Surfactantless synthesis of multiple shapes of gold nanostructures and their shape-dependent SERS spectroscopy

A useful method for the synthesis of various gold nanostructures is presented. The results demonstrated that flowerlike nanoparticle arrays, nanowire networks, nanosheets, and nanoflowers were obtained on the solid substrate under different experimental conditions. In addition, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) on the as-prepared gold nanostructures of various shapes were measured, and their shape-dependent properties were evaluated. The intensity of the SERS signal was the smallest for the gold nanosheets, and the flowerlike nanoparticle arrays gave the strongest SERS signals.

An approach for fabricating self-assembled monolayer of Ag nanoparticles on gold as the SERS-active substrate

In this paper, an approach for fabricating an active surface-enhanced Raman scattering (SERS) substrate is adopted. This approach is based on the assembling of silver nanoparticles film on gold substrate. Rhodamine 6G (R6G) and p-aminothiophenol (P-ATP) were used as probe molecules for SERS experiments, showing that this new active substrate has sensitivity to SERS response. Tapping-mode atomic force microscopy (AFM) was also used to investigate the surface morphology following the fabricating process of the active SERS substrate, which showed that large quantities of silver nanoparticles were uniformly coated on the substrate.

In situ electrochemical SERS studies on electrodeposition of aniline on 4-ATP/Au surface

The electrochemical polymerization of 0.01 M aniline in 1 M H2SO4 aqueous solution on roughened Au surface modified with a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) has been investigated by in situ electrochemical surface-enhanced Raman scattering spectroscopy (SERS). The repeat units and possible structures of the electrodeposited polyaniline (PANI) film were proposed; i.e., aniline monomer is coupled in head-to-tail predominately at the C-4 of aniline and amine of 4-ATP, and the thin PANI film is orientated vertically to substrate surface. Simultaneous Raman spectra during potential scanning indicate clearly that the ultrathin PANI film (in initial growth of the film) consists of semiquinone radical cation (IP+), para-disubstituted benzene (IP and IP+) and quinine diimine (NP) while it is oxidized, and without quinine diimine and semiquinone radical cation while reduced. Meanwhile, the results confirm that 4-ATP monolayer shows a strong promotion on the electrodeposition of aniline monomer, and a possible polymerization mechanism was proposed.

Photoelectrochemical reduction of CO2 mediated with methylviologen at roughened silver electrodes

The photoelectrocatalytic effect for the reduction of CO2 mediated with methylviologen (MV) was studied at mercury, polished silver and roughened silver electrodes using electrochemical and surface-enhanced Raman scattering (SERS) techniques. A large photoelectrocatalytic effect for the reduction of CO2 in the presence of MV was observed at the roughened silver electrode, whereas there was only a very small photoelectrocatalytic current at a more negative potential on mercury and polished silver electrodes. The SERS spectra of MV in the presence and absence of CO2, along with the electrochemical results, demonstrate that the surface adsorbed complexes, MV+ -Ag and MV0-Ag, played a role as the mediator for photoinduced electron transfer to CO2 in the solution. The results also suggest that the surface plasmon resonance of the nanoscale silver particle contributes to the overall photoelectrocatalytic effect on a roughened silver electrode.

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified class slide: A strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

REEVALUATION OF 2,2-BIPYRIDINE AND PYRAZINE AS PROMOTERS FOR DIRECT ELECTRON-TRANSFER BETWEEN CYTOCHROME-C AND METAL-ELECTRODES

Results from previous electrochemical studies have indicated that 2,2'-bipyridine and pyrazine do not function as promoters for heterogeneous electron transfer between cytochrome c and metal electrodes. Their lack of activity was attributed to the improper positioning of the two functional groups in 2,2'-bipyridine and the inefficient length of pyrazine. In the present study it was determined that both 2,2'-bipyridine and pyrazine act as promoters when self-absorbed over a sufficiently long dipping time or at roughened electrodes. The promoter characteristics of these two molecules were studied and compared with those of 4,4'-bipyridine. The difference in their promoter behavior appears to result primarily from their different strengths of adsorption and not because electrodes modified with 2,2'-bipyridine or pyrazine are unsuitable for accelerating direct electron transfer reactions in cytochrome c. These results have implications regarding the mechanism(s) of promoter effects in electrochemical reactions of cytochrome c.

Surface-enhanced resonant Raman spectroscopy (SERRS) of single-walled carbon nanotubes absorbed on the Ag-coated anodic aluminum oxide (AAO) surface

In this paper, we developed a new kind of substrate, the silver-coated anodic aluminum oxide (AAO), to investigate the characters of surface-enhanced resonant Raman scattering (SERRS) of the dilute single-walled carbon nanotubes. Homogeneous Ag-coated AAO substrate was obtained by decomposing the AgNO3 on the surface of AAO. single-walled carbon nanotubes (SWNTs) were directly grown onto this substrate through floating catalyst chemical vapor deposition method (CVD). SERRS of SWNTs was carried out using several different wavelength lasers. The bands coming from metallic SWNTs were significantly enhanced. The two SERRS mechanisms, the "electromagnetic" and "chemical" mechanism, were mainly responsible for the experiment results. (c) 2005 Elsevier B.V. All rights reserved.

Surface-enhanced resonance Raman spectroscopic study of yeast iso-1-cytochrome c and its mutant

The structural stability and redox properties of yeast iso-1-cytochrome c and its mutant, F82H, were studied by surface-enhanced resonance Raman scattering (SERRS) spectroscopy. Phenylalanine, which exists at the position-82 in yeast iso-1-cytochrome c, is replaced by histidine in the mutant. The SERRS spectra of the proteins on the bare silver electrodes indicate that the mutant possesses a more stable global structure with regard to the adsorption-induced conformational alteration. The redox potential of the mutant negatively shifts by about 400 mV, relative to that of yeast iso-1-cytochrome c. This is ascribed to axial ligand switching and higher solvent accessibility of the heme iron in the mutant during the redox reactions.

Micro-Raman study on hydrogenated protocrystalline silicon films

Good quality hydrogenated protocrystalline silicon films were successfully prepared by radio frequency plasma enhanced chemical vapor deposition (PECVD) with various hydrogen dilution ratios (R = ([H-2]/[SiH4]) from 10 to 100). The photosensitivity of the films is up to 10(6) under the light intensity of 50mW.cm(-2). The microstructure of the films was studied by micro-region Raman scattering spectra at room temperature. The deconvolution of the Raman spectra by Gaussion functions shows that the films deposited under low hydrogen dilution ratios (R < 33) exhibit typical amorphous properties, while the films deposited under high hydrogen dilution ratios (R > 50) possess a diphasic structure, with increasing crystalline volume fraction with R. The size of the crystallites in the diphasic films is about 2.4 mm, which was deduced from the phonon confinement model. The intermediate range order of the silicon film increases with increasing hydrogen dilution ratio.

Raman study of low-temperature-grown Al0.29Ga0.71As/GaAs photorefractive materials

We report on the observation of resonant Raman scattering in low-temperature-grown AlGaAs/GaAs structure. Two kinds of excitation lights, 632.8 and 488 nm laser lines, were used to detect scattering signal from different regions based on different penetration depths. Under the outgoing resonant condition, up to fourth-order resonant Raman peaks were observed in the low-temperature-grown AlGaAs alloy, owing to a broad exciton luminescence in low-temperature-grown AlGaAs alloy induced by intrinsic defects and As cluster after post-annealing. These resonant peaks were assigned according to their fundamental modes. Among the resonant peaks, besides the overtones of the GaAs- or AlAs-like mode, there exist combination bands of these two kinds of modes. In addition, a weak scattering peak similar to the bulk GaAs longitudinal optical mode was observed in low-temperature Raman experiments. We consider the weak signal correlated with GaAs clusters appearing in AlGaAs alloys. The accumulation of GaAs in AlGaAs alloys was enhanced after annealing at high temperatures. A detailed study of the dependence of vibration modes on measuring temperature and post-annealing conditions is given also. In light of our experiments, it is suggested that a Raman scattering experiment is a sensitive microscopic probe of local disorder and, especially performed at low temperature, is a superior method in detecting and analyzing the weak interaction between phonons and electrons.

Microstructure of SiOx : H films prepared by plasma enhanced chemical vapor deposition

The micro-Raman spectroscopy and infrared (IR) spectroscopy have been performed for the study of the microstructure of amorphous hydrogenated oxidized silicon (alpha-SiOx,:H) films prepared by Plasma Enhanced Chemical Vapor Deposition technique. It is found that a-SiOx:H consists of two phases: an amorphous silicon-rich phase and an oxygen-rich phase mainly comprised of HSi-SiO2 and HSi-O-3. The Raman scattering; results exhibit that the frequency of TO-like mode of amorphous silicon red-shifts with decreasing size of silicon-rich region. This is related to the quantum confinement effects, similar to the nanocrystalline silicon.

Microarray based Raman spectroscopic detection with gold nanoparticle probes

microarray approach based on surface-enhanced Raman spectroscopic (SERS) was developed for detection of spotted peptide, peptide-protein or protein-antibody interaction. The procedure involves the attachment of peptide-capped gold nanoparticles followed by silver deposition for signal enhancement. The attachment of the gold nanoparticles is achieved by standard avidin-biotin chemistry. The well-known biomolecular recognition pairs, IgG/protein A and biotin/avidin, were used to demonstrate proof-of-concept of the SERS assay.

Novel Hybrid Electrocatalyst with Enhanced Performance in Alkaline Media: Hollow Au/Pd Core/Shell Nanostructures with a Raspberry Surface

In this paper, a hollow Au/Pd core/shell nanostructure with a raspberry surface was developed for methanol, ethanol, and formic acid oxidation in alkaline media. The results showed that it possessed better electrocatalyst performance than hollow Au nanospheres or Pd nanoparticles. The nanostructure was fabricated via a two-step method. Hollow Au nanospheres were first synthesized by a galvanic replacement reaction, and then they were coated with a layer of Pd grains. Several characterizations such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS) were used to investigate the prepared nanostructures.

R6G单分子表面增强共振拉曼散射光谱探测研究

以共焦显微系统为平台，研究了不同浓度的R6G银溶胶的表面增强共振拉曼散射（SERRS）光谱，结果表明不同浓度溶液中的R6G分子表现出了不同的光谱特性。在浓度为10^-13mol·L^-1的R6G银溶胶中得到了R6G单分子的表面增强共振拉曼散射光谱，观察到了一些光谱非均匀变化现象，如谱色散、谱线的强度起伏、拉曼谱的偏振化以及分子的闪烁等，并对这些现象进行了分析，证明得到的是R6G单分子的SERRS光谱。文章还对单分子检测中的一些关键问题进行了分析与讨论，确定了单分子SERRS光谱检测的适当条件。

Raman spectroscopy and luminescent properties of ZnO nanostructures fabricated by femtosecond laser pulses

In this paper, we report the laser-induced periodic structure with different spatial characteristics on the surface of polished ZnO single-crystalline by high repetition rate femtosecond laser pulses. This study demonstrates that, using different laser parameters and irradiation conditions, ZnO nanoripples and nanorods were successfully prepared. We have investigated the surface by means of scanning electron microscope (SEM), Raman scattering and photoluminescence (PL). We propose that second-order harmonic has a strong influence on the formation of nanostructures. (c) 2007 Elsevier B.V All rights reserved.