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Amino-acid-based, lipid-directed, in situ synthesis and fabrication of gold nanoparticles on silica: a metamaterial framework with pronounced catalytic activity

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IOP PUBLISHING Nanotechnology 23 (2012) 495301 (8pp)

NANOTECHNOLOGY

doi:10.1088/0957-4484/23/49/495301

Amino-acid-based, lipid-directed, in situ synthesis and fabrication of gold nanoparticles on silica: a metamaterial framework with pronounced catalytic activity
Sudipta Ray1 , Makoto Takafuji1,2 and Hirotaka Ihara1,2
1

Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami Chuo-ku, Kumamoto 860-8555, Japan 2 Kumamoto Institute for Photo-Electro Organics (PHOENICS), 3-11-38 Higashimachi Higashiku, Kumamoto 862-0901, Japan E-mail: ihara@kumamoto-u.ac.jp

Received 30 July 2012, in nal form 1 October 2012 Published 13 November 2012 Online at stacks.iop.org/Nano/23/495301 Abstract We introduce a new example of the in situ preparation and fabrication of stable gold nanoparticles on silica in an aqueous medium, by using only lipid-grafted silica particles in HAuCl4 solution without addition of any external reducing agent. The lipid-grafted silica particles have been synthesized by graft-to methodology and characterized by elemental analysis, thermogravimetric analysis and Fourier-transform infrared spectroscopy. The metamaterial particles show high catalytic activity for the reduction of p-nitrophenol to p-aminophenol. S Online supplementary data available from stacks.iop.org/Nano/23/495301/mmedia (Some gures may appear in colour only in the online journal)

1. Introduction
Metal composites have attracted a great deal of interest because of their various applications in biology, such as in bioimaging [1], optical sensing [2], biomedicine [3], and catalysis [49]. The use of gold-nanoparticle building blocks for the creation of electrochemical sensing devices is also promising [1017]. Although gold is a poor catalyst in its bulk form, nanometre-sized gold particles can exhibit excellent catalytic activity owing to their large surface-to-volume ratio and different interface-dominated electronic properties compared to the corresponding bulk metal [1821]. Despite their high reactivity and efciency as homogeneous colloids, large-scale applications of gold nanoparticles are limited because of particle aggregation and their poor re-use probability. These disadvantages have often been overcome
0957-4484/12/495301+08$33.00 1

by immobilizing the catalytic nanoparticles on solid supports such as silica [2229], alumina [30], zeolite [31], and metal oxide [32]. In particular, metal-nanoparticle-coated silica composites are interesting because of their stability and inactivity with reacting molecules. There are some known methods available for synthesizing various kinds of silicametal-based composite materials such as metal-core silica cells [33, 34], silica-core metal cells [35], and nanoparticles embedded in porous silica [36]. Preparation of supported gold nanoparticles in a one-step manner and without utilization of external reducing agents has been previously reported by Shi et al [37]. However, there are very few references to the synthesis of gold-nanoparticlesilica composite materials using only functionalized silica particles without the addition of any external reducing agent [38]. Various multi-step wet chemical methods have been developed; all these
c 2012 IOP Publishing Ltd Printed in the UK & the USA

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synthetic methods involve the pre-treatment of silica, complex processing, and special experimental conditions. Hence, it is essential to have a simple, scalable protocol for the synthesis of silicagold composite materials. Taking this into consideration, we designed one novel lipid-grafted silica molecule (Sil-DYS) having two parts: a reductant part and a stabilizer part. We selected the amino acid tyrosine as the reductant part, as we have previously reported that it can be used as a reducing and capping agent for the synthesis of various nanostructures [39, 40]. We also selected a long-chain alkyl group (stearyl group) to stabilize the nanoparticles against multidimensional aggregation, and used silica particles as the solid support for fabrication. Here, we propose a new aqueous-phase method for the in situ preparation of stable gold nanoparticles using silicaTyrlipid as both the reductant and stabilizer.

max (KBr) (cm1 ) 3332, 2917, 2849, 1752, 1648, 1558, 1463, 1229, 1165. ESI-HR-mass [M + H]+ = 462.28, [M + Na]+ = 484.12, [M + K]+ = 500.05, Mcalc. = 461. 2.2.2. N-stearyl-D-tyrosinamide (SDY) (2). To 5.4 g (11.7 mmol) of 1, 20 ml of MeOH and 10 ml of 2 M NaOH were added. The reaction mixture was stirred and the progress of saponication was monitored by thin layer chromatography (TLC). After 10 h, methanol was removed under vacuum and the residue was dissolved in 50 ml of water and washed with diethyl ether (2 50 ml). Then the pH of the aqueous layer was adjusted to 2 using 1 M HCl and it was extracted with ethyl acetate (3 50 ml). The extracts were pooled, dried over anhydrous sodium sulfate, and evaporated in vacuo to yield 2 as a solid compound. Yield = 2.3 g (5.14 mmol, 44%). C27 H45 NO4 (447) requires C, 72.48, H, 10.06, N, 3.13%. Found C, 72.28, H, 9.87, N, 2.98%. m.p. 129130 C. 1 H NMR (400 MHz, DMSO-d ): 9.21 (PhOH, 1 H, b); 6 8.028.00 (Tyr NH, 1H, d, J = 8 Hz); 7.006.98 (ring Hs of Tyr, 2H, d, J = 8 Hz); 6.646.62 (ring Hs of Tyr, 2H, d, J = 8 Hz); 4.324.31 (C H of Tyr, 1H, m); 2.922.88 (C Hs of Tyr, 2H, dd); 2.192.15 (COCH2 , 2H, t); 1.401.36 (COCCH2 , 2H, b); 1.23 ((CH2 )14 , 28 H, b); 0.860.83 (CH3 , 3H, t). 13 C NMR (100 MHz, DMSO-d6 ): 174.43, 173.31, 172.09, 155.86, 129.90, 127.68, 114.86, 53.61, 40.12, 39.9138.87, 35.99, 35.0, 33.64, 31.27, 29.0228.49, 25.17, 24.47, 22.07, 13.92. FT-IR data: max (KBr) (cm1 ) 3313, 3240, 2917, 2849, 1708, 1645, 1542, 1516, 1462, 1235. ESI-HR-mass [M +H]+ = 447.41, [M +Na]+ = 470.27, [M + K]+ = 486.43, Mcalc. = 447. 2.2.3. Immobilization of lipid compound analogue on to silica surface (Sil-DYS). 3-aminopropyltrimethoxysilane (APS)-grafted silica was prepared by reuxing porous silica gel (3.0 g) and APS (1.5 ml) in toluene for 24 h. After successive washing with toluene, ethanol and diethyl ether the particles were dried in vacuum. The dried particles were characterized by elemental analysis: H2.05, C4.96, N 1.65%. Silica-APS was then coupled with SDY. Silica-APS (3.0 g) and SDY (3.0 g) were dissolved in 100 ml dry THF and stirred. DEPC (1.5 g) and TEA (1.1 g) were added to the solution and stirred at 60 C. After being stirred for 1 day the grafted particles (Sil-DYS) were washed with chloroform and methanol several times to remove the unreacted lipid molecules and dried in vacuum. The grafting was conrmed by elemental analysis. 2.3. In situ preparation of gold nanoparticles and simultaneous fabrication First we take 20 mg of Sil-DYS in a vial then dissolve it in 8.5 ml of Millipore water. Then 0.5 ml of HAuCl4 (10 mmol) aqueous solution was added dropwise to the above solution with constant magnetic stirring. The pH of the solution was adjusted to alkaline by addition of freshly prepared NaOH solution. A colour change was observed from yellow to purple (supporting information gure S1 available at stacks. iop.org/Nano/23/495301/mmedia), indicating the formation of silicaDYSgold nanoparticle conjugate through reduction of the tyrosine residue of the lipid part [40].
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2. Experimental section
2.1. Materials Starting from D-tyrosine, all chemicals for the synthesis of lipids were purchased from Wako Pure Organic Chemical Industries, Sigma Aldrich, Tokyo Kasei Kogyo (Tokyo, Japan) and Nacalai Tesque (Kyoto, Japan) and used as received. 3-aminopropyltrimethoxysilane (APS) was purchased from Azmax (Chiba, Japan). Porous silica particles (YMC-GEL), whose average diameter, pore size and surface area are 5 m, 12.0 nm and 300 m2 g1 respectively, were purchased from YMC (Kyoto, Japan). 2.2. Synthesis of Sil-DYS particles 2.2.1. N-stearyl-D-tyrosinamide-methyl ester (1). 4.3 g (15 mmol) of stearic acid in 10 ml of DMF was cooled in an ice-water bath. HD-TyrOMe was isolated from 5.85 g (30 mmol) of the corresponding methyl ester hydrochloride by neutralization, subsequent extraction with ethyl acetate and concentration to 10 ml and it was added to the reaction mixture, followed immediately by 3.09 g (15 mmol) of DCC and 2.2 g (15 mmol) of HOBt. The reaction mixture was stirred for two days. The residue was dissolved in ethyl acetate (60 ml) and the DCU was ltered off. The organic layer was washed with 2 M HCl (3 50 ml), brine (2 50 ml), 1 M sodium carbonate (3 50 ml) and brine (2 50 ml) again, then dried over anhydrous sodium sulfate and evaporated in vacuo to yield 1 as a white solid. Yield = 5.6 g (12.1 mmol, 80%). C28 H47 NO4 (461) requires C, 72.88; H, 10.1; N, 3%. Found C, 72.62; H, 9.91; N, 2.97%. 1 H NMR (400 MHz, DMSO-d6 ): 8.258.23 (Tyr NH, 1H, d, J = 8 Hz); 6.986.96 (ring Hs of Tyr, 2H, d, J = 8 Hz); 6.676.65 (ring Hs of Tyr, 2H, d, J = 8 Hz); 4.34 (C H of Tyr, 1 H, m); 3.57 (OCH3 , 3H, s); 2.892.76 (C Hs of Tyr, 2H, dd); 2.062.02 (COCH2 , 2H, t); 1.64 (COCCH2 , 2H, b); 1.39 ((CH2 )14 , 28 H, b); 0.850.83 (CH3 , 3H, t). 13 C NMR (100 MHz, DMSO-d6 ): 172.38, 171.85, 130.1, 127.33, 53.80, 51.62, 40,12, 39.738.87, 35.39, 33.54, 31.24, 29.00, 28.8828.44, 25.11, 22.05, 13.92. FT-IR data:

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Scheme 1. Schematic representation of the synthesis of Sil-DYS particles.

2.4. Characterizations 2.4.1. NMR experiments. All NMR studies of the lipid molecules in CDCl3 and DMSO-d6 at 25 C were carried out with JEOL JNM-LA 400 (Japan) spectrometers at 400 MHz. Chemical shifts ( ) of 1H are expressed in parts per million (ppm) with use of the internal standard Me4 Si ( = 0.00 ppm). 2.4.2. Mass spectrometry. Mass spectra were recorded on a Br uker Daltonics mass spectrometer by positive mode electrospray ionization. 2.4.3. DRIFT mode Fourier-transform infrared spectroscopy and elemental analysis. FT-IR measurements were conducted with a JASCO FT/IR-4100 (Japan). For DRIFT measurement accessory DR PRO410-M (JASCO, Japan) was used. Samples were prepared by mixing the corresponding dried samples with KBr in a 1:100 (wt/wt) ratio. Elemental analyses were carried out on a Yanaco CHN Corder MT-6 Apparatus (Japan). 2.4.4. Calculation relates to surface coverage. Surface coverage of organic phase was calculated by using the equation below and data given in table S1 (available in supporting information at stacks.iop.org/Nano/23/495301/ mmedia). The molar amount of organic phase per gram of silica (M ) can be calculated as M (mol g1 ) = 106 (Pc /100)/12n (1)
3

where Pc is the percentage of carbon element according to elemental analysis and n is the number of carbons present in the grafted organic phases. The weight percentage of the grafted phase Pw in each case can be calculated as Pw = m 104 M (n/n1 ) (2)

where m is the molecular mass and n1 is the number of carbons in each molecule of the organic phases grafted onto the silica surface. N (mol m2 ) = M /[S{(100 Pw )/100}] = 106 Pc /[12nS(100 Pw )] (3)

where S is the surface area of 1.00 g of nonmodied silica. 2.4.5. UVvisible absorption spectroscopy. UVvisible absorption spectra of lipidAu conjugate and silicalipidAu conjugate in water were recorded with a JASCO-V560 UVvisible spectrophotometer. 2.4.6. Field emission scanning electron microscopy. One drop of as-prepared water suspension of silicalipidAu nanoconjugate was placed on glass coverslip and allowed to vacuum dry. It was then coated with osmium by using Filgen OPC6ON. Then the micrographs were observed under a Hitachi (S4800) scanning electron microscope. 2.4.7. Transmission electron microscopic study. The transmission electron microscopic studies of all the silicalipidAu

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iop.org/Nano/23/495301/mmedia), Sil-APS presented a mass loss of 7.99%, and after the lipid grafting the weight loss observed is 12.9%, indicating that the organic content had greatly increased. 2.4.9. Catalytic reduction of 4-nitrophenol. The reduction of 4-nitrophenol was selected as a model reaction system for testing the catalytic activity of the in situ formed and fabricated silicalipidAu conjugate. Aqueous solutions of 4-nitrophenol (1 ml, 0.001 M) and NaBH4 (5 ml, 0.1 M) were added to 40 ml Millipore water in a beaker under constant magnetic stirring. After adding silicalipidAu conjugated catalyst particle (5 mg), the bright yellow solution gradually faded as the reaction proceeded. The progress of the catalytic reduction experiment was recorded at regular intervals using UVvis spectra.
Figure 1. UVvisible absorption spectra of DYSAu solution and silicaDYSAu conjugate in water. The inset shows the silicaDYSAu conjugate in aqueous medium.

3. Results and discussion

3.1. In situ formation and fabrication of gold nanoparticles The synthetic routes for the lipid stearyl-D-tyrosinamide (SDY) and the immobilization process of this lipid analogue on silica are shown in scheme 1. The chemical structures of all the nal compounds were identied by meltingpoint measurements, Fourier-transform infrared (FT-IR) spectroscopy, 1 H-NMR spectroscopy, thermal gravimetric analysis (TGA) (supporting information gure S2 available at stacks.iop.org/Nano/23/495301/mmedia) and elemental analysis. The in situ preparation of gold nanoparticles and the fabrication of conjugate particles on silica were achieved by the simple addition of HAuCl4 aqueous solution to the silicaDYS aqueous solution and the adjustment of the pH of the solution under stirring. First, silicaDYS (20 mg) was put in a vial and dissolved in Millipore water (8.5 ml). Then, an aqueous solution of HAuCl4 (0.5 ml, 10 mmol) was added dropwise to the above solution with constant magnetic stirring. The pH of the solution was adjusted to be just alkaline by the addition of freshly prepared NaOH solution. Within 5 min, the colour of the reaction mixture changed distinctly from pale yellow to purple. This purple colour arises because of the appearance of gold-nanoparticlesilica conjugate particles, and occurs as a result of the excitation of the surface plasmons of the gold nanoparticles. The lipid (DYS) can be used to synthesize gold nanoparticles by the same procedure, but it coagulates readily with time, whereas the conjugate particles are colloidally stable in water for a long time and are purple in colour, as shown in the inset of gure 1. It seems that the synthesis of gold nanoparticles and the fabrication of the conjugate particles occurred simultaneously. These conjugate particles can be collected easily by simple centrifugation. 3.2. UV analysis The UVvis spectrum (gure 1) of the lipidDYSgold solution shows a sharp peak at max = 535 nm. These data
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Figure 2. DRIFT mode FT-IR spectra of silica, silicaDYS and silicaDYSAu conjugate.

conjugate were done by placing one drop of water suspension of the corresponding compounds on carbon-coated copper grids and drying by slow evaporation. The grid was then allowed to dry in vacuum for two days. Images were taken at an accelerating voltage of 200 kV. TEM was carried out with a JEOL JEM-2000 FX electron microscope. 2.4.8. Thermogravimetric analysis (TGA). Thermograms of the dry powdered samples were recorded by using a Seiko EXSTAR 6000 TG/DTA 6300 thermobalance in static air from 40 to 800 C at a heating rate of 10 C min1 under a N2 atmosphere. Thermogravimetric curves are usually used to determine the thermal stability and to conrm the amounts of immobilized organic components. The weight loss observed can be associated with the loss of organic groups attached to the silica surface. As shown in gure S1 (available at stacks.

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Figure 3. (a) Scheme of the procedure used to produce gold nanoparticles on silica and (b) SEM image of a silica particle covered with gold nanoparticles.

Figure 4. (a) TEM picture of gold nanoparticles synthesized by lipidSDY in water and (b) corresponding histogram showing the particle size distributions.

indicate the presence of well dispersed gold nanoparticles less than 20 nm in size [41]. In the case of the silicaDYSAu conjugate the peak is observed at max = 552 nm. This slight shift in the surface plasmon band for gold nanoparticles might be due to the change of their size after conjugation with silicaDYS [42, 43].
5

3.3. DRIFT mode FT-IR analysis The DRIFT mode FT-IR spectra (gure 2) show bands for silicaDYS at 2980 and 2899 cm1 , occurring as a result of the asymmetric and symmetric stretching of the grafted CH2 groups, respectively. Bands in the same region are also

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Figure 5. TEM image of (a) silicaDYSAu conjugate in water and (b) layer of Au nanoparticles on silica surface. (c) High resolution TEM image of silicaDYSAu conjugate and (d) corresponding histogram showing the particle size distribution.

observed for the silicaDYSAu conjugate, but with slight changes in peak positions (3057 and 2907 cm1 , respectively) due to the change in conformation of the grafted phase after nanoparticle fabrication and conjugation. Both the silicaDYS conjugate and silicaDYSAu conjugate show amide I (due to stretching vibration of CO group) and amide II (due to bending vibration of NH group) bands. In the case of silicaDYS the amide I and amide II bands appear at 1643 and 1540 cm1 , respectively, whereas for the silicaDYSAu conjugate they appear at 1602 and 1507 cm1 , respectively; the peak intensity also decreases. These data indicate that this amide functionality has some role in stabilizing the gold nanoparticles for their facile fabrication over the silica surface. Moreover, the peak for the phenolic OH group at
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1447 cm1 is clearly present in the silicalipid conjugate, but is barely visible in the silicalipidAu conjugate. This clearly suggests that the phenolic OH group of tyrosine in the lipid acts as the main reducing agent for the in situ formation of gold nanoparticles. This result proves that the DYS molecule plays the key role in the formation and fabrication of gold nanoparticles over silica particles. 3.4. SEM morphological characterizations The FE-SEM study showed that gold nanoparticles were selectively fabricated on the surface of the silica particles. Figure 3(a) gives a schematic presentation of the deposition procedure of gold nanoparticles over silica, and gure 3(b)

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shows that spherical gold nanoparticles are dispersed evenly over the silica surface. An SEM picture of Sil-DYS particles and a high resolution one are also given in supporting gures S3(a) and (b) (available in supporting information at stacks. iop.org/Nano/23/495301/mmedia). 3.5. TEM morphological characterizations The morphology and distribution of the gold nanoparticles on the silica surface can be directly observed by transmission electron microscopy (TEM). Figures 4(a) and (b) show that the DYSgold conjugate can form well dispersed spherical gold nanoparticles with an average diameter of 7.9 nm, in the range 310 nm. From gure 5(a), it can be observed that highly dispersed gold nanoparticles, which appear as dark dots, are nicely arranged on the silica surface. Actually, the gold nanoparticles form a layer-like array on the silica surface, as observed in gure 5(b). High resolution TEM pictures of SilDYSAu conjugate particles are also given in gure 5(c), and gure 5(d) shows the corresponding histogram. A slight increase in particle size has been observed, with an average diameter of 14 nm, in the range of 820 nm, after fabrication on the silica surface. 3.6. Catalytic efciency

Figure 6. Time-dependent UVvisible spectral changes of the p-NP reaction mixture catalysed by silicaDYSAu conjugate. The inset shows the plot of ln(C/C0 ) versus time for the p-NP to p-AP reaction mixture.

reaction mixture by simple centrifugation, and can be used repeatedly by re-dispersion in water through a brief sonication procedure.

4. Conclusion
The obtained silicaDYSAu conjugate particles were applied for the catalytic reduction of p-nitrophenol by NaBH4 . It is well known that this reaction is simple and fast in the presence of metallic surfaces [44, 45]. It was conrmed that this reaction did not occur without the silicaDYSAu conjugate catalysts, even after a period of four days. The kinetics of p-nitrophenol reduction in the presence of the silicaDYSAu conjugate was studied by UVvis spectroscopy. The reaction progress was monitored by taking small portions of the reaction mixture at regular time intervals. Figure 6 shows the typical UVvis absorption change of the reaction mixture upon addition of silicaDYSAu conjugate particles at regular intervals. After the addition of the silicaDYSAu conjugate in the reaction medium, it was observed that the intensity of the peak at 400 nm (characteristic for p-nitrophenol) decreased, and a new peak at 300 nm (characteristic for p-aminophenol) increased gradually with time. The successive decrease in the intensity of the 400 nm peak with time was considered to obtain the rate constant. The ratio of C/C0 , where C and C0 are the p-nitrophenol concentrations at times t and 0, respectively, was measured from the relative intensity of the respective absorbance, A/A0 , at 400 nm. A linear relationship of ln(C/C0 ) versus time was observed, indicating that the reactions followed rst-order kinetics. The observed rate constant for the catalyst was 5.95 104 s1 , as calculated directly from the slope of the straight line shown in the inset of gure 6. The conversion yield of p-nitrophenol to p-aminophenol was almost 60% within 5 min and almost 90% within 1 h. The advantages of these silicaDYSAu nanocomposite catalyst particles are their easy preparation, dispersion, and separation in the reaction mixture. These composite catalyst particles can be collected easily from the
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In conclusion, we have reported a facile method for the environment friendly, in situ preparation and fabrication of noble-metal nanoparticles over a silica support. In this synthesis, the silicalipid conjugate acts as the reducing agent, stabilizing agent, and template in the aqueous medium. This metalsilica framework can be applied successfully in the catalytic reduction of p-nitrophenol as a model reaction, and may nd numerous applications in the eld of heterogeneous catalysis. Because of the simple synthetic approach, we believe that this new smart Au-nanoparticle-fabricated silica support material is promising for a range of applications for which a thin lm of metal is required, such as in electrically conductive metamaterials.

Acknowledgments
SR (ID-P11034) gratefully acknowledges the Japan Society for the Promotion of Science (JSPS) for providing nancial support to carry out this research.

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