Mater. Res. Soc. Symp. Proc. Vol.

901E © 2006 Materials Research Society

0901-Ra16-55-Rb16-55.1

Novel Synthesis of Gold Nanoparticles in Aqueous Media

A. Sugunan and J. Dutta Microelectronics, School of Engineering and Technology, Asian Institute of Technology, Pathumthani, 12120, Thailand ABSTRACT

Aqueous synthesis of glutamate functionalized single crystal gold nanoparticles was achieved by reducing a solution of chloroauric acid with monosodium glutamate. Highly uniform size distributions of the nanoparticles can be obtained by having an excess of monosodium glutamate in the starting solution. Similar to the conventional synthesis of gold nanoparticles by reduction of chloroauric acid with trisodium citrate, the obtained particle sizes were varied in the range of 14 – 25 nm without loosing the uniformity in its size distribution by varying the concentration of the reducing agent. INTRODUCTION

Colloidal gold nanoparticles have been studied for over 100 years, mostly directed towards a better understanding of their physical and chemical properties like surface plasmon absorption and catalytic activities [1]. The ‘near monodisperse’ size distribution of the particles of these colloids was of special interest in order to test various theoretical models of colloidal stability and acquire knowledge on the nature of particle agglomeration process [2], self assembly of colloidal particles in two dimensional or more complex three dimensional (3D) superstructures [3], amongst others. In recent years, application of colloidal gold nanoparticles as sensors for a wide variety of analytes, like heavy metal cations [4] and biological molecules [5] has attracted a renewed attention from researchers. One of the most widely used precipitation methods for the synthesis of gold colloids , proposed by Turkevich, in water involves the reduction of an aqueous solution of chloroauric acid (HAuCl4) by trisodium citrate [1,6]. These nanoparticles are known to be stabilized by a physical adsorption of excess citrate ions from the medium [6]. For most biological applications like bio-sensors and novel assemblies based of biological structures, use of conventional gold nanoparticles involves an additional step of ligand exchange with a bio-molecule that often leads to de-stabilization of the colloidal suspension. This can be avoided by employing bio-available molecules like acidic amino acids to reduce chloroauric acid to form gold nanoparticles with bio-compatible surface properties. Successful attempts to use amino acids as a reducing agent for chloroauric acid have been reported for aspartic acid [7]. To the best of our knowledge this is the first report on the precipitation and characterization of gold nanoparticles utilizing the amino acid derivative, monosodium glutamate (MSG). Morphology, crystallinity and surface properties of the synthesized gold nanoparticles obtained at varying experimental conditions are presented and discussed.

9].3. This can be . described in details later). 1a) show a red-shift in the absorption peak with decreasing molar ratio from 6. 2 ml of Solution A was added and the mixture was heated till boiling. and subsequent drying in ambient temperature. while maintaining similar precursor molar ratio as explained above. when the color of the colloid stabilized (no change in visible color for over 60 sec). Synthesis of glutamate stabilized gold nanoparticles: In 50 ml of de-ionized water. it was rapidly quenched in ice. The obtained colloidal suspension was placed in a freezing chamber to de-stabilize nanoparticles leading to their flocculation. 3. Cu–Kα radiation (λ = 1. 5.5 until a ratio of 3 due to a nominal increase in particle size and an increase in the number of non-spherical particles (as observed TEM of the nanoparticles. The solution pH for all the cases was found to be in the range of 4 – 5.8. Optical absorption spectroscopy was done with a dual beam spectrophotometer (ELICO-SL164) operating between 350 – 1000 nm range. The sediment was separated by centrifuging (4000 rpm) and was repeatedly washed with water and acetone (for XRay diffraction studies only) to remove excess organic salts from the nanoparticle surfaces. A blue shift was observed in the peak absorption wavelength for the gold colloid synthesized with a precursor molar ratio smaller than three as shown in figure 1a. coagulation among the particles. aliquots of solution B (such that the molar concentration ratio of monosodium glutamate to chloroauric acid was adjusted to 7. Transmission electron microscopy (TEM) was carried out at 200KV on samples prepared by dropping aliquots of the obtained colloidal solution on a ‘holey’ carbon coated copper grid. In separate experiments. Preparing dry powder for FTIR and X-ray analysis: Larger volumes (250 ml) of colloidal gold nanoparticles were synthesized to ensure sufficient solid product. The color changes variably according to the specific molar ratio used in the synthesis. the washed powder was collected and compressed with potassium bromide to form a pellet which was used in the transmission mode for FTIR (Perkin Elmer Spectrum one) spectroscopy. 4. Gold colloids studied here are stable for prolonged periods (over several months to a year). 6. RESULTS AND DISCUSSIONS Gold colloids are known to absorb specific band of light (with peak absorption wavelength around 520 nm to 540 nm) due to surface plasmon resonance (SPR). and 2 following our experimental design). shape and uniformity). The washed powder was collected and dried on a Si (111) wafer for X-Ray analysis (Siemens D5000. thus coagulation and also the changes in their dielectric environment can be neglected in our case. was added to this mixture and heating was continued at boiling conditions. In general. A comparison of the peak of the absorption spectra of the colloids (Fig. with a JEOLJEN2010. Hence all changes in the absorption spectra due to the synthesis conditions can be attributed to variation in particle morphology.0901-Ra16-55-Rb16-55. The width of the absorption band and the position of the maximum absorption peak depend on the morphology of the particles (size.2 EXPERIMENTAL DETAILS Stock solutions of 5 mM chloroauric acid (Sigma-Aldrich) in de-ionized water (Solution A) and 25 mM monosodium glutamate (Sigma-Aldrich) in deionised water (Solution B) was prepared in clean and dry glass bottles.54 Å) at a scanning rate of 3s/degree (2 θ) within the range of 35 – 85 degrees (2 θ)). Upon boiling. and also the dielectric environment [1.

observed as a discontinuity in the plot of peak absorption wavelengths of the colloids around molar ratio 3. 2). during the synthesis of gold colloids with precursor molar ratio 2. . (a) Peak absorption wavelengths of glutamate stabilized gold colloids for the studied ranges of precursor molar ratio. 5. Average diameter of the nanoparticles varied from 14. It was found that the average diameter of the colloidal gold nanoparticles and the number of non-spherical gold particles increased with the decrease in the concentration of monosodium glutamate (Fig. corresponding to the progress of the reduction process. However. From transmission electron microscopy it was observed that similar to the conventional trisodium citrate reduction process (Turkevich process) [6. From the observed similarity in the reaction parameters for molar ratio higher than 3 and the discontinuities observed at precursor molar ratio of 3 we logically conclude that a minimum of three glutamate ions are needed to reduce one Au3+. the reaction is significantly delayed (reaction starts after 131 s) and is much slower (slope ~ 0. The rise in peak absorption (Fig. see figure 1b). and the rise in the peak absorption intensity for all the three cases has a slope of ~ 0. the particle sizes in the colloids synthesized with monosodium glutamate also depend on the concentration of the reducing agent employed during the synthesis (Fig.003. and 2. 2a). 62 s.0901-Ra16-55-Rb16-55. Optical absorption of the gold colloids for various conditions.007). The size distribution of the obtained nanoparticles were found to be nominally wider (σ = 14 – 20 %) than what is reported for the most optimum trisodium citrate reduction process (σ = ~15 % [6]). a scheme for the reaction is proposed: HAuCl 4 + ( x + 3) NaC 4 H 8 O4 N ⎯100⎯→ Au 3[C 4 H 8 O4 N ]− + 3 NaCl + HCl + x[C 4 H 8 O4 N ]− + xNa + ⎯°C ---. the reaction starts at 40 s.3 Figure 1. and 75 s respectively for molar ratios 7.1b) at various stages of particle growth are notably different in case of syntheses with a molar ratio less than 3. and 3. (b) Increase of the plasmon absorption maxima at various intervals of time for precursor molar ratios 7. the complete process of nucleation and growth of nanoparticles is extremely fast (Extrapolating from the plot. 5. 1b).8]. The increases in peak plasmon absorption intensities (Fig.5 nm to 24 nm for a molar ratio (MR) of monosodium glutamate to chloroauric acid kept between 10 and 2.(1) where (x+3) implies molar ratio of monosodium glutamate to chloroauric acid. 3. indicates that at relatively high concentrations of monosodium glutamate. Based on this stiochiometry.

The diffuse layer of the electric double layer that stabilizes the nanoparticles. is known to have a high concentration of Na+ to balance the strongly negative stern layer of adsorbed citrate ions in the Turkevich process or in this case glutamate ions [6]. The formation of anisotropic gold nanoparticles for lower concentration of MSG with respect to chloroauric acid in the starting solution can be attributed to the reduction in the concentration of counter ions (Na+) at lower molar ratio synthesis process.1. and 3. 5. Further experiments are being conducted to test this hypothesis by providing external source of Na+ ions during the nucleation stages. while in case of MR-2 colloids (lowest concentration studied). (b).1. were found to have 90 % of the particles with an aspect ratio less than 1.1). only 52 % of the nanoparticles were found to have an aspect ratio less than 1. which will be reported elsewhere. and (d) TEM micrograph of nanoparticles synthesized with molar ratios 7. (c).3a). Incomplete surface coverage due to lower Na+ concentrations (in case of synthesis with low precursor molar ratios. Though over 50 % of the nanoparticles in all cases were found to be fairly spherical (with aspect ratio of 1. MR-7 colloids (high concentration of MSG). . The appearance of non-spherical particles in the colloidal solution was found to be inversely dependant on the concentration of monosodium glutamate in the reaction mixture. and also in these experiments.0901-Ra16-55-Rb16-55. where the reducing agent supplies one Na+ ion per molecule) would lead to anisotropic diffusion of the Au3+ leading to the formation of non-spherical nanoparticles.4 Figure 2 (a) Variation of particle size with the precursor molar ratio (MR). it was observed that the occurrences of larger aspect ratio particles became common only when low concentrations of monosodium glutamate were used to reduce chloroauric acid (Fig. Preliminary results by employing NaOH as the external source of Na+ ions in the starting solution show a marked narrowing of the size distribution of the synthesized gold nanoparticles. a sufficient concentration of Na+ ions in the diffuse layer ensures a complete surface coverage that would serve to control the diffusion of gold ions onto the growing nanocrystals. This leads to a nearly isotropic growth as commonly observed for the synthesis of spherical gold nanoparticles by trisodium citrate reduction. During the growth of a nanoparticle.

4b).0901-Ra16-55-Rb16-55. A typical FTIR spectrum of the glutamate stabilized gold nanoparticles (for molar ratio 7) is shown in Figure 3b. Typical X-ray diffractogram of glutamate stabilized gold nanoparticles is shown in figure 4a. Other absorption peaks in the obtained FTIR spectrum matching with the data from the chemical supplier have also been marked in the figure. which is similar for all other synthesized particles. In comparison. with the particle sizes obtained from TEM analysis (Fig 2a) for monosodium glutamate (MSG) and trisodium citrate (TSC). X-Ray diffraction analysis of gold nanoparticles synthesized with trisodium Figure 4 (a) Typical X-ray diffractogram of gold nanoparticles synthesized with a precursor molar ratio of 7 (b) A comparison of the crystallite sizes determined from the X-Ray diffractogram. It was found that for all molar ratios the average crystallite sizes matched fairly well with the particle sizes obtained from TEM analysis in figure 2a (Fig. by comparing the absorption peaks in the spectra of the colloidal nanoparticles.2 degrees) was employed to calculate the average crystallite sizes of the nanoparticulate samples using the Debye Scherer equation. The presence of glutamate moiety on the nanoparticle surfaces was confirmed by FTIR spectroscopy. Gold nanoparticles obtained by the glutamate reduction technique were found to be highly crystalline.5 Figure 3 (a) Comparison of the aspect ratios of the obtained colloidal nanoparticles with various molar ratios of the precursors(MR implies the molar ratio of the precursors). with available IR absorbance data of monosodium glutamate from the chemical suppliers [10]. (b) A typical FTIR spectrum of glutamate stabilized gold nanoparticles. The width of the most intense peak ((111) peak at 2θ = 38. . synthesized with a molar ratio of 7. shows strong absorption at 1405 cm-1 which is a characteristic stretching vibration of the N – H bond in the amino acid. Particle sizes for TSC were obtained from the literature [11].

Gold bulletin 18. V. Materials Today 7. Link. S. in Encyclopedia of Nanoscience and Nanotechnology. J. Chem.) 114. Sci. The obtained spherical colloidal particles were comparable in size and shape to the gold nanoparticles synthesized by the reduction of chloroauric acid by trisodium citrate in water. Indian Acad.A. M. S. Anal. The particle size and anisotropy can be controlled by the varying molar ratio of the reactants in the starting solution. Goia. and J. Annu. 293 (2004). 2004) p. Edited by H. M. Selvakannan. A more detailed study on this aspect will be reported elsewhere. Dutta.6 citrate (molar ratio 7. Dutta. Nath and A. Chem. which will be reported elsewhere. (Chem. Matijevic. 2.M. R. Pasricha. Daniel and D. Proc. Colloid Interface Sci. J. J. and 1) indicated that the nanoparticles had a highly agglomerated structure. 74. Turkevich. 377 (2004). Sci. Hofmann. comparable or less than three times the number of free gold ions in the reacting solution leads to the formation of anisotropic nanoparticles. El-Sayed.com/spectra/rair/RAIR013285. Sasry. Phadtare. Chilkoti. D.V. Nalwa (American Scientific Publisher. 14. Rev. N. 617. Nath and A. Rev. 125 (1985). and E. ACKNOWLEDGEMENTS The authors would like to thank the Swedish International Development Agency (SIDA) for financial support. N. The sizes of the colloidal nanoparticles synthesized by employing trisodium citrate obtained from the literature [11] was found to be in the order of two times the crystallite sizes as determined from the diffractogram. CONCLUSIONS We report for the first time a simple aqueous precipitation process to synthesize amine functionalized gold nanoparticles by the reduction of chloroauric acid by monosodium glutamate. J. 7. C. 504 (2002). J. Further experiments are being carried out to prove this hypothesis. Hilborn. Park. REFERENCES 1.R. S. Fluorec. Sugunan.G. L. 3. 2. A. . P.C. 4. Astruc. Mandal.0901-Ra16-55-Rb16-55. That is attributed to arise due to the incomplete coverage of the growing gold nanoparticles with sodium ions in the diffuse layer of the double layer. Liz-Marzan. employing the Debye Scherer equation. S.sigmaaldrich. http://www. 213. 54. 36 (1999). 5. and M. and Prof. Privman. Single crystalline gold nanoparticles can be obtained by this synthetic route which was corroborated with TEM and X-Ray diffraction analysis. J. 331 (2003). 4. Chem. G. Science and Technology of Advanced Materials 6. Thanachayanont. 10. 6.PDF 11. Chilkoti. 8. H. 9. 26 (2004). 513 (2002). At molar ratios of monosodium glutamate. 104. Phys. Hilborn for discussions. 335 (2005). J. California.

Sign up to vote on this title
UsefulNot useful