应用TLC—FT—SERS对萝芙木中利血平成分的研究

本文报道了应用薄层色谱（ＴＬＣ）与傅里叶变换表面增强拉曼光谱（ＦＴ－ＳＥＲＳ）联用技术,获得了中草药萝芙木有效成分利血平光谱研究的新方法。研究表明：在薄层原位约２μｇ的样品即可获得利血平分子的特征振动谱带,并阐述了样品分子在表面增强基底银微粒表面的吸附模式,从而说明ＴＬＣ－ＳＥＲＳ结合对中草药化学成分进行高灵敏度指纹检测的可靠性和优越性。     

马尾松毛虫核型多角体病毒粒子的SERS谱研究

获得并研究了马尾松毛虫核型多角体病毒粒子在银胶中的表面增强拉曼散射（ＳＥＲＳ）谱。ＳＥＲＳ谱的增强特性与ｐＨ值有关，其ＳＥＲＳ谱在ｐＨ＝８时获得了最好的增强，该粒子是通过其衣壳蛋白的ＣＯＯ和ＮＨ２基因吸附的银表面上，色氨酸（Ｔｒｐ）和酪氨酸（Ｔｙｒ）残基侧链远离银表面，酰胺Ｉ和酰胺Ⅲ的光谱带在ＳＥＲＳ谱中未出现，增强机制以化学增强为主。     

咪唑在铜电极上吸附行为的SERS研究

咪唑在铜电极上吸附行为的ＳＥＲＳ研究张传飞，徐知三，旷富贵，王小华，刘海林（武汉大学分析测试中心武汉４３００７２）（武汉大学环境科学系武汉４３００７２）ＳｔｕｄｙｏｎＴｈｅＡｄｓｏｒｐｔｉｏｎＢｅｈａｖｉｏｕｒｏｆＩｍｉｄａｚｏｌｅｏｎＣｏｐｐｅｒＥ...     

Ag2O胶体上SERS增强机制的研究

通过研究分别加入Ｎａ２Ｓ２Ｏ３和ＮａＯＨ对Ａｇ２Ｏ胶体上吸附分子ＳＥＲＳ的影响以ＳＥＲＳ随时间的变化发现；Ａｇ２Ｏ作为ＳＥＲＳ的活性载体，化学增强起决定作用，吸附分子与Ａｇ２Ｏ胶体表面的小银离子簇（如Ａｇ＾４＋）形成或强或弱的难溶于水的银离子簇络合物，构成ＳＥＲＳ活性中心，它们之间的电荷转移是增强的重要因素，应用激发态电荷转移模型初步估算了Ｄ２６６分子增强因子的量级，得到了与实验值基本一致的结果。     

银溶胶吸附的R一藻红蛋白的表面增强共振拉曼散射

现已获得银溶胶吸附的Ｒ一藻红蛋白的表面增强共振拉曼散射（ＳＥＲＲＳ），在它的ＳＥＲＲＳ谱图上共有３５根谱线，而它的拉曼光谱图仅有一个“荧光包”，所有的谱线都被这个“包”所覆盖。由于银溶胶一藻红素复合物的形成及与ＳＥＲＳ的金属基活性表面的相互作用，该ＳＥＲＲＳ谱线增强及荧光淬灭。Ｒ一藻红蛋白是由藻红素和它周围的蛋白基质组成，但是在Ｒ一藻红蛋白的ＳＥＲＲＳ谱上仅有藻红素的一些谱线。这再一次表明在带有发色团组份的蛋白质（Ｒ一藻红蛋白）与银溶胶的结合中存在着竞争结合；发色团藻红素（ＰＥＢ）是对ＳＥＲＲＳ效应负主要责任的。因此，表面增强共振拉曼散射技术对研究带发色团的蛋白质是非常有用的     

表面增强拉曼光谱在非水体系中的研究进展

本文论述了表面增强拉曼光谱（ＳＥＲＳ）在非水体系中的研究历史、现状及应用前景,系统阐述了非水体系固／液界面结构、无机离子和有机分子的吸附以及非水电极过程方面ＳＥＲＳ技术的研究进展。     

四种D-氨基葡萄糖甘氨酸混配金属配合物与DNA作用的SERS光谱研究

研究了四种Ｄ－氨基葡萄糖甘氨酸混配金属配合物的表面增强喇曼光谱（ＳＥＲＳ），发现它们在银胶上的吸附方式基本相同，因而ＳＥＲＳ光谱也基本相似，并用ＳＥＲＳ光谱研究了它们与ＤＮＡ的相互作用，发现这四种化合物与ＤＮＡ的作用能力有很大不同，Ｃｏ（Ⅲ）ＧｌｕＧ是值得进一步研究的可能抗癌药物。     

四种D—氨基葡萄糖甘氨酸混配金属配合物与DNA作用的SERS光…

研究了四种Ｄ－氨基葡萄糖甘氨酸混配合金属配合物的表面增强喇曼光谱（ＳＥＲＳ），发现它们在角胶上的吸附方式基本相同，因而ＳＥＲＳ光谱也基本相似，并用ＳＥＲＳ光谱研究了它们与ＤＮＡ的相互作用，发现这四种化合物与ＤＮＡ的作用能力有很大不同，Ｃｏ（Ⅲ）ＧｌｕＧ是值得进一步研究的可能抗癌药物。     

罗丹明6G在银纳米线阵列上的SERS光谱研究

制备出有序、均匀的活性衬底一直足表面增强拉曼散射(SERS)研究中的关键.阳极氧化法制备的多孔氧化铝膜的结构有序、均匀,为纳米金属SERS基底的制备提供了模板.以沉积了银的多孔氧化铝组装体为衬底,研究了罗丹明6G(Rh6G)分子的表面增强拉曼散射光谱.结果表明,沉积了银的多孔氧化铝模板是很好的SERS衬底,Rh6G分子在此衬底上的SERS谱强度与银纳米线在表面的显露高度有关,而其拉曼频移未受表面状态的影响,而PO43-离子的存在使SERS强度得到很大提高.     

银胶中结晶紫分子吸附动力学过程及氯离子的影响

同在吸附银镜上相似，ＣＶ在银胶上均相吸附，表面形态对化学吸附的多相性无必然影响。氯离子的存在有助于银表面上产生ＳＥＲＳ活位，使ＣＶ的ＳＥＲＳ强度增强－１０＾２倍，活位上分子的喇曼散射截面较普通吸附位置上的分子增加了１０＾５倍，吸附动力学计算结果表明所有ＳＥＲＳ活位是等价的。     

Photochemical decoration of silver nanoparticles on ZnO nanowires as a three‐dimensional substrate for surface‐enhanced Raman scattering measurement

To increase the sensitivity in surface‐enhanced Raman scattering (SERS) measurement, a three‐dimensional (3D) SERS substrate was prepared by the decoration of silver nanoparticles (AgNPs) on the side walls of ZnO nanowires. The prepared 3D SERS substrates provide the advantages of highly loaded density of AgNPs, with a large specific surface area to interact with analytes, and the ease for the analytes to access the surfaces of AgNPs. To prepare the substrates, ZnO nanowires were first grown on a glass plate by wet chemical method. By treating SnCl₂ on the surfaces of ZnO nanowires, Ag seeds could be formed on the side wall of the ZnO nanowires, which were further grown to a suitable size for SERS measurements via photochemical reduction. To optimize and understand the influences of the parameters used in preparation of the substrates, the reaction conditions were systematically adjusted and examined. Results indicated that AgNPs could be successfully decorated on the side wall of the ZnO nanowires only by the assistances of SnCl₂. The size and density of AgNPs were affected by both the concentration of silver nitrate and the irradiation time. With optimized condition, the prepared 3D substrates provided an enhancement factor approaching 7 orders of magnitude compared with conventional Raman intensity. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface-enhanced Raman scattering from silver nanostructures with different morphologies

Scanning electron microscopy and X-ray diffraction reveal that four different types of crystalline silver nanostructures including nanoparticles, nanowires, nanocubes, and bipyramids are synthesized by a solvothermal method by reducing silver nitrate with ethylene glycol using poly(vinylpyrrolidone) as an adsorption agent and adding different quantities of sodium chloride to the solution. These nanostructures which exhibit different surface plasma resonance properties in the ultraviolet–visible region are shown to be good surface-enhanced Raman scattering (SERS) substrates using rhodamine 6G molecules. Our results demonstrate that the silver nanocubes, bipyramids with sharp corners and edges, and aggregated silver nanoparticles possess better SERS properties than the silver nanowires, indicating that they can serve as high-sensitivity substrates in SERS-based measurements.     

Improved performance of surface‐enhanced Raman scattering on silver substrates prepared in nitric acid solutions

In this work, we propose a new electrochemical method to prepare surface‐enhanced Raman scattering (SERS)‐active silver substrates in nitric acid solutions. Experimental results indicate that the SERS intensity of adsorbed Rhodamine 6G (R6G) can be significantly increased, as compared with that of R6G adsorbed on a SERS‐active Ag substrate prepared by an electrochemical method in a chloride‐containing solution, which was generally employed in the literature. Moreover, the SERS of R6G on the newly developed substrate (prepared in a nitric acid solution) still performs well at a high temperature of 250 °C. However, the enhancement capability of the SERS‐active substrate prepared in a chloride‐containing solution is seriously destroyed at temperatures higher than 150 °C. Further investigations indicate that the oxidation states of roughened Ag substrates prepared in nitric acid solutions under different experiment conditions have less influence on the corresponding SERS performances. Instead, different surface morphologies of roughened Ag substrates and different contents of nitrogen‐containing dopping ions on the roughened Ag substrates demonstrate significant effects on the corresponding SERS performances. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation,characterization, and electrochemical performances of graphene/Ni(OH)2 hybrid nanomaterials

We report a class of core–shell nanomaterials that can be used as efficient surface-enhancement Raman scattering (SERS) substrates. The core consists of silver nanowires, prepared through a chemical reduction process, that are used to capture 4-mercaptobenzoic acid (4-MBA), a model analyte. The shell was prepared through a modified Stöber method and consists of patchy or full silica coats. The formation of silica coats was monitored via transmission electron microscopy, UV–visible spectroscopy, and phase-analysis light-scattering for measuring effective surface charge. Surprisingly, the patchy silica-coated silver nanowires are better SERS substrate than silver nanowires; nanomolar concentration of 4-MBA can be detected. In addition, “nano-matryoshka” configurations were used to quantitate/explore the effect of the electromagnetic field at the tips of the nanowire (“hot spots”) in the Raman scattering experiment.     

Improved performances on surface‐enhanced Raman scattering based on electrochemically roughened gold substrates modified with SiO2 nanoparticles

In this work, we use electrochemical oxidation–reduction cycles (ORC) methods to prepare surface‐enhanced Raman scattering (SERS)‐active gold substrates modified with SiO₂ nanoparticles to improve the corresponding SERS performances. Based on the modified substrates, the SERS of Rhodamine 6G (R6G) exhibits a higher intensity by 3‐fold of magnitude, as compared with that of R6G adsorbed on a SERS‐active Au substrate without the modification of SiO₂ nanoparticles. Moreover, the SERS enhancement capabilities of the modified and the unmodified Au substrates are seriously destroyed at temperatures higher than 250 and 200 °C, respectively. These results indicate that the modification of SiO₂ nanoparticles can improve the thermal stability of SERS‐active substrates. The aging in SERS intensity is also depressed on this modified Au substrate due to the contribution of SiO₂ nanoparticles to SERS effects. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation of silver nanoparticles on zinc oxide nanowires by photocatalytic reduction for use in surface‐enhanced Raman scattering measurements

To increase the sensitivity in surface‐enhanced Raman scattering (SERS) measurements, the high surface area of zinc oxide nanowires (ZnO NWs) was used. ZnO NWs on silicon substrates were prepared and used as substrates for further growth of silver nanoparticles (AgNPs). Ultraviolet (UV) irradiation was used to reduce silver ions to AgNPs on the ZnO wires. With proper growth conditions for both ZnO NWs and AgNPs, the substrates exhibit SERS enhancement factors greater than 10⁶. To understand the influences of the morphologies of the ZnO NWs on the growth of AgNPs, the growing time and temperature were varied. The concentration of silver nitrate and irradiation time of UV radiation were also varied. The resulting AgNPs were probed with para‐nitrothiophenol to quantify the SERS enhancements obtained from the varying conditions. The results indicate that ZnO NWs could be grown at temperatures higher than 490 °C and higher growth temperatures result in smaller diameter of the formed ZnO NWs. Also, the morphologies of ZnO NWs did not significantly alter the SERS signals. The concentration of silver nitrate affects the SERS signals significantly and the optimal concentration was found to be in the range of 10–20 mM. With irradiation times longer than 90 s, the resulting AgNPs showed similar SERS intensities. With optimized conditions, the AgNPs/ZnO substrates are highly suitable for SERS measurements with a typical enhancement factor of higher than 10⁶. Copyright © 2010 John Wiley & Sons, Ltd.     

打印技术制备表面增强拉曼散射活性基底的研究进展

表面增强拉曼散射(SERS)是一种先进的表面分析技术,可以极大提高吸附在金属表面或附近分子的拉曼散射信号。SERS技术由于其快速准确、灵敏度高、选择性好、样品制备要求低等特点,成为当前的研究热点,在化学、食品、生物、医疗等领域展现出重要的应用前景。而利用SERS技术作为一种常规分析和诊断工具面临的一个主要挑战是如何制备均匀、可重复、稳定的活性基底。打印技术操作简单、效率高、成本低,有助于设计等离激元纳米结构。通过优化“热点”增强电磁场,获得重复性好、稳定性高、增强能力强的SERS活性基底。近年来,印刷技术逐渐被应用于SERS基底的制备。主要综述了制备SERS基底的几种常用印刷技术,包括喷墨印刷、凹版印刷、丝网印刷等。分析了衬底表面润湿性、干燥温度、油墨粘度、表面张力、溶剂等因素对SERS性能的影响。总结了印刷技术制备SERS基底的研究进展,并对其潜在应用和未来发展作了展望。     

Effects of solid substrate on the SERS‐based immunoassay: a comparative study

A comparative study of the solid substrates used in surface‐enhanced Raman scattering (SERS) based immunoassay is made in this paper. Five different substrates were prepared and divided into two groups with and without SERS activity. They are (1) a poly‐L ‐lysine slide, (2) a glutaraldehyde (GA)‐aminosilane slide, (3) a substrate assembled with silver nanoparticles, (4) a substrate assembled with silver nanoparticles and functionalized with GA–aminosilane and (5) a substrate assembled with gold nanoparticles, of which the first two are substrates are without SERS activity and the latter three are with SERS activity because of the existence of the metallic nanoparticles. The SERS experimental results show that the immunoassay performed on an SERS‐active substrate is more effective than that employing the inactive substrate. Among the inactive substrates, the GA–aminosilane slide with a better ability for antibody immobilization leads to a more sensitive immunoassay than the poly‐L ‐lysine slide. Moreover, for SERS‐based immunoassay, the substrate with assembled silver nanoparticles has an advantage of higher SERS enhancement capacity over the substrate assembled with gold nanoparticles. This work indicates that SERS‐active substrates play important and positive roles in sensitive SERS‐based immunoassay. Copyright © 2010 John Wiley & Sons, Ltd.     

An improved self‐assembly gold colloid film as surface‐enhanced Raman substrate for detection of trace‐level polycyclic aromatic hydrocarbons in aqueous solution

To detect trace‐level polycyclic aromatic hydrocarbons, some investigations of an improved self‐assembly method are carried out using gold colloid films for the preparation of the surface‐enhanced Raman scattering (SERS)‐active substrate. Extinction spectra and scanning electron microscopy images reveal that controllable surface plasmonic metal substrates can be obtained by increasing the temperature of (3‐aminopropyl)trimethoxysilane solution up to 64.5 °C. The SERS‐active substrates have a high enhancement factor, and they can be both easily prepared and reproducible. With the use of these substrates, different concentrations of pyrene and anthracene in aqueous solutions were detected by SERS. A further enhancement can be supported by shifted excitation Raman difference spectroscopy. Raman signals of pyrene and anthracene adsorbed on gold colloid substrates up to limits of detection at 5 and 1 nmol/l, respectively, can be obtained. The quantitative analysis shows the possibility of in situ detection of polycyclic aromatic hydrocarbons while such gold colloid film serves as a SERS‐active substrate. Copyright © 2012 John Wiley & Sons, Ltd.     

茶叶表面增强拉曼光谱的初步研究

以铁观音为例,测试其表面增强拉曼(SERS)光谱,并从增强能力、背景噪声、光谱重复性和信噪比等方面,研究探讨铁观音茶叶SERS光谱测试时活性基底选择;不同吸附时间对光谱测试的影响。结果表明：以柠檬酸三钠还原硝酸银制得的银溶胶为活性基底的增强效果更好,吸附时间对于铁观音茶叶SERS光谱的测试没有直观的影响。SERS光谱的茶叶研究方法有可能为茶叶的判别和质量鉴定提供一种新的方法。