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Materials Letters 62 (2008) 3103 3105 www.elsevier.com/locate/matlet

Solventless synthesis and optical properties of Au and Ag nanoparticles using Camellia sinensis extract
Alfredo R. Vilchis-Nestor a , Victor Snchez-Mendieta a,, Marco A. Camacho-Lpez a , Rosa M. Gmez-Espinosa a , Miguel A. Camacho-Lpez b , Jess A. Arenas-Alatorre c
c

Facultad de Qumica, Universidad Autnoma del Estado de Mxico, Toluca, Mexico, 50120 Facultad de Medicina, Universidad Autnoma del Estado de Mxico, Toluca, Mexico, 50120 Instituto de Fsica, Universidad Nacional Autnoma de Mxico A. P. 20-364, Mexico, 01000, D.F.
b

Received 5 December 2007; accepted 31 January 2008 Available online 19 February 2008

Abstract A facile bottomup green synthetic route using green tea (Camellia sinensis) extract as reducing and stabilizing agent produced gold nanoparticles and silver nanostructures in aqueous solution at ambient conditions. Colloidal systems of silver and gold nanoparticles exhibit highly efficient single photon-induced luminescence. This optical response can be manipulated by changing concentrations of metal ions and the quantity of reducing agent, which plays a crucial role in formation, growth and luminescence response of these noble-metal nanostructures. 2008 Elsevier B.V. All rights reserved.
Keywords: Nanomaterials; Luminescence; Green nanochemistry

1. Introduction Inorganic nanoparticles exhibit size and shape-dependent properties that are of interest for applications ranging from catalysts [1] and sensing [2,3] to optics [4] and data storage [5]. There has also been an increasing interest in studying the optical properties of gold and silver colloids by UVVisNIR and fluorescence spectroscopies [6]. There is an ever-growing need to develop eco-friendly nanostructures synthetic procedures (green nanochemistry) [7]. Recently, biosynthetic methods employing either biological micro-organism such as bacteria [8] and fungus [9] or plants extract [1013], have emerged as a simple and viable alternative to more complex chemical synthetic procedures to obtain nanomaterials. In this work, the easy synthesis of silver and gold nanoparticles by a simple and environmentally friendly procedure involving the in situ reduction of aqueous Ag(I) and Au(III) by green tea (Camellia sinensis) extract, is reported.
Corresponding author. Tel.: +52 722 2175109. E-mail address: vsm@uaemex.mx (V. Snchez-Mendieta). 0167-577X/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2008.01.138

2. Experimental A conventional green tea bag (Lagg's), containing 1.5 g of the plant, was boiled in 100 mL of de-ionized water. Aliquots of this extract, 1 to 4 mL, were added separately to 5 mL of 10 3M aqueous HAuCl4 solutions and the volume was made up to 10 mL by adding the appropriate amount of de-ionized water. Similarly, for the synthesis of silver nanostructures, 2.5 mL of ammonia solution was added to 5 mL of 10 3M AgNO3 solution, followed by addition of C. sinensis extract, 1 to 10 mL and the final volume was adjusted to 50 mL with de-ionized water. Addition of C. sinensis extract to aqueous HAuCl4 solutions quickly turned the initial yellowish solution into pink, grey-blue and pale violet, respectively (inset of Fig. 1a). For silver nanoparticles, the solution turned from yellowish to bright yellow and to dark brown (inset of Fig. 1b). UVVisNIR absorption spectra were recorded on a CARY 5000 spectrophotometer operated at a resolution of 1 nm. TEM studies were performed on a JEM-100CX transmission electron microscope. Luminescence spectra of all the samples were obtained using a Horiba Jovin Yvon Spectrofluorimeter (Fuoromax-P) with dual

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excitation and emission monochromators in a wavelength range between 350 and 800 nm.
3. Results and discussion It is well known that C. sinensis contains polyphenols, a green tea aqueous extract contains 59.8mg CAE/g of phenolic compounds (CAE = chlorogenic acid equivalents in milligrams per gram dry material) [14] and terpenoids, such as -cariophyllene ( 800 g/mL), linalool ( 1600 g/mL), cis-jasmone( 800 g/mL), -terpineol ( 800 g/mL), -cadinene ( 1600 g/mL), indole ( 800 g/mL), geraniol ( 400 g/mL), among the major bio-components, which have bactericidal and antioxidant activity, and several other useful properties [15,16]. These type of compounds contribute to the metal ion reduction processes, as stated in previously reported bio-reduction methods [10,11], and can also control the size and the stability of the nanostructures formed. For instance, gallic acid, a secondary phenolic metabolite present in plants like green tea with powerful antioxidant properties, has been successfully used to obtain water soluble Au and Ag nanostructures, and has proved to be an efficient capping agent of these noble-metal nanoparticles [17,18]. UVVis spectra of Au and Ag nanoparticles in aqueous solution are shown in Fig. 1a and 1b, respectively. The absorption peaks at around 550 nm for Au and around 430 nm for Ag are characteristic of these noble-metal particles [913]. Red shift is observed in both spectra (Fig. 1), which could be due to an increment in the particle size. In other words, the wavelength shift observed in the plasmon bands is a consequence of the different volume of C. sinensis extract added to the metal ions solution; however, the initial metal ion concentrations and the reaction time play also a crucial role in the optical properties and size obtained for these nanostructures. The reduction of silver ions and the formation of stable nanoparticles occur rapidly within 4h of reaction (Fig. 1b), being, thus, one of the fastest bio-reducing methods to produce silver nanostructures reported so far. Meanwhile, stable gold nanoparticles are obtained until 24h of reaction (Fig. 1a). A good control of optical properties of gold nanotriangles, synthesized with lemongrass extract, was also achieved with a simple variation of the extract concentrations [18]. TEM images of poly-disperse gold nanoparticles are shown in Fig. 2a. Some anisotropic nanotriangles and nanoparticles with irregular contours could be observed in Fig. 2a, with an average particle size of around 40 nm. TEM studies also revealed that the concentration of tea extract plays the main role in the size of the metal nanoparticles. When 1 mL of green tea extract was used for the formation of Au nanoparticles, more

Fig. 1. (a) UVVisNIR absorption spectra of gold nanoparticles formed after 24 h adding 4, 2 and 1 mL of Camellia sinensis extract, curves 13, respectively, and 5 mL of 10 3 M aqueous solution HAuCl4, the final volume was adjusted to 10 mL to reach a concentration of 5 10 4 M of HAuCl4. (b) UVVis absorption spectra of silver nanostructures formed after 4 h adding 1, 5 and 10 mL of Camellia sinensis extract, curves 13, respectively, and 5 mL of 10 3 M aqueous solution AgNO3, the final volume was adjusted to 50 mL to reach a concentration of 1 10 4 M of AgNO3.

Fig. 2. (a) TEM images of gold nanoparticles formed after 24 h of reaction, using 1 mL of Camellia sinensis extract and 5 mL of 10 3 M aqueous solution HAuCl4. (b) Silver nanostructures formed after 24 h of reaction, using 2 mL of Camellia sinensis extract and 5 mL of 103 M aqueous solution AgNO3.

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out electrostatic interactions. Although good efforts have been done to elucidate these reduction and stabilization mechanisms [17] further studies are required.

4. Conclusion Gold and silver nanoparticles have been successfully prepared using a simple and efficient green nanochemistry methodology. Furthermore, we have demonstrated that use of a natural, renewable and low cost biological reducing agent, such as C. sinensis plant can produce metal nanostructures in aqueous solution at ambient temperature, avoiding the presence of hazardous and toxic solvents and waste. The colloidal systems of silver and gold nanoparticles, stabilized by the bio-molecules present in the C. sinensis aqueous solution, are currently under evaluation as prospective useful bioimaging agents for medical applications due to their characteristic optical properties exhibited. References
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Fig. 3. Fluorescence spectra of Au (solid line) and Ag (dashed line) nanoparticles. The excitation wavelengths were 328 nm and 380 nm, respectively.

anisotropic particles were obtained (Fig. 1a). However, by doubling the amount of C. sinensis extract from 1 to 2 mL, the resulted nanoparticles are slightly bigger and more spherical. It is believed that, when a larger concentration of bio-reducing agent is used, a relatively fast nucleation process occurs, which is followed by a slower growing stage due to stronger interactions between protective bio-molecules and growing Au nanocrystals, leading to the formation of more isotropic particles [11]. On the contrary, when a larger volume of C. sinensis extract is added to a silver ions solution, the resultant nanocrystals exhibit anisotropy, which is mainly attributed to both, a rapid reduction of the Ag ions and fast sinter of growing crystals into anisotropic nanostructures (Fig. 2b). This last outcome can be explained by weaker interactions of Ag growing nanoparticles and protective bio-molecules compared to those with Au nanoparticles. This also explains the different rate of formation of stable Au and Ag nanoparticles using this methodology, as followed by the plasmon absorption resonance studies. Fluorescence spectra of Au and Ag colloids are shown in Fig. 3. In both spectra the most noticeable feature is the intense broad peak at 448 nm for the Au colloid and 470 nm for the Ag colloid, corresponding to emission energy of 2.7 and 2.6 eV, respectively. These energy bands are formed due to the fact that as the size of the metal particles become smaller, quantum size effects become noticeable and dominant. For example, for Au nanoparticles, this occurs when the particles are in the size regime of 0.52.0 nm [19]. Therefore, gold and silver nanoparticles exhibit highly efficient single photon-induced luminescence, which may be due to their ability to sustain resonating surface plasmons with minimal damping. Control of the size and morphology of the resultant nanostructures can be related to the interactions between biomolecules (e.g., terpenoids, polyphenols and phenolic acids) and metal atoms [20]. Therefore, it is thought that phenolic acid-type biomolecules present in C. sinensis extract, are responsible for the reduction of silver and chloroaurate ions, and also for the stabilization of the nanoparticles through-