g of freshly prepared dry powder of each spice were suspended in 100 ml of double distilled water and boiled at 80C temperature for one hour. Then filtered the solution through a Whatman No. 1 filter paper and the solution was used as stock solution for further experimental use. Plant mediated synthesis of silver nanoparticles: The silver nitrate (AgNO3) was purchased from Merck India Ltd and it was used as a precursor in the silver nanoparticles synthesis process. Five millilitre of spice extract was added to 95 ml 1 mM silver nitrate solution and allowed to react at ambient conditions. The same protocol was followed for all the twelve spice extracts. The colour change of the extracts from pale yellow to dark brown was observed periodically. The colour change in the solutions occurred indicating the formation of silver nanoparticles. UV-visible spectral analysis: The reduction of pure Ag+ ions was monitored by measuring the UV-vis spectrum of the solution by diluting a small aliquot of the sample. UV-vis spectral analysis was performed through a UV-vis spectrophotometer (Shimadzu UV-1601PC) at the range of 300-700 nm and observed the absorption peaks at 420-460 nm regions, which are identical to the characteristics UV-visible spectrum of metallic silver and it was recorded. pH analysis: Change in pH of silver nanoparticle solution due to synthesis of silver nanoparticles using extracts of spices was determined by digital pH meter (Jenway 3510). RESULTS AND DISCUSSION Twelve spices extracts were used to produce silver nanoparticles (AgNPs) (Table 1). The synthesized silver nanoparticles were confirmed by visual observation. The colours of the all extracts were changed into different yellowish-brown due to reduction of silver ions (Figure 2 and Table 2). The reduction of various complexes with Ag+ ions leads to the formation of silver atoms (Ag0), which is followed by agglomeration into oligomeric clusters 28. UVvis spectroscopy is an indirect method to study the bioreduction of silver nanoparticles from aqueous AgNO3 solution. One of the most considerable features in optical absorbance spectra of metal nanoparticles is surface plasmon band, which appear as a result of collective electron oscillation around the surface mode of the particles. Table-1: Details of spices used for silver nanoparticles (AgNPs) synthesis S. 1 2 3 4 5 6 7 8 9 10 11 12 Scientific name Cuminum cyminum Foeniculum vulgar Nigella sativa Trigonella foenum-graecum Trachyspermum roxburghianum Trachyspermum ammi Coriandrum sativum Elettaria cardamomum Syzygium aromaticum Cinnamomum verum Cinnamomum tamala Piper nigrum Common name Cumin Fennel Black cumin Fenugreek Ajmod Ajwain Coriander Cardamom Clove Cinnamon Indian bay leaf Black pepper Local name Jeera Mouri Kalo jeera Methi Radhuni Jowan Dhone Elaichi Labanga Darchini Tej pata Gol morich Family name Apiaceae Apiaceae Ranunculaceae Fabaceae Apiaceae Apiaceae Apiaceae Zingiberaceae Myrtaceae Lauraceae Lauraceae Piperaceae Part used Seed Seed Seed Seed Seed Seed Seed Seed pod Flower bud Bark Leaf Fruit

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Figure 2: Colour change of twelve spices extracts containing AgNO3 solution: A. 1 mM AgNO3 solution, B. before synthesis, C. after synthesis of nanoparticles. (a) Cuminum cyminum, (b) Foeniculum vulgara, (c) Nigella sativa, (d) Trigonella foenum-graecum,(e) Trachyspermum roxburghianum, (f) Trachyspermum ammi,(g) Coriandrum sativum, (h) Elettaria cardamomum, (i) Syzygium aromaticum, (j) Cinnamomum verum, (k) Cinnamomum tamala, (l) Piper nigrum Table-2: Change of colour of the solution due to silver nanoparticles synthesis Sl. no 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12 Plants used for AgNPs synthesis Change of colour Before After Pale yellow Pale yellow Pale yellow Pale yellow Light yellow Pale yellow Whitish Whitish Dark yellow Pale yellow Pale yellow Dark yellow Reddish brown Deep brown Yellowish brown Yellowish brown Reddish brown Brown Yellowish brown Deep brown Blackish brown Yellowish brown Deep brown Deep brown Colour Absorption intensity maxima ( max) ++ 443 +++ 460 ++ 440 ++ 456 ++ 466 ++ 458 ++ 439 + 447 +++ 469 ++ 436 +++ 453 +++ 445

Cuminum cyminum Foeniculum vulgara Nigella sativa Trigonella foenum-graecum Trachyspermum roxburghianum Trachyspermum ammi Coriandrum sativum Elettaria cardamomum Syzygium aromaticum Cinnamomum verum Cinnamomum tamala Piper nigrum

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Previous studies have reported that silver exhibits yellowish-brown colour due to the excitations of their surface plasmon response (SPR) 29, when dissolved in water. In this work all of the twelve spices extract showed characteristics band in UV-vis region (Figure 3 and Figure 4) such as Cuminum cyminum at 443 nm, Nigella sativa at 440 nm, Elettaria cardamomum at 447 nm, Cinnamomum tamala at 453 nm etc which are identical to the characteristics UV-vis spectrum of metallic silver. Similar types of observation were also reported by many researchers 30, 31.

Figure 3: UV-vis absorption spectrum of different silver nanoparticles solutions (A) Cuminum cyminum, (B) Foeniculum vulgara, (C) Nigella sativa, (D) Trigonella foenum-graecum, (E) Trachyspermum roxburghianum, (F) Trachyspermum ammi 405 IJGHC, March 2014 - May-2014; Section A; Vol.3, No.2, 401-408.

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Figure 4: UV-vis absorption spectrum of different silver nanoparticles solutions (G) Coriandrum sativum, (H) Elettaria cardamomum, (I) Syzygium aromaticum, (J) Cinnamomum verum, (K) Cinnamomum tamala, (L) Piper nigrum In this work almost all silver nanoparticles solutions were showed characteristic increase in pH after incubation at room temperature (Figure 5). The increased pH indicated the formation of nanoparticles by the reduction of silver nitrate by aqueous extract of spices. This may be probably due to the availability of more H+ from the metabolites at higher pH which enables quicker reduction of silver nitrate and hence the oxidation of the metabolites 32 . Similar type of observation was also reported by Priya et al. 33. Maximum increase in pH was showed in case of Piper nigrum. 406 IJGHC, March 2014 - May-2014; Section A; Vol.3, No.2, 401-408.

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P. nigrum C. tamala C. verum S. aromaticum E. cardamomum C. sativum T. ammi T. roxburghianum T. foenum-graecum N. sativa F. vulgara C. cyminum 0 2 pH 4
5.42 3.56 4.46 4.69 4.66 5.42

6.01 5.95 5.82

6.93

5.66 6.19 5.89 6.08 6.14 6.24 6.06 6.03 6.2 6.51

5.73 5.32 5.25

5.68

After AgNPs synthesis

Before AgNPs synthesis

Figure 5: Change of pH of the solution due to synthesis of silver nanoparticles CONCLUSION The reduction of Ag+ ion by these spices extracts resulted in the formation of stable nanoparticles. The rate of reduction for the synthesis of nanoparticles by this method was rapid. Synthesis of silver nanoparticles by the green chemistry approach reported in this study using twelve spice extracts may find potent use in biomedical applications. Furthermore, we demonstrated that use of natural, renewable and low cost biological reducing agent, such as these spices could produce metal nanostructures in aqueous solution at ambient temperature, avoiding the occurrence of hazardous and toxic solvents. ACKNOWLEDGEMENT The authors thank to University of Kalyani, West Bengal, India for providing necessary facilities for doing this research. Authors acknowledge the financial support received under the grant from DST PURSE, New Delhi, India for this study. REFERENCES
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*Corresponding Author: Sankar Narayan Sinha; Environmental Microbiology Research Laboratory, Department of Botany, University of Kalyani, Kalyani-741235, W.B., India

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