金银纳米粒子的复合组装及表面增强拉曼光谱研究

采用自组装技术在硅基底上进行金银纳米粒子的混合组装, 通过控制组装溶液中金银溶胶的体积比而控制基底上金银纳米粒子的密度. SEM结果显示金银呈亚单层均匀分布, 以吡啶为探针分子, 在不同波长的激发光下研究了纯金、银以及混合组装时的SERS效应. 利用金银在不同激发线下增强效应的不同以及探针分子吸附在金银纳米粒子表面主要谱峰相对强度差别的特点, 通过一系列校正以及差谱方法研究了金银共存时SERS效应的变化, 并分离出混合体系中金的增强行为, 结果表明在金银同时组装时吡啶的SERS谱峰特征主要表现为银纳米粒子的行为, 分离出的金SERS光谱特征接近银的行为, 说明金银纳米粒子之间产生了一定的耦合作用.     

帽状铜纳米粒子的制备及表面增强拉曼散射活性研究

采用真空热蒸发法在SiO₂纳米粒子自组装单层膜上沉积铜薄膜制备了帽状铜纳米粒子。用扫描电镜、原子力显微镜和紫外-可见-近红外分光光度计对帽状复合纳米粒子的表面形貌和光学性质进行了表征。以亚甲基蓝和吡啶-(2-偶氮-4)间苯二酚为探针分子,研究了该复合纳米粒子的表面增强拉曼散射(SERS)活性。通过比较吸附在不同基底上的吡啶-(2-偶氮-4)间苯二酚的谱峰强度,探讨了SERS效应与表面等离子体共振(SPR)的关系。     

Characterization of Labeled Gold Nanoparticles for Surface-Enhanced Raman Scattering

Noble metal nanoparticles (NP) such as gold (AuNPs) and silver nanoparticles (AgNPs) can produce ultrasensitive surface-enhanced Raman scattering (SERS) signals owing to their plasmonic properties. AuNPs have been widely investigated for their biocompatibility and potential to be used in clinical diagnostics and therapeutics or combined for theranostics. In this work, labeled AuNPs in suspension were characterized in terms of size dependency of their localized surface plasmon resonance (LSPR), dynamic light scattering (DLS), and SERS activity. The study was conducted using a set of four Raman labels or reporters, i.e., small molecules with large scattering cross-section and a thiol moiety for chemisorption on the AuNP, namely 4-mercaptobenzoic acid (4-MBA), 2-naphthalenethiol (2-NT), 4-acetamidothiophenol (4-AATP), and biphenyl-4-thiol (BPT), to investigate their viability for SERS tagging of spherical AuNPs of different size in the range 5 nm to 100 nm. The results showed that, when using 785 nm laser excitation, the SERS signal increases with the increasing size of AuNP up to 60 or 80 nm. The signal is highest for BPT labelled 80 nm AuNPs followed by 4-AATP labeled 60 nm AuNPs, making BPT and 4-AATP the preferred candidates for Raman labelling of spherical gold within the range of 5 nm to 100 nm in diameter.     

Controlled Self-Assembly of Metallacycle-Bridged Gold Nanoparticles for Surface-Enhanced Raman Scattering

In this work, well-defined two-dimensional metallacycles have been successfully employed for the well-controlled self-assembly of gold nanoparticles (AuNPs) into discrete clusters such as dimers, trimers, tetramers, pentamers and even hexamers at the water–oil interface for the first time. Furthermore, the modular construction of metallacycle molecules allows precise control of spacing between the gold nanoparticles. Interestingly, it was found that interparticle spacing below 5 nm created by molecular metallacycles in the resultant discrete gold nanoparticle clusters led to a strong plasmon coupling, thus inducing great field enhancement inside the gap between the NPs. More importantly, different discrete clusters with precise interparticle spacing provide a well-defined system for studying the hot-spot phenomenon in surface-enhanced Raman scattering (SERS); this revealed that the SERS effects were closely related to the interparticle spacing.     

Ag Nanoparticles Decorated CuO@RF Core-Shell Nanowires for High-Performance Surface-Enhanced Raman Spectroscopy Application

Vertical-aligned CuO nanowires have been directly fabricated on Cu foil through a facile thermal oxidation process by a hotplate at 550 °C for 6 h under ambient conditions. The intermediate layer of resorcinol–formaldehyde (RF) and silver (Ag) nanoparticles can be sequentially deposited on Cu nanowires to form CuO@RF@Ag core-shell nanowires by a two-step wet chemical approach. The appropriate resorcinol weight and silver nitrate concentration can be favorable to grow the CuO@RF@Ag nanowires with higher surface-enhanced Raman scattering (SERS) enhancement for detecting rhodamine 6G (R6G) molecules. Compared with CuO@Ag nanowires grown by ion sputtering, CuO@RF@Ag nanowires exhibited a higher SERS enhancement factor of 5.33 × 10⁸ and a lower detection limit (10⁻¹² M) for detecting R6G molecules. This result is ascribed to the CuO@RF@Ag nanowires with higher-density hot spots and surface-active sites for enhanced high SERS enhancement, good reproducibility, and uniformity. Furthermore, the CuO@RF@Ag nanowires can also reveal a high-sensitivity SERS-active substrate for detecting amoxicillin (10⁻¹⁰ M) and 5-fluorouracil (10⁻⁷ M). CuO@RF@Ag nanowires exhibit a simple fabrication process, high SERS sensitivity, high reproducibility, high uniformity, and low detection limit, which are helpful for the practical application of SERS in different fields.     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼（SERS）性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼(SERS)性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

Au@PVP核壳纳米粒子作为表面增强拉曼散射基底检测孔雀石绿

采用水热法合成了粒径均一、壳层厚度可控的Au@PVP核壳纳米粒子,利用壳层PVP分子分散纳米粒子的特性,使其形成均一、排列致密的单层结构,利用其内核金纳米粒子的等离子共振效应实现了孔雀石绿( MG)分子的表面增强拉曼检测。通过优化吸附时间与壳层厚度,在致密的、均匀的核壳纳米粒子表面增强拉曼散射(SERS)基底上实现MG分子高灵敏分析检测,检测线性范围1×10-10~1×10-5 mol/L,线性相关系数R2达到0.98,检出限可达1×10-12 mol/L。将本方法用于罗非鱼鱼肉中MG含量检测,样品未检出,样品加标回收率为70.8％~126.0％。结果表明,本方法快速准确、操作简单,可用于鱼肉中MG的快速检测。     

多晶铂电极表面硫吸附物种的原位表面增强拉曼光谱研究(英文)

本工作首次报道了在酸性或碱性电解质中高粗糙度多晶铂电极表面硫物种的吸附、电氧化过程的原位表面增强拉曼光谱研究.分别在两种情况下采集了粗糙铂电极的表面增强拉曼光谱:(a)循环伏安处理后控制一定电位(0.2V)下;(b)逐步控制不同电位.酸性电解质条件下,两种情况均观察到位于300cm-1的Pt—S振动.Pt—S键较强,阻止了氢在铂电极表面的吸附,需多次循环伏安处理才能完全将表面吸附的硫去除.同时还观察到位于470cm-1处的少量多聚S物种(S8或者其他类型).这些多聚S物种仅仅微弱地键合在铂电极的表面,可以容易地除去.在碱性电解质中,同样也在(a)和(b)情况下观察到位于310cm-1的Pt—S振动吸收.本工作了获得了有关硫在粗糙多晶铂电极表面吸附和电氧化重要信息,证明了原位表面增强拉曼光谱在研究铂表面的适用性.     

氧化石墨烯/金银纳米粒子复合材料的制备及其SERS效应研究

近年来,氧化石墨烯/金银纳米粒子复合材料由于其优异的表面增强拉曼散射（SERS）性能引起了人们极大的关注,在污染物检测、化学传感和癌症诊断等领域具有重要的应用价值。本文综述了氧化石墨烯片层上修饰金银纳米粒子、氧化石墨烯包覆金银纳米粒子、氧化石墨烯附着在金银纳米粒子层三种氧化石墨烯/金银纳米粒子复合材料的制备方法,对其SERS效应进行了详细介绍。SERS研究表明,结合了金银纳米粒子与氧化石墨烯两种材料各自在SERS研究与应用中的优势,氧化石墨烯/金银纳米粒子复合材料的SERS性能比单纯金银纳米粒子更加优异。氧化石墨烯在其中起到了化学增强、分子富集、钝化保护、荧光猝灭的重要作用。氧化石墨烯/金银纳米粒子复合材料在表面增强拉曼光谱中具有广阔的应用前景。     

Surface-Enhanced Raman Scattering of Benzoic and Thiosalicylic Acids Adsorbed on Fine Ag Particle-Impregnated Cellulose Gel Films

Cellulose acetate gel film impregnated with fine Ag particles has been prepared by a counter diffusion method. Surface-enhanced Raman scattering (SERS) of benzoic and thiosalicylic acids was observed using the impregnated films. It seems likely that these acids adsorb dissociatively on the surface of impregnated films. The impregnated film can be used as a highly sensitive substrate for Raman scattering.     

金@银核壳纳米粒子的制备和形貌的精确控制及其表面增强拉曼光谱性能

用种子生长法制备了金@银核壳结构的纳米粒子。在制备过程中通过控制氯金酸的浓度和硝酸银的体积,得到了不同粒径的金核和不同厚度的银壳构成的核壳纳米粒子。从而得到了具有不同SERS性能的金@银核壳纳米粒子。选取具有最佳SERS性能的金@银核壳纳米粒子实现了对罗丹明6G的微量检测。     

金@银核壳纳米粒子的制备和形貌的精确控制及其表面增强拉曼光谱性能

用种子生长法制备了金@银核壳结构的纳米粒子。在制备过程中通过控制氯金酸的浓度和硝酸银的体积,得到了不同粒径的金核和不同厚度的银壳构成的核壳纳米粒子。从而得到了具有不同SERS性能的金@银核壳纳米粒子。并选取具有最佳SERS性能的金@银核壳纳米粒子实现了对罗丹明6G的微量检测。     

牛血红蛋白与银纳米粒子相互作用的光谱研究

运用紫外-可见吸收光谱(UV-Vis)、荧光光谱、同步荧光光谱、圆二色光谱(CD)及傅立叶变换红外光谱(FTIR)等手段, 研究牛血红蛋白(Bovine Hemoglobin, 简称BHb)与银纳米粒子的相互作用. 结果表明, BHb能吸附在银纳米粒子的表面, 使其415 nm处的特征等离子体共振吸收峰强度下降, 峰位红移. 随银纳米粒子的浓度增大, BHb分子中Soret带的吸收持续降低, 说明银纳米粒子可能使部分血红素辅基从它们的键腔中脱离出来. Stern-Volmer方程分析表明, 银纳米粒子静态猝灭BHb的内源荧光. 由UV-Vis和荧光光谱的变化, 计算BHb与银纳米粒子的结合常数, 其数量级达到10⁹～10¹⁰. 同步荧光光谱的蓝移说明, 银纳米粒子扰动BHb分子内部的酪氨酸、色氨酸残基所处的微环境, 使之包埋于疏水腔中. 拟合计算远紫外CD数据发现, 银纳米粒子诱导BHb产生轻微的二级结构改变, α-螺旋含量降低. FTIR光谱结果提示, BHb中半胱氨酸残基的硫、羧基氧、酰胺及氨基酸残基中的氮原子与银纳米粒子可能有表面键合作用.     

Au/Ag核-壳结构纳米粒子的制备及其SERS效应

随着大量有关表面增强拉曼散射 (SERS)的实验和理论研究的开展 ,金属纳米粒子作为一类重要的 SERS增强介质 ,已引起了人们浓厚的研究兴趣 [1] .而 Au和 Ag作为最常用的活性基底物质 ,更是研究的热点 [2 ,3 ] .最近 ,美国印第安那大学的 Nie等 [4 ] 在单个银纳米粒子上 ,观察到高达 1 0 14 ～ 1 0 15的SERS因子 .同时 ,他们的另外一项工作表明银纳米粒子的形状和大小对 SERS活性有很大影响 [5] .但是 ,由于 Ag溶胶制备的重复性较差 ,且粒度分布不均匀 ,通过控制银颗粒大小而调控 SERS活性是相当困难的[6] .与 Ag相比 ,Au在可见光…     

Replacement of Poly(vinyl pyrrolidone) by Thiols: A Systematic Study of Ag Nanocube Functionalization by Surface-Enhanced Raman Scattering

In this work, we used surface-enhanced Raman scattering (SERS) to monitor the replacement of poly(vinyl pyrrolidone) (PVP) on Ag nanocubes by cysteamine, thiol-terminated PEG, and benzenedithiol. PVP is widely used as a colloidal stabilizer and capping agent to control the shape of Ag (as well as many other noble metals) nanocrystals during synthesis, and to stabilize the final colloidal suspension. However, the surface chemistry of Ag nanocrystals often needs to be tailored for specific applications, so the PVP coating must be removed and/or replaced by other ligands. By monitoring the signature peak from the carbonyl groups of PVP, we show, for the first time, that the PVP adsorbed on the surface of Ag nanocubes was completely replaced by the thiol molecules at room temperature over the course of a few hours. We observed the same trend no matter if the Ag nanocubes were suspended in an aqueous solution of the thiol or supported on a silicon substrate and then immersed in the thiol solution.     

耐尔蓝A在银溶胶上的表面增强拉曼光谱特征

研究了在不同耐尔蓝Ａ浓度，银溶胶，激发波长和ｐＨ值以及碘离子存在下，耐尔蓝Ａ在银溶胶上的表面增强拉曼光谱特征。     

应用于基因分析的最新SERS技术*

表面增强拉曼散射（SERS）是一种基于拉曼散射原理识别生物及化学分子的分析方法。SERS具有灵敏度高、水干扰小、分辨率高、稳定性好等优点,广泛应用于生物分析和生物医学研究领域。近年来,SERS技术在基因分析领域得到迅速的发展,成为国内外研究的热点。本文对应用于基因分析的一些最新SERS技术（包括基因的免标记检测和标记检测）进行较为全面的综述,着重介绍了免标记检测中基于金属纳米粒子和针尖增强拉曼散射的SERS技术,标记检测中基于拉曼活性物、PCR技术、分子信标、基底和标记物的SERS信号放大技术,并概括了基因多组分检测技术及SERS技术的应用前景。     

蜂窝状Ag纳米颗粒膜制备及应用于表面增强拉曼散射基底

通过静态呼吸图法制备了具有高度有序微结构的聚苯乙烯-嵌段-聚4-乙烯吡啶共聚物(PS-b-P4VP)膜。以该嵌段共聚物膜为模板,可制得金属纳米粒子阵列。借助光化学还原途径制得了具有蜂窝状微结构的Ag纳米颗粒膜。以罗丹明6G(R6G)为探针分子,考察了蜂窝状Ag纳米颗粒膜用作表面增强拉曼散射(SERS)基底的性能。蜂窝状Ag纳米颗粒膜对R6G分子的表面拉曼散射增强因子高达1.31×10~9。另外,该SERS基底还显示了较低的检测限,检测限低至10~(-10)mol·L~(-1)。拉曼信号面扫显示了基底很好的信号均匀性。在此SERS基底上30μm×30μm范围内随机收集的120个拉曼信号强度的相对标准偏差仅为～12%。     

Self-Assembled Monolayers of Organoselenium Compounds on Gold: Surface-Enhanced Raman Scattering Study

To understand the binding nature of organoselenium compounds on gold, we have examined the adsorption behavior of several representative organoselenium compounds, i.e., benzeneselenol (BSe), diphenyl diselenide, dibenzyl diselenide, dioctyl diselenide, and benzyl phenyl selenide (BPSe) on the Au surface by virtue of surface-enhanced Raman spectroscopy (SERS). BSe chemisorbs on gold as selenolate with a tilted orientation. Upon adsorption, the Se–Se bonds of diselenides are cleaved to form selenolates, analogous to the formation of thiolate monolayers from disulfides. BPSe adsorbs on gold without any C–Se bond scission. The benzyl moiety of BPSe assumes a rather vertical stance while the phenyl moiety is more tilted to the gold surface.