共焦显微拉曼光谱在界面研究中的应用

本研究的重点是拓宽共焦显微拉曼光谱技术在液／气、液／固界面研究中的应用。通过合理地设计实验,利用共焦显微拉曼光谱技术高的纵向分辨率研究了液／气界面水溶性的卟啉（ＴＳＰＰ）的聚集行为,发现ＴＳＰＰ在本体中和在界面上的行为有着显著的区别。同时,对甲醇电化学氧化过程中电极表面附近的溶液成分进行了剖层分析。利用其高的横向分辨率,借助表面增强效应对沉积在玻碳上的金薄层进行拉曼成像研究,发现光学成像和拉曼成像     

非水体系中金电极表面增强拉曼光谱研究新进展

利用共焦显微拉曼系统,进行了甲醇溶液中硫氰酸根离子（SCN^-）在金电极上吸附行为的表面增强拉曼光谱（SERS）研究,结果表明：SCN^-与电极之间的相互作用非常强烈,在整个研究电位范围内都可以检测到其SERS信号。在－0．1～－0．6V区间内,SCN^-主要是以S端吸附在电极表面：而在－0．7V～－1．2V区间内,SCN^-主要是以N端吸附在电极表面。     

表面增强拉曼光谱在铁腐蚀与防护研究中的应用

综述了近年来表面增强拉曼光谱(SERS)在铁表面腐蚀与防护方面的应用和研究进展。作为一种能够在分子水平上提供物质结构信息的技术,SERS被广泛应用在金属特别是铁腐蚀与防护的研究中。文章主要从铁表面SERS增强理论模型、缓蚀剂在铁表面的吸附方式和铁电极上氧化或钝化膜的结构３个方面来展示SERS技术的应用,并展望了进一步研究的方向。     

元代铜镜腐蚀情形的拉曼光谱研究

应用显微拉曼光谱和电子探针技术 ,对云南禄丰出土的元代铜镜腐蚀情形进行研究 ,确定了铜镜本体及其表面腐蚀产物的成分 ,并初步分析了元代青铜镜采用的防腐技术。拉曼实验结果表明 ,铜镜表面腐蚀产物的主要成分有CuCO3 ·Cu(OH) 2 和Cu2 O。实验还发现铜镜表面有一层铁铝合金 ,具有较好的防腐作用。对金属文物的研究 ,拉曼光谱被证明是一种很有效的方法     

非水乙腈体系中CO在铂电极表面吸附的SERS研究

在非水乙腈体系中，借助LabRam Ⅰ型共焦显微拉曼系统，尝试用表面增强拉曼光谱（SERS）对作为燃料电池中毒化中间体的CO在过渡金属铂电极表面的催化氧化进行了研究，并考察了在电极电位的变化过程中CO的催化氧化与周围环境分子的相互作用。不仅观察到CO在铂金属表面的吸附和氧化，还得到溶剂乙腈分子发生解离的表面增强拉曼光谱，并对CO和CH3CN分子在铂电极上的竞争吸附进行了分析。     

腺苷在银电极上的原位拉曼光谱

本文利用原位表面增强拉曼光谱电化学技术研究了DNA理论水解产物之一腺苷在银电极上吸附行为,光谱数据表明在0.4～-0.2V电位区间内腺苷的腺嘌呤部分在电极上是平躺构型。     

铁电极表面拉曼光谱的初步研究

本文成功地把表面 Raman光谱研究拓宽到重要的过渡金属之一的铁电极上。实验尝试了多种粗糙处理方法 ,如 :化学刻蚀、现场和非现场电化学氧化还原等法对铁电极表面进行处理 ,并首次获得吸附在粗糙铁电极上的吡啶分子的高质量表面拉曼光谱。经过比较发现表面拉曼光谱信噪比的提高与电极表面粗糙度有很大的关系 ,合适的表面粗糙度极有可能诱导出弱的表面增强拉曼散射效应     

拉曼光谱技术的应用及研究进展

本文简述了拉曼光谱产生的机理以及与红外光谱的区别,讨论了拉曼光谱在聚合物、生物分子、蛋白质和无机物等方面研究及应用,介绍了傅立叶变换拉曼、共焦显微拉曼、表面增强激光拉曼、固体光声拉曼光谱的原理及其应用以及拉曼光谱和其他检测手段的联用技术。     

现场拉曼光谱研究乙腈在金电极上的解离吸附行为

利用共焦显微拉曼系统、结合合适的电极表面粗糙方法研究了非水体系 0 1mol/LLiClO4 /CH3CN溶液中 ,乙腈分子在金表面的吸附和解离行为。结果表明非水体系中乙腈可在金表面发生还原反应 ,产物CN- 离子与电极表面作用形成的表面配合物可在较宽的电位区间吸附于电极表面。溶液中的微量水、激光照射以及电极电位均对该反应有较大的影响。通过拉曼谱图的比较得出乙腈分子解离出的CN- 在金电极表面比在银电极表面有更强的吸附作用。     

非水体系中甲酸在铂电极上催化氧化的表面增强拉曼光谱研究

采用共焦显微拉曼系统研究了甲酸在非水体系中的纯多晶铂电极上的表面增强拉曼光谱,实验发现电位较低时甲酸首先在粗糙铂电极表面生成CO中间体,当电位逐渐变正并高于0.1 V时CO开始氧化,但是此时新生成的CO足以弥补其氧化的消耗,表现在Raman强度和一定覆盖度下的耦合作用并没有减少。当电位达到约0.6 V时CO的氧化速度进一步加剧并完全氧化为最终产物CO₂。     

基于表面增强拉曼光谱技术的金表面耐腐蚀性分析

金属表面耐腐蚀性能与其微观结构密切相关。以金为分析对象,采用不同粒径氧化铝抛光粉抛光处理金片表面,经扫描电镜和原子力显微镜观察,表明金片表面具备与实际工件类似的微观结构,在此基础上,研究金片表面微观划痕结构对表面增强拉曼散射(SERS)以及耐腐蚀性能的影响。以罗丹明B为探针分子,对不同特征尺寸的微观划痕进行SERS分析,获得了罗丹明B的SERS信号强度随划痕平均特征尺寸的变化规律。通过改变拉曼激发光偏振方向与划痕方向的夹角大小,发现SERS信号主要归因于激发光与划痕相互作用产生的横向表面等离激元。划痕平均特征尺寸在50 nm附近时,横向表面等离激元最强,之后随着划痕平均特征尺寸增加,横向表面等离激元逐渐变弱。另一方面,对具有不同特征尺寸微观划痕的金片进行电化学极化测试,获得了各样品的自腐蚀电位,发现金片的自腐蚀电位随着划痕平均特征尺寸增大而降低。结果表明,当划痕平均特征尺寸大于50 nm,金表面的SERS信号与自腐蚀电位间存在良好的线性对应关系,这为SERS技术用于工件耐蚀性分析提供了依据。通过在工件表面滴涂探针分子并使用便携式拉曼光谱仪测量有望可以对工件耐蚀性进行现场快速预判。     

Photonic nanojet‐mediated SERS technique for enhancing the Raman scattering of a few molecules

We report a two‐step enhancement of Raman scattering signal (η) of a few dye molecules. In the first step, high‐quality surface‐enhanced Raman scattering (SERS) substrates have been used. The SERS substrates were fabricated by direct current sputtering of Au followed by thermal annealing. The role of thermal annealing of the SERS substrates and numerical aperture of Raman microscopic objective lens on the enhancement has been studied for optimizing the enhancement in the SERS technique. In the second step, the value of η obtained with conventional SERS technique has been improved significantly with the help of photonic nanojet (PNJ) of an optical microsphere (PNJ‐mediated SERS technique). The signal to noise ratio and reproducibility of the experimental results have been found to be very high. Based on our theoretical simulations on PNJ, a few suitable parameters have been proposed for obtaining better enhancement using this technique. To the best of our belief, this report will enable the SERS community to improve η value with ease. Copyright © 2016 John Wiley & Sons, Ltd.     

Sensitive Raman spectroscopy of lipids based on drop deposition using DCDR and SERS

Raman spectroscopy is widely used for study of lipids and membrane models. A severe limitation of this technique lies in the low Raman cross section requiring high sample concentrations. We report sensitive detection of synthetic 1,2‐dimyristoyl‐3‐trimethylammonium‐propane (DMTAP) lipid employing two Raman techniques with improved sensitivity: drop coating deposition Raman (DCDR) and surface‐enhanced Raman scattering (SERS) spectroscopies. DCDR provided well‐reproducible DMTAP spectra without considerable loss of its solution properties if measured from the ‘coffee ring’ pattern of a drop dried on a SpectRIM^TM plate. DMTAP was detected at ~10 μM initial solution concentration, which is about three orders of magnitude lower than that for conventional Raman spectroscopy. Moreover, SERS spectra from dried ring of Ag hydrosol/DMTAP system were obtained down to ~0.3 μM DMTAP concentration, which means that sensitivity of SERS is about five orders of magnitude higher than that of conventional Raman spectroscopy. In contrast to the DCDR technique, good SERS spectra of DMTAP were obtained only from some spots of the ring containing big nanoparticle aggregates, and the structural properties of DMTAP were significantly perturbed by adsorption on the Ag nanoparticles. Copyright © 2013 John Wiley & Sons, Ltd.     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.     

金膜表面等离激元诱导邻巯基苯甲酸脱羧反应的表面增强拉曼光谱研究

贵金属纳米结构表面等离激元共振（SPR）因其广泛的用途而备受关注,它不仅可以催化某些特殊的表面反应,同时还能产生表面增强拉曼散射效应（SERS）,极大增强分子的表面拉曼信号,因此两者结合后可在纳米结构表面采用SERS光谱跟踪SPR催化反应。目前此类研究主要集中在氮氮（N═N）偶联,因此亟待拓展SPR反应种类及提高催化活性和效率。采用SERS光谱研究邻巯基苯甲酸（OMBA）分子在金纳米粒子单层膜（Au MLF）表面的脱羧行为。通过气液界面组装法制备“热点”分布均匀的金纳米粒子单层膜,以此作为基底,探讨了溶液pH值、激光功率及激光照射时长对该基底表面脱羧反应的影响。研究结果表明,吸附在Au MLF表面的OMBA分子在表面等离激元驱动下碱性和中性介质中发生脱羧基反应,生成苯硫酚（TP）,且碱性中反应活性大于中性溶液。在酸性介质中几乎不发生脱羧反应。较强的激光功率,脱羧反应的活性越高;产物SERS强度的增加与激光照射时间成线性关系,时间延长可提高脱羧反应的产率。这为拓展SPR驱动的光催化反应及深入理解其反应机理提供了实验依据。     

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。     

非水体系的表面增强拉曼光谱研究

本文主要报告了本研究小组自八十年代末至今应用SERS效应对电极/非水溶液界面现象进行研究的一些结果。研究电极从具有强SERS效应的金、银、铜等贵金属,拓宽至铁、镍、铂等过渡金属。借助非水体系SERS的特殊性,我们主要开展了非水体系中溶剂的界面特性、溶质的表面吸附及表面化学反应如C1分子在铂族金属表面的解离反应等研究。此外,对作为非水体系中无法彻底去除的水分子的表面吸附模型也进行了较详细的研究。     

FT-Surface-Enhanced Raman Scattering of Phenylalanine Using Silver-Coated Glass Fiber Filters

A simple and facile method has been developed to produce surface-enhanced Raman scattering (SERS) active surfaces. Tollen's reagent was used to coat silver onto the surface of glass fiber filters. Using a Fourier transform (FT) Raman instrument, strong surface-enhanced Raman signals have been observed for L-phenylalanine on these surfaces. The use of an FT-Raman instrument combined with this new SERS method allows for a method with both high sensitivity and selectivity. A linear dependence of the Raman signal on L-phenylalanine concentration (0.01–1.0 mM) has been demonstrated. The SERS technique presented here is both novel and promising for biochemical analysis.