Self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol adsorbed on silver nanoparticles: Surface-enhanced Raman scattering study

Self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol (1,4-BDT) adsorbed on silver nanoparticles were investigated experimentally with surface-enhanced Raman scattering (SERS) and theoretically with density functional theory (DFT) and finite difference time domain (FDTD) method. The absorption spectroscopy of 1,4-BDT in silver sol at different time intervals was measured, which give the indirect evidence of self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol (1,4-BDT) adsorbed on silver nanoparticles. To obtain the direct evidence of self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol (1,4-BDT) adsorbed on silver nanoparticles, the SERS of 1,4-BDT were measured experimentally and investigated theoretically. The appearances of S–S stretching band (revealing the formation of multilayers of 1,4-BDT), and strongly enhanced S–C stretching, C–C ring stretching vibrational modes clearly show self-assembled dynamics of 1,4-BDT.     

银纳米粒子有序自组装体中偶联分子的表面增强拉曼光谱研究

采用自组装方法,分别以1,4-二巯基苯和对巯基苯胺为偶联分子,在光滑银基底表面上构筑了银纳米粒子的单层和双层有序结构.表面增强拉曼光谱研究表明,在有序银纳米粒子组装体中偶联分子的拉曼散射得到很大增强,其中1,4-对巯基苯的拉曼散射增强效应主要来自光滑银基底表面与单层银纳米粒子间的电磁耦合,而对巯基苯胺的拉曼散射增强效应则主要由两层银纳米粒子之间耦合作用所致.两种不同的耦合作用所产生的增强效应大致相近.     

Adsorption of 1,4-Benzenedithiol on Gold and Silver Surfaces: Surface-Enhanced Raman Scattering Study

The adsorption behavior of 1,4-benzenedithiol (1,4-BDT) on colloidal gold and silver surfaces has been investigated by means of surface-enhanced Raman scattering (SERS). 1,4-BDT chemisorbed dissociatively on both gold and silver surfaces but as mono- and dithiolate, respectively. Regardless of the bulk concentration of 1,4-BDT, only a monolayer was assembled on the silver surface with a flat orientation by forming two Ag–S bonds. On the gold surface, the monothiolate species,1,4-BDT⁻¹, appeared to assume a rather flat orientation at a very low surface coverage, but as the surface coverage was increased, the adsorbate took a perpendicular orientation. Furthermore, when the bulk concentration of 1,4-BDT was close to that required for a full-monolayer coverage limit, a band assignable to the S–S stretching vibration appeared at 536 cm⁻¹ in the gold sol SERS spectra. A separate ellipsometry measurement performed with vacuum-evaporated gold substrates revealed that up to tetralayers could be assembled on gold in 1 mM n-hexane solution of 1,4-BDT while at best a bilayer formed in either methanol or ethanol solution. The different adsorbate structure of 1,4-BDT on gold and silver was overall quite comparable to that of p-xylene-α,α′-dithiol.     

银纳米粒子自组装结构的光谱性质研究

采用自组装方法在玻璃基底表面上构筑了银纳米粒子二维亚单层结构, 进而以对巯基苯胺为耦联分子进行银粒子的二次组装, 构成具有分子尺寸间隙的银粒子簇. 银粒子表面等离子体共振依赖于粒子间距、表面吸附分子和粒子组装方式. 同层内的银粒子相互间电磁偶合可导致银粒子偶极子等离子体共振蓝移; 对巯基苯胺的吸附则使得表面等离子体共振红移. 表面增强拉曼光谱结果表明, 具有分子尺寸间隙的银粒子簇对耦联于粒子间的对巯基苯胺分子的拉曼散射具有极大的增强效应, 同时也使耦联的对巯基苯胺与银粒子间产生更大程度的电荷转移.     

Effect of substrate on surface-enhanced Raman scattering of molecules adsorbed on immobilized silver nanoparticles

Silver nanoparticles were assembled on polyvinylpyridine (PVP) derivatized glass slides. Charge transfer between the adsorbed 4-aminothiophenol (PATP) and the immobilized silver nanoparticles was studied by surface-enhanced Raman spectroscopy with 1064 nm excitation, and compared with that of the silver nanoparticles in the colloid. It was demonstrated that the positive charges of the PVP layer could alter the charge distribution in the immobilized nanoparticles and induce the formation of the dipole in the nanoparticles, leading to less charge transfer from the metal to the adsorbed molecules. The coadsorption of chloride ions on the surface of the immobilized silver nanoparticles resulted in the redistribution of the charges in the nanoparticles and, in turn, altered the charge transfer between the adsorbed PATP molecules and the silver nanoparticles.     

Ultraviolet-visible and Surface-enhanced Raman Scattering Spectroscopy Studies on Ruthenium Phthalocyanine Monolayer Films Formed on Terephthalonitrile-modified Silver Substrates

A self-assembled monolayer film(SAM) of ruthenium phthalocyanine (RuPe) fabricated on a silver sub-strate premodified with an SAM of terephthalonitrile (TPN) was studied by means of surface-enhanced Ra-man seattering(SERS) and ultraviolet-visible (UV-Vis) speetroseopies. TPN was used as a ligand to linkRuPe since it can not only modify the silver suhstrate but also deliver the nitrile groups protruding from thesilver surface. Therefore, we can explore the relationship between the structure and the orientation of RuPeand the TPN-modified substrate. The UV-Vis spectra indicate a strong interaction between RuPe and TPN inthe composite film. The result is further confirmed by the SERS spectra of RuPe-TPN SAM, in which the vi-brational bands arising from both the RuPe and TPN moieties appear clearly, indicating that the RuPe is suc-cessfully assembled on the TPN film.     

Investigation of p-hydroxybenzoic acid from a new surface-enhanced Raman scattering system

In this paper, we developed a new kind of substrate, silver-coated indium tin oxide (ITO), to investigate the character of surface-enhanced Raman scattering (SERS) of p-hydroxybenzoic acid (PHBA). Homogeneous Ag-coated ITO substrate was obtained by decomposing AgNO(3) on the surface of ITO. A SERS spectrum of very good quality of "silver nanoparticles/PHBA/silver-coated ITO" was reported by adding PHBA aqueous solution and silver colloid onto the surface of silver-coated ITO repeatedly. PHBA molecules absorbed onto the surface of the silver nanoparticles through ionized carboxyl, and the PHBA molecules tended to tilt on the surface in this system. The rich information obtained from the silver nanoparticles/PHBA/silver-coated ITO system indicates that this is a highly SERS-active system. Not only was the number of the vibrational modes increased, but also were the frequencies of Raman bands shifted. The two SERS mechanisms, the "electromagnetic" and "chemical" mechanism, were mainly responsible for the experimental results. Furthermore, the silver nanoparticles modified on the silver-coated ITO surface play an important role in magnifying the surface local electric field near the silver film surface through resonant surface plasmon excitation.     

Characteristics of polypyrrole electrodeposited onto roughened substrates composed of gold–silver bimetallic nanoparticles

In this work, the characteristics of polypyrrole (PPy) films electrodeposited onto an electrochemically roughened gold substrate with bimetallic silver and gold nanoparticles were first investigated. First, a silver substrate was roughened by a triangular‐wave oxidation–reduction cycle (ORC) in an aqueous solution containing 0.1 M HCl. Subsequently, a gold substrate was roughened by a similar ORC treatment in this used solution. The results revealed that the surface of the roughened gold substrate demonstrated two different kinds of deposition domains because of the modification of silver nanoparticles. Encouragingly, some novel characteristics of PPy deposited onto this substrate were observed, in comparison with those on the roughened gold substrate without the modification of silver nanoparticles. They included a denser and more compact surface morphology, higher oxidation degree, increased conductivity, and improved surface‐enhanced Raman scattering. Furthermore, the nucleation and growth mechanism for PPy electropolymerization on this silver‐modified roughened gold substrate was distinguishable from that on the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2724–2731, 2006     

新型银胶基底研究HSA的近红外表面增强拉曼散射

用紫外—可见两步光化学还原法，合成了等离子体共振峰出现在近红外区的新 型绿色银胶．首次用该银胶作为基底研究人血清白蛋白(HSA)的近红外表面增强拉 曼散射(NIR—SERS)，发现银胶中的线状银纳米粒子聚集体有较强的NIR—SERS效应 和生物兼容性，这为研究生物大分子的结构、构象和界面作用提供了一种较为理想 的活性基底．由所得到的NIR—SERS光谱可发现，吸附在银纳米粒子表面的HSA的肽 链骨架仍以α—螺旋结构为主，其二级构象特征基本不变；吸附作用诱导部分芳香 氨基酸残基所处的微环境发生改变，趋于银纳米粒子表面．此外，明显观察到 COO^-与C—S的特征谱带说明HSA中去质子的羧基氧、二硫桥键的硫直接与银纳米粒 子表面作用．     

利用去湿现象制备具有SERS活性的银纳米粒子图案

构建了具有表面增强拉曼散射(SERS)活性的二维有序环状与盘状的银纳米粒子结构, 利用CTAB包覆银纳米粒子的氯仿溶液直接在图案化的金基底上进行去湿, 当改变银纳米粒子的浓度时可以得到不同的图案. 利用原子力显微镜(AFM)对其结构进行了表征, 以4-巯基吡啶作为探针分子, 采用表面增强拉曼成像技术研究了这种基底的SERS活性, 这将为SERS的研究开拓新的领域.     

Ag纳米粒子在TiO2四棱柱阵列上的可控生长及其SERS效应

采用水热法在导电玻璃FTO导电面上沉积TiO₂四棱柱阵列; 并以其为基体, 分别采用聚乙烯基吡咯 烷酮(PVP)还原Tollens试剂以及柠檬酸三钠(TSC)还原硝酸银溶液, 将Ag纳米粒子(AgNPs)沉积在TiO₂四棱柱阵列上形成TiO₂@AgNPs-PVP和TiO₂@AgNPs-TSC微纳结构作为表面增强拉曼散射(SERS)基底. 实验结果表明, Ag纳米粒子在TiO₂四棱柱阵列上的尺寸和分布可通过改变Tollens试剂的浓度和TSC还原硝酸银溶液的反应时间来调控, 进而优化基底的SERS灵敏度. TiO₂@AgNPs-PVP微纳结构对罗丹明6G(R6G)的检出限为10^-12 mol/L, 对低活性小分子三聚氰胺的检出限为0.01 mg/mL; TiO₂@AgNPs-TSC微纳结构对R6G的检出限为10^-10 mol/L, 对三聚氰胺的检出限为0.01 mg/mL. TiO₂@AgNPs-PVP和TiO₂@AgNPs-TSC微纳结构基底的SERS活性、 循环可回收性与还原剂种类紧密相关: 包覆在Ag纳米粒子上的PVP可以作为隔离层避免Ag纳米粒子直接接触, 防止电磁场耦合作用减弱, 增强基底的SERS活性; 同时, PVP是一种水性聚合物, 有较强的亲水性, 作为循环可回收SERS基底使用时, 吸附小分子物质清洗难度较大.     

Raman scattering of 4-aminobenzenethiol sandwiched between Ag/Au nanoparticle and macroscopically smooth Au substrate

Raman scattering measurements were conducted for a 4-aminobenzenethiol (4-ABT) monolayer assembled on a macroscopically smooth Au substrate. Although no peak was detected at the beginning, Raman peaks were distinctly observed by attaching Ag or Au nanoparticles onto the 4-ABT monolayer (Ag(Au)@4-ABT/Au(flat)). Considering the fact that no Raman signal is observed when Ag (Au) nanoparticles are adsorbed on a (4-aminophenyl)silane monolayer assembled on a silicon wafer, the Raman spectrum observed for Ag(Au)@4-ABT/Au(flat) must be a surface-enhanced Raman scattering (SERS) spectrum, derived from the electromagnetic coupling of the localized surface plasmon of Ag (Au) nanoparticles with the surface plasmon polariton of the underneath Au metal. The electromagnetic coupling responsible for SERS appeared to be governed more by the bulk Au substrate than the sparsely distributed Ag or Au nanoparticles. The chemical enhancement appeared on the other hand to be derived more from the formation of Au-S bonds than any charge-transfer interaction between the protonated amine group and the Au or Ag nanoparticles. The enhancement factors derived from the attachment of a single Ag or Au nanoparticle onto 4-ABT on Au were estimated to be as large as 8.3 x 10(5) and 5.0 x 10(5), respectively, (for the ring 3 band (b(2)) near 1390 cm(-1)) in which a factor of approximately 10(2) was presumed to be due to the chemical effect, with the remaining contributed by the electromagnetic effect.     

硫化镉钠米微粒在聚合物网络中的组装

硫化镉钠米微粒在聚合物网络中的组装黄金满，杨毅，杨柏，刘式墉，沈家骢（吉林大学分子光谱与分子结构重点实验室、集成光电子国家重点实验室，长春，１３００２３）关键词组装，纳米微粒，离子交换，透射电子显微镜，电子衍射由于纳米半导体微粒的物理和化学性质介于分...     

A simple method to synthesize triangular silver nanoparticles by light irradiation

We describe a simple method to synthesize triangular silver nanoparticles by photoreducing the silver ions by citrate. A noteworthy difference of the present method as compared with the previous photo-induced methods is that good shape control over the nanoparticles can be realized in the absence of soft templates or polymer directing agents. The formation process of the silver nanoparticles was investigated by UV-vis spectroscopy and transmission electron microscopy (TEM). It was found that the concentration of reactant plays important role in the morphology control of produced silver nanoparticles. As one of the applications of these nanoparticles, they were used as surface-enhanced Raman scattering substrates and 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BVPP) was used as a Raman probe to evaluate the enhancement ability of the triangular silver nanoparticles.     

Quantitative surface enhanced Raman scattering detection based on the "sandwich" structure substrate

A sandwich structured substrate was designed for quantitative molecular detection using surface enhanced Raman scattering (SERS), in which the probe molecule was sandwiched between silver nanoparticles (SNPs) and silver nanoarrays. The SNPs was prepared using Lee-Meisel method, and the silver nanoarrays was fabricated on porous anodic aluminum oxide (AAO) using electrodepositing method. The SERS studies show that the sandwich structured substrate exhibits good stability and reproducibility, and the detection sensitivity of Rhodamine 6G (R6G) and Melamine can respectively reach up to 10(-19) M and 10(-9) M, which is improved greatly as compared to other SERS substrates. The improved SERS sensitivity is closely associated with the stronger electromagnetic field enhancement, which stems from localized surface plasmon (LSP) coupling between the two silver nanostructures. Furthermore, the SERS intensity increased almost linearly as the mother concentration increased, which indicates that such a sandwich structure may be used as a good SERS substrate for quantitative analysis.     

Adsorption Behaviors of 4-Mercaptobenzoic Acid on Silver and Gold Films

The adsorption behaviors of 4-mercaptobenzoic acid on silver and gold nanoparticles were studied by surface-enhanced Raman scattering (SERS) and density functional theory. The silver and gold films by electrodeposition have the same excellent characteristics as SERS-active substrates. At the same, the SERS spectra indicate that 4-mercaptobenzoic acid molecules are adsorbed on the surfaces of gold nanoparticles through the S atom, and that the carboxyl group is far away from surface of gold nanoparticles, and that there is a certain angle between the plane of benzene ring and gold film. However, 4-mercaptobenzoic acid molecules are adsorbed on the surfaces of silver nanoparticles through the carboxyl group, and the S atom is far away from surface of silver nanoparticles, and there is also a certain angle between the plane of benzene ring and the surface of silver nanoparticles. Here it is demonstrated the calculated Raman frequencies are in good agreement with experimental values, and the calculated Raman frequencies are also helpful to infer the adsorption behaviors of 4-mercaptobenzoic acid molecules.     

Effect of the Spherical Silica Surface on the Photoluminescence of the Loaded CdS Nanoparticles

CdS nanoparticles were formed on the surface of silica microspheres by the improved layer‐by‐layer self‐assembled technique. High‐resolution electron microscope (HRTEM) image and energy dispersive x‐ray analysis (EDX) confirmed formation of a quasi‐continuous CdS nanoparticles film on the silica microspheres. The results of UV‐vis and fluorescence spectra display that the spherical silica surface has a great effect on the photoluminescence of the loaded CdS nanoparticles. In contrast to the CdS nanoparticles powder, the composite can exhibit the emission ascribed to the band gap transition when the CdS nanoparticles film is relatively thick. This phenomenon is probably due to an enhancement of the crystallinity of CdS nanoparticles induced by the silica spheres.     

Self-assembly of lambda-DNA networks/Ag nanoparticles: hybrid architecture and active-SERS substrate

In this article, highly rough and stable surface enhanced Raman scattering (SERS)-active substrates had been fabricated by a facile layer-by-layer technique. Unique lambda-DNA networks and CTAB capped silver nanoparticles (AgNP) were alternatively self-assembled on the charged mica surface until a desirable number of bilayers were reached. The as-prepared hybrid architectures were characterized by UV-vis spectroscopy, tapping mode atomic force microscopy (AFM) and confocal Raman microscopy, respectively. Linear increases of the maximum absorbance of DNA band with the number of bilayers present a common LBL assembly feature. The red-shift of surface plasmon of silver nanoparticles within the hybrid films was mainly due to the aggregation effect. With the increase of number of bilayers, the surface coverage of nanoparticles on the substrate became larger, as well as the rising of total amount of nanoparticles and the surface roughness of hybrid films. These rough metallic hybrid architectures could be utilized as SERS-active substrates. A significant enhanced Raman scattering effect of the adsorbed analytes, e.g., methylene blue (MB), on these hybrid films was easily exploited by the confocal Raman microscopy. The enhancement factor depended on the surface coverage of nanoparticles and number of bilayers of lambda-DNA/AgNP.     

Surface-enhanced Raman scattering of 4-aminobenzenethiol on silver nanoparticles substrate

Active surface-enhanced Raman scattering (SERS) silver nanoparticles substrate was prepared by multiple depositions of Ag nanoparticles on glass slides. The substrate is based on five depositions of Ag nanoparticles on 3-aminopropyl-trimetoxisilane (APTMS) modified glass slides, using APTMS sol–gel as linker molecules between silver layers. The SERS performance of the substrate was investigated using 4-aminobenzenethiol (4-ABT) as Raman probe molecule. The spectral analyses reveal a 4-ABT Raman signal enhancement of band intensities, which allow the detection of this compound in different solutions. The average SERS intensity decreases significantly in 4-ABT diluted solutions (from 10⁻⁴ to 10⁻⁶ mol L⁻¹), but the compound may still be detected with high signal/noise ratio. The obtained results demonstrate that the Ag nanoparticles sensor has a great potential as SERS substrate.     

Silver CD-R based substrate as a SERS active material

A silver Compact Disc Recortable (CD-R) based substrate has been proposed as an alternative to silver colloids as active material successfully used in surface-enhanced Raman spectroscopy (SERS). Scanning Electron Microscope (SEM) and Energy-Dispersive X-ray Spectroscopy (EDXS) measurements revealed that silver nanoparticles are present over the entire surface of the uncovered reflective layer of commonly used CD-R. The process of preparation of the CD-R based surface is simple, fast and repeatable. Recorded Raman spectra of 10 µM Rhodamine 6G applied to the substrate corroborate strong enhancement of Raman signal. The maximum value of EF was calculated to be about 5.76 × 10⁶. Raman maps are consistent with SEM micrographs and confirmed the presence of a numerous SERS hot spots occurring on the trucks of CD-R based substrate.