TiO_2/Ag composite nanowires for a recyclable surface enhanced Raman scattering substrate

Multifunctional TiO2/Ag composite nanowires are fabricated with a hydrothermal method by precipitating Ag nanoparticles （NPs） on the surfaces of TiO2 nanowires. This hierarchical one-dimensional （1D） nanostructure can be used as a surface enhanced Raman scattering （SERS） substrate with high sensitivity, for detecting the rhodamine 6G （R6G） in a wide range of low concentrations （from 1 × 10 6 M to 1 × 10-12 M）. In addition, the substrate can be self-cleaned under the irradiation of ultraviolet （UV） light due to the superior photocatalytic capacity of the TiO2/Ag composite nanostructure, making the recycled use of SERS substrates closer to reality. With both the evident SERS performance and high efficiency of photocatalytic capacity, such TiOz/Ag composite nanowires demonstrate considerable potential in the chemical sensing of organic pollutants.     

Synthesis of silver nanowires via electroplating technology and its surface enhanced Raman scattering effect

This very paper is focusing on the preparation of silver nanostructures and the surface enhanced Raman scattering effect of the silver nanostructures produced. Via electroplating technology, silver nanowires and nanoparticles were prepared on silicon wafers. Characterization was performed by X-ray diffraction, scanning electron microscope, transmission electron microscope equipped with X-ray energy dispersion spectroscope and selected area electron diffraction, which reveals that the formation of silver nanostructures depends on the over-potential. The produced silver nanowires are of crystalline FCC structure and grow in 〈0 1 1〉 direction. The growth mechanism has been further discussed. The surface enhanced Raman scattering effect is achieved with the silver nanostructures produced.     

Deposition of Ag nanoparticles on porous anodic alumina for surface enhanced Raman scattering substrate

Ag nanoparticles were exclusively deposited inside the pores of the porous anodic alumina (PAA) template through the deposition cycle including the incubation and the subsequent reduction of Ag(NH₃) . Both the density and size of the produced Ag nanoparticles increased as the deposition cycle number increased. A field‐emission scanning electron microscopeand an ultraviolet‐visible spectrometer were applied, respectively, to study the morphology and the extinction spectra of the Ag nanoparticles. The optimum deposition number was found from the scanning electron microscope (SEM) analysis. Surface enhanced Raman scattering (SERS) spectra of p‐aminothiophenol recorded on the Ag–PAA substrates prepared under increasing number of deposition cycles, manifested an enlarging trend of peak intensity. A point‐by‐point SERS mapping of p‐aminothiophenol on the Ag–PAA substrate was acquired to characterise the homogeneity of the substrate. Copyright © 2008 John Wiley & Sons, Ltd.     

可循环表面增强拉曼光谱基底的制备及其应用

以氨基硅烷为偶联剂,硅酸钠为硅源,合成了一种以金为核,二氧化硅为壳的核壳纳米粒子。通过调节硅酸钠的量,反应温度和反应时间控制二氧化硅壳层厚度,获得理想的表面增强效应。通过研究表面增强拉曼光谱(SERS)信号强度和二氧化硅层厚度之间的关系优化基底的制备条件。采用对巯基苯和联吡啶作为探针分子进行SERS实验,在一定浓度范围内得到SERS信号强度和浓度的对数之间的线性关系,实验结果表明此组装有Au@SiO2的ITO基底作为可循环利用基底可定量分析吸附物种的浓度。     

唾液表面增强拉曼光谱用于肺癌的诊断

表面增强拉曼光谱已经展示了其在低浓度体液的检测方面的优势。对21例肺癌患者和22例正常人的唾液进行了检测和区分。肺癌患者在多处波数位的峰强较正常人有所下降,只有少数峰强度上升且幅度较小。这些峰主要归属为蛋白质和核酸,表明肺癌患者唾液中这些成分的含量较正常人为少。主成分分析法(PCA)和线性辨别分析(LDA)被用于两组数据的降维和区分,所得结果准确度为84%,灵敏度为94%,特异性为81%。     

Engineering of IrO2 nanofiber for surface enhanced Raman scattering

In this paper, we demonstrate the use of nano-engineered Ir/IrO₂ nanofibers (NFs) as substrates for surface-enhanced Raman scattering (SERS). We employed the electrospinning and annealing process to fabricate the IrO₂ nanofibers featuring of interconnected nanoparticles. The obtained IrO₂ NFs were subjected to reduction process as a function of time (5–180 min). IrO₂ NFs were fully converted to Ir metal after 120 min of reduction. The resulting structures were examined as SERS substrates using rhodamine 6G (R6G) molecule excited by 632.8 nm laser. A distinct Raman signal of R6G was identified and its intensity gradually increased as a function of the reduction time of IrO₂ NFs. UV/vis spectrum of Ir NFs showed increase of absorption at 632.8 nm, concluding that the enhanced Raman signal is due to the electromagnetic field enhancement at the Ir metal. This work is the first to report the nano-engineering of Ir/IrO₂ nanofibers for a SERS application.     

基于银胶纳米颗粒的痕量三硝基甲苯的表面增强拉曼光谱的实验研究

近年来对作为典型的硝基苯环类炸药的三硝基甲苯(TNT)的痕量检测受到越来越多的关注。将银胶纳米颗粒作为表面增强拉曼散射(SERS)基底,研究了10-6 mol.L-1的TNT的表面增强拉曼光谱的优化实验条件,重点研究了氯化钠溶液(NaCl)的含量以及碱性水解对TNT的表面增强拉曼光谱的影响。实验发现SERS样品中如果没有加入NaCl溶液,将观察不到TNT的SERS谱。加入的NaCl的含量必须在某一个范围之内才能观察到TNT的SERS谱,而且在这个范围之内,随着NaCl含量的增加,TNT的1 392cm-1处的拉曼峰出现先增大后减小的现象。对NaCl在TNT的SERS中的作用给予了理论解释。研究还发现TNT分子经过碱性水解后,与银纳米颗粒之间的吸附作用增强,其SERS谱的强度明显优于未经碱性水解的SERS结果。     

表面等离子激元非线性表面增强拉曼散射效应

本文采用热蒸发法制备得到纳米Ag颗粒作为增强拉曼衬底, 利用入射光子与纳米颗粒表面价电子的相互作用机理, 激发出高能表面等离子激元, 其表面等离子形成的高能"热点"起到表面增强拉曼散射效果. 通过比较不同入射光强下的拉曼峰强, 指出纳米Ag颗粒的增强拉曼散射效果可以实现低探测光强下的高散射强度, 即纳米Ag颗粒的表面等离子激元具有非线性的表面增强拉曼散射效果, 可降低对样品的光、热损伤, 以利于拓展拉曼散射光谱的应用范围. 同时比较不同纳米Ag颗粒衬底的表面增强拉曼散射效果表明, 采用的热蒸发工艺具有较大的工艺域度, 具有较强的工艺兼容性.     

小牛胸腺DNA分子Langmuir-Blodgett复合膜的表面增强拉曼光谱研究

本文利用Langmuir-Blodgett(LB)技术将小牛胸腺DNA分子沉积在银基底上,测试并讨论了它的π-A等温曲线,原子力图及表面增强拉曼光谱(SERS)。通过利用LB技术,获得了DNA分子的LB复合膜的高质量的SERS。在DNA分子LB膜的表面增强拉曼光谱中,DNA的核糖和碱基腺嘌呤是吸附活性部位,它们的振动光谱得到增强。DNA的其它碱基和磷酸基团的拉曼光谱强度也明显的得到增强。分析认为DNA分子增强的拉曼光谱主要是由于LB膜的有序结构的贡献,使得SERS效应得到进一步的增强。因此利用LB技术是得到DNA的高质量SERS很好的方法。     

A simple method to prepare the magnetic Ni@Au core‐shell nanostructure for the cycle surface enhanced Raman scattering substrates

We have developed a simple and efficient approach to synthesize Ni@Au core‐shell nanostructures using the simple redox transmetalation reaction. The as‐synthesized nanomaterial with clean and reproducible properties was used as the surface enhanced Raman scattering (SERS) substrate. In addition, these nanostructures are stable for at least a 30‐day period, and the long‐term stability is of the great importance in practical application. The magnetic behavior serves as an added advantage of its easy separation from the analytes. So that it can be reused. This novel multifunctional hybrid nanostructure will open up an exciting opportunity in multiple uses SERS measures. Copyright © 2013 John Wiley & Sons, Ltd.     

Hole arrayed metal-insulator-metal structure for surface enhanced Raman scattering by self-assembling polystyrene spheres

A fabrication process based on the self-assembling polystyrene spheres is proposed to obtain hole arrayed metal-insulator-metal （HA-MIM） structure for surface enhanced Raman scattering （SERS）. The localized field enhancement aroused by the gap resonance in the HA-MIM structure is analyzed by finite-different time domain （FDTD） method. With reference to the theory result, the structure is experimentally fabricated and the Raman scattering spectrum of rhodamine 6G （R6G） is measured by a miniaturized Raman spectrometer. The results shows that the enhancement factor is 3.85 times higher than the control sample with single layered metal hole array. The fabrication process to obtain the HA-MIM SERS substrate is reproducible, fast, large area and low cost.     

Porous silicon as efficient surface enhanced Raman scattering (SERS) substrate

Silver nanocrystallites are obtained through immersion of porous silicon samples in AgNO₃ solutions and a successive thermal annealing. The efficiency of nanostructures as surface enhanced Raman scattering (SERS) substrates is checked on cyanine-based dyes and horseradish peroxidase, evidencing detectable concentrations as low as 10⁻⁷ to 10⁻⁸ M. The substrate efficiency is strictly related to the Ag particle morphology, which could yield to either local surface plasmons (LSP) coupled to individual particles or to inter-particle short-range interaction.     

纳米Ag材料表面等离子体激元引起的表面增强拉曼散射光谱研究

用热蒸发的方法制备了纳米Ag材料,并用扫描电子显微镜对纳米粒子进行了形貌的表征,通过紫外—可见分光光度计得到Ag纳米粒子的透过谱,得到了Ag纳米粒子的表面等离子体共振的峰值位置.以罗丹明6G为探针分子测定Ag纳米粒子衬底的表面增强拉曼散射效应,通过拉曼散射光谱与透过谱研究了由表面等离子体激元的强极化场引起的表面增强拉曼散射效应,结合透过谱与拉曼增益因子提出了一种描述表面等离子体光学和电学特性的方法,并结合扫描电镜的结果给出了不同结构的纳米Ag材料对表面等离子体激元强度的影响. 关键词： 热蒸发 纳米Ag材料 表面等离子体 表面增强拉曼散射     

Highly efficient silver particle layers on glass substrate synthesized by the sonochemical method for surface enhanced Raman spectroscopy purposes

A fast method for preparing of silver particle layers on glass substrates with high application potential for using in surface enhanced Raman spectroscopy (SERS) is introduced. Silver particle layers deposited on glass cover slips were generated in one-step process by reduction of silver nitrate using several reducing agents (ethylene glycol, glycerol, maltose, lactose and glucose) under ultrasonic irradiation. This technique allows the formation of homogeneous layers of silver particles with sizes from 80 nm up to several hundred nanometers depending on the nature of the used reducing agent. Additionally, the presented method is not susceptible to impurities on the substrate surface and it does not need any additives to capture or stabilize the silver particles on the glass surface. The characteristics of prepared silver layers on glass substrate by the above mentioned sonochemical approach was compared with chemically prepared ones. The prepared layers were tested as substrates for SERS using adenine as a model analyte. The factor of Raman signal enhancement reached up to 5·10⁵. On the contrary, the chemically prepared silver layers does not exhibit almost any pronounced Raman signal enhancement. Presented sonochemical approach for preparation of silver particle layers is fast, simple, robust, and is better suited for reproducible fabrication functional SERS substrates than chemical one.     

pH‐sensing nanostar probe using surface‐enhanced Raman scattering (SERS): theoretical and experimental studies

Local pH environment has been considered to be a potential biomarker for tumor diagnosis because solid tumors contain highly acidic environments. A pH‐sensing nanoprobe based on surface‐enhanced Raman scattering (SERS) using nanostars under near‐infrared excitation has been developed for potential biomedical applications. To theoretically investigate the effect of protonation state on SERS spectra of p‐mercaptobenzoic acid (pMBA), we used the density functional theory (DFT) with the B3LYP functional to calculate Raman vibrational spectra of pMBA‐Au/Ag complex in both protonated and deprotonated states. Vibrational spectral bands were assigned with DFT calculation and used to investigate SERS spectral changes observed from experiment when varying pH value between five and nine. The SERS peak position of pMBA at ~1580 cm⁻¹ was identified to be a novel pH‐sensing index, which has small but noticeable downshift with pH increase. This phenomenon is confirmed and well‐explained with theoretical simulation. The study demonstrates that SERS is a sensitive tool to monitor minor structural changes due to local pH environment, and DFT calculations can be used to investigate Raman spectra changes associated with minor differences in molecular structure. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface enhanced Raman scattering based molecule detection using self-assembled DNA nanostructures

A novel method of Surface Enhanced Raman Scattering (SERS) based molecular detection was developed using self-assembled DNA nanostructures. Molecule detection using rigid, shape-controllable DNA nanostructures provides significant advantages such as accurate control of the particle distance and geometrical programmability of the DNA nanostructure. We successfully detected the Cy3 dye, a Raman-active molecule, at 1461, 1590, and 1619 cm⁻¹ using a Ag-enhanced Au-DNA nanostructure. Consequently, DNA-guided SERS detection is expected to contribute significantly to molecular detecting systems in the near future.     

A hybrid substrate for surface‐enhanced Raman scattering spectroscopy: coupling metal nanoparticles to strong localised fields on a micro‐structured surface

Electromagnetic coupling between localised plasmons on metal nanoparticles and the strong localised fields on a micro‐structured surface is demonstrated as a means to increase the enhancement factor in surface‐enhanced Raman scattering (SERS) spectroscopy. Au nanoparticles of diameter 20 nm were deposited on a micro‐structured Au surface consisting of a periodic array of square‐based pyramidal pits (Klarite). The spectra of 4‐aminothiophenol (4‐ATP) were compared before and after deposition of Au nanoparticles on the micro‐structured surface. The addition of Au nanoparticles is shown to provide significantly higher signal intensities, with improvements of the order of ∼10³ per molecule compared with spectra obtained from the micro‐structured substrate alone. This hybrid approach offers promise for combining nanoparticles with micro‐ and nano‐structured surfaces in order to design SERS substrates with higher sensitivities. Copyright © 2011 John Wiley & Sons, Ltd.     

非水体系中哌啶在银电极表面的表面增强喇曼散射

本文测定了哌啶在甲醇溶液中吸附在银电极表面的表面增强喇曼散射(SERS)光谱,及其随电位的变化,同时还测定了电极经不同氧化-还原循环(ORC)预处理时的SERS谱,对所得结果进行了分析比较,并进一步研究了非水体系和水体系SERS谱之间的关系.实验结果表明:哌啶在甲醇体系中比在水体系中SERS谱的增强因子要小,并且它们的SERS谱线随电位的变化也有一定的差别.     

Surface enhanced Raman scattering (SERS): Annealing the silver substrate

Silver films, deposited at 120 K in UHV, were slowly warmed to room temperature, Characteristic intensity variations of the inelastic background (I), of disorder induced Raman scattering from phonons (II) and of the SERS signal from adsorbed pyridine have been observed. In the case of (I) and (II) these are explained by the bulk concentration of point defects, in the SERS case by annealing of atomic scale surface roughness.     

Aluminium nanohole arrays enhanced resonance Raman scattering spectra in the near ultraviolet region

Aluminium nanohole arrays with fixed diameter were fabricated by focused ion beam and the periodicities were turned.Aluminium nanohole arrays enhanced resonance Raman scattering spectra in the near ultraviolet region were studied experimentally and theoretically,which revealed that the SERRS enhancement factor was as high as 6 orders.