SERS活性表面荧光增强或淬灭的机制研究

利用银胶和银镜两种SERS活性表面,对吸附分子的荧光增强或淬灭机制进行了实验和理论研究.结果表明,荧光增强或淬灭主要取决于局域电磁场增强和分子到金属表面无辐射能量转移过程的竞争效应.当满足吸收共振增强和辐射共振增强时,荧光被增强,反之荧光被淬灭.荧光增强最大一般只为10—10²倍,远小于喇曼截面的增强. 关键词：     

研究界面多相吸附动力学的一个新方法——表面增强喇曼散射方法

提出利用表面增强喇曼散射(SERS)效应研究化学吸附动力学,给出了理论模型和实验方法。研究了结晶紫(CV)和对氨基苯甲酸(PABA)在银镜及银胶表面吸附。发现在银镜和银胶表面上,CV的吸附是匀相的,PABA则是多相的;表面形态的差异不影响表面多相因子和脱附速率常数(K_d=0),只对吸附速率常数有影响。讨论了表面多相因子的意义。 关键词：     

对氨基苯甲酸分子在银表面多相吸附及氯离子影响的SERS研究

研究对氨基苯甲酸(PABA)在银表面上的吸附动力学过程以及氯离子对其的影响,发现PABA在银表面上呈多相吸附。与匀相吸附的情况相似,表面形态的差异较大地改变吸附速率常数,而对多相因子的影响不明显。氯离子的竞争吸附改变PABA吸附的多相性质,随着氯离子浓度的增加,PABA分子从多相吸附逐渐转变为匀相吸附。根据吸附等温线估算了PABA的吸附能,U≈-9.6kJ/mol。结果分析进一步证实:化学吸附时多相吸附意味着表面上存在非单一的吸附形式。 关键词：     

Surface Enhanced Raman Scattering on Self-assembled Nano Silver Film Prepared by Electrolysis Method

用一种廉价的电解方法制备了纳米银膜,并详细研究了在这种银膜上的表面增强拉曼散射效果．结晶紫为本实验的检测性分子．通过实验发现,这种银膜用便携式拉曼光谱仪测试并计算出的表面增强拉曼散射的增强因子为603,并对结晶紫的最小检出限为0.1 nmol/L     

SERS studies of 1-butylaminoanthraquinone in silver sol

SERS studies of 1-butylaminoanthraquinone in silver sol have been made to understand the nature of adsorption. The enhancement mechanism is explained on the basis of charge transfer process. The molecule is adsorbed through the binding sites but not flat on to the surface.     

Surface-enhanced Raman scattering and DFT theoretical studies on the adsorption behavior of plumbagin on silver nanoparticles

The comparative study of normal Raman spectrum with the SERS along with the DFT calculations predicts the adsorption geometry of plumbagin on silver surface. The surface geometry of plumbagin molecule was studied by analysis of the SERS spectra adsorbed on silver colloid surfaces. The large enhancement of inplane ring stretching and C-H in-plane bending modes in the surface-enhanced Raman scattering spectrum indicates that the molecule is adsorbed on the silver surface in a stand-on orientation of PLBN on a silver surface.     

银微粒表面吸附若丹明B分子荧光增强和淬灭的研究

研究了若丹明B分子的530.0和572.0nm两个荧光峰在银微粒表面的增强和淬灭效应,发现若丹明B分子的530.0nm荧光峰获得了30倍的增强,而与此同时,572.5nm荧光峰则强烈淬灭。对其快速动力学过程的研究表明,这两个荧光峰的增强和淬灭过程在每一时刻都是互逆的。 关键词：     

A STUDY ON SURFACE-ENHANCED HYPER-RAMAN SCATTERING OF BASIC FUCHSIN ADSORBED ON THE SILVER COLLOID

This paper presents the surface-enhanced hyper-Raman scattering (SEHRS) effect of basic fuchsin (BF) adsorbed on the silver colloid. On the basis of the absorption spectra, a new absorption band at 1000nm has been observed in the case of BF adsorption on the silver colloid, The result indicates that surface electromagnetic enhancement also appears at the incident photon frequency in the near-IR region, which plays an important role in the SEHRS signals. The electromagnetic enhancement factor (2.0×l0⁴) is estimated by using electromagnetic model. Additionally, surface-enhanced second-harmonic generation (SHG) effect in the cases of pure silver colloid, silver colloid plus adsorbed molecule and KCl solution has been detected.     

Adsorption of aniline on silver mirror studied by surface‐enhanced Raman scattering spectroscopy and density functional theory calculations

The adsorption of aniline on a silver mirror was studied by surface‐enhanced Raman scattering (SERS) spectroscopy and density functional theory (DFT) calculation methods. The normal Raman and SERS spectra of pure aniline liquid and its solutions were recorded by a micro‐Raman spectrometer with excitation at 514.5 nm. Orientation of the aniline molecule adsorbed on the Ag mirror is discussed. The results indicate that pure aniline is adsorbed on the surface of the Ag mirror with a tilted orientation. The conformer with the nitrogen atom interacting with the metal surface would be dominant. DFT calculations further confirm the experimental results that charge transfer (CT) takes place from the highest occupied molecular orbital(HOMO) of aniline to the singly occupied molecular orbital (SOMO) of the silver surface. In this paper, the frontier molecular orbital theory has been successfully used to explore the interaction between the aniline molecule and the silver surface. Copyright © 2011 John Wiley & Sons, Ltd.     

KCI对银胶形态影响的电子显微镜研究

借助透射电子显微镜研究了银胶中加入KCl时对银胶的影响。发现KCl的加入引起了银原子的输运,使胶体颗粒变大,表面上覆上一层疏松原子集团。同时引起胶体发生链状凝聚。和加入吡啶引起的银胶的变化做了比较,表明KCl和吡啶对银胶的作用结果有很大差异。同时也讨论了这些差异对表面增强喇曼散射信号的影响。 关键词：     

Study on Adsorption States by Surface-Enhanced Raman Spectroscopy

Abstract

SERS has been used as a state-resolving probe to study the adsorption states. in the case of pyridine (Py) adsorbed on the Ag electrode surface, the equilibrium and transition between two adsorbed states, i.e., the perpendicular mode adsorbed through the nitrogen lone-pair electrons and the flat mode through the π electrons of the aromatic ring, were studied. It was found that in the low pyridine concentration or the initial stage of adsorption, the flat mode was favored. While the concentration became higher and the adsorption tended to equilibrium, the adsorbed molecules would transit to the perpendicular mode. The similar phenomenon was also observed when changing the applied electric potential and the pH value of the solution. In the case of the adsorption of Methylene Blue (MB) on the HNO₃-etched silver surface, the influence of Cl^? ions on the adsorption states of MB was investigated. It showed that MB molecules adsorbed on the silver surface tended to transform from the “lying-down” state to the “end-on” state while adding Cl^? ions.     

酸性条件下染料结晶紫分子的近红外表面增强拉曼散射研究

比较了染料分子结晶紫(CV)在酸性与中性条件下的金胶体系中的近红外表面增强拉曼光谱(NIR-SERS)。结果表明,结晶紫分子-金胶体系中结晶紫分子在1064nm近红外光激发条件下,其荧光得以大大淬灭,同时拉曼得到了至少不低于105倍的增强;当进一步加入硝酸使得其处于酸性气氛下时,由于部分结晶紫分子与硝酸发生了化学作用形成了结晶紫分子的单替代衍生物(HCV),而HCV与结晶紫分子相比,更容易吸附在金属表面,因此结晶紫分子NIR-SERS还将有很大的增强。这可以给我们很大的启示:改变体系的酸碱度也可以达到改变其SERS的增强效果的目的。     

二硫化四甲基秋兰姆的表面增强拉曼光谱研究

制备了两种简单常用的具有表面增强拉曼(SERS)活性的银基底—银镜和硝酸刻蚀银箔,并应用于二硫化四甲基秋兰姆(福美双)的检测及其结构变化的分析。SERS技术提供了不同浓度下的二硫化四甲基秋兰姆分子的振动信息,发现当其与金属银基底作用后,二硫键断裂,并且通过化学作用吸附在银基底表面。通过分析不同浓度福美双分子吸附在银表面的拉曼光谱,证明其在金属表面存在两种吸附方式即表现为单齿形和双齿形两种几何形状。这些光谱及结构信息有助于理解和检测自然环境中二硫化四甲基秋兰姆及其分解产物。同时也对二硫代氨基甲酸盐类化合物的研究有一定的借鉴意义。     

维生素K3的表面增强拉曼光谱研究

首次报道了维生素K3 (VK3 )分子的常规拉曼光谱 (NRS)及该分子在活性衬底银镜上的表面增强拉曼散射 (SERS) ,并对它的拉曼特征谱带进行了初步的指认和归属。通过对比VK3 的常规拉曼光谱和SERS谱 ,发现VK3 分子吸附在银表面后拉曼散射强度被大大增强了。另外 ,VK3 的羰基与银粒子发生电荷转移后形成负离子自由基 ,碳氧双键打开。受VK3 分子吸附在银镜表面的影响 ,萘环结构发生了很大的扰动 ,导致一些拉曼特征峰产生位移 ,环变形振动对应的拉曼散射强度得到了增强。这些研究结果为SERS技术今后对VK3进行药物检测以及痕量分析方面的应用提供了依据。     

Entropic effects in diffusion-adsorption processes in micropores

We analyze the kinetics of diffusion-adsorption processes of one component systems in micropores. In realistic situations, the pores exhibit irregular forms which give rise to inhomogeneous adsorption with preferred sites for the adsorbing particles. By modeling the tortuosity of the pores by means of entropic barriers, we obtain a kinetic equation for the averaged concentration of particles along the pore and on its surface. The analysis performed yields expressions for the adsorption rate, the effective diffusion coeffcient, the adsorption isotherms and the concentration of the adsorbed particles. It is shown that this last quantity strongly depends on the form of the pore. This feature opens the possibility to design micropores with an optimal adsorption rate at selected sites. Our results show that to consider the geometry of the pore in the reaction-diffusion scheme is crucial to reproduce experimental observations of the concentration of adsorbed particles in micropores.     

The influence of pH and anions on the adsorption mechanism of rifampicin on silver colloids

The influence of pH and anions on the adsorption mechanism of rifampicin on colloidal silver nanoparticles has been analysed by electronic absorption, resonance Raman (RR) and surface‐enhanced resonance Raman spectroscopy (SERRS). Rifampicin is a widely used antibiotic with a zwitterionic nature. SERRS spectra of rifampicin adsorbed on silver sols, prepared using hydroxylamine hydrochloride as reducing agent, undergo dramatic changes upon lowering the pH. The spectral form changes progressively from that characteristic of chemisorbed rifampicin (at pH > 7) to one very similar to the rifampicin RR spectrum (at lower pH), indicative of a modification of the adsorption mechanism on the surface of the Ag nanoparticles. The RR‐type SERRS spectrum is proposed to result from formation of an ion pair between rifampicin and Cl⁻ anions, which, deriving from the colloid preparation, are adsorbed on the Ag surface. The addition of anions to the hydroxylamine hydrochloride sol facilitates conversion from the chemisorbed to ion pair form and leads to an order of magnitude increase in the SERRS signal. Copyright © 2007 John Wiley & Sons, Ltd.     

2-氨基苯硫酚NIR-SERS光谱及其在纳米银表面吸附行为分析

本文采用静电自组装的方法制备了二维纳米银膜。UV-vis吸收光谱显示其等离子体共振吸收带位于400+900nm的光谱范围,延伸到了近红外区,可以较好的匹配785nm的近红外激发光源。以该纳米银膜为基底,对2-氨基苯硫酚(2-ATP)分子进行了近红外表面增强拉曼散射(NIR-SERS)检测,获得了重复性良好的NIR-SERS光谱图。实验表明:以2-ATP为探针分子时,该纳米银膜的NIR-SERS增强因子达到2.19×109。同时,本文采用密度泛函理论(DFT),以B3LYP/6-31G为基函数,对2-ATP分子进行结构优化和普通拉曼光谱(NR)计算,发现理论值和实验值吻合较好。此外,对2-ATP的NIR-SERS谱带进行了归属分析,发现当2-ATP分子在纳米银表面吸附时,是以-SH基团吸附到银表面,且同时-SH基团会被纳米银氧化。     

Surface enhanced infrared spectral investigation of 2,3-bis(chloromethyl)anthracene-1,4,9,10-tetraone on silver nanoparticles

The size effect of silver nanoparticles on photophysical properties of 2,3-bis(chloromethyl)anthracene-1,4,9,10-tetraone (BCMAT) has been investigated using an IR technique. Silver colloids of different sizes have been prepared by two different methods. Mechanisms for adsorption and complex formation have been elucidated from surface-enhanced infrared absorption spectra. The observation shows that BCMAT is adsorbed on silver nanoparticles through a C = O group and that its orientation is stand-on. Surface enhancement factors have been calculated. As the particles decrease in size their total surface area grows, which leads to the gain in the enhancement factor.     

Diffusion-influenced reactions

We summarize three of our recent results on diffusion-influenced reactions in solutions. All deal with the concentration dependence of the reaction rate when the reactants must first diffuse together before reaction can occur. When one species (the sink species) is not dilute, the rate cannot be obtained by solution of a pair diffusion equation; the correlations among the sinks for the diffusing species must be accounted for. First, we consider fluorescence quenching when the quenchers are not dilute. For charged quenchers and fluorophores we discuss how the solution dielectric constant and ionic strength can strongly influence the deviations from the linear Stern-Volmer behavior (the dilute sink result) which arise due to the sink correlations. Second, we consider heterogeneous catalysis where a reactive species is adsorbed onto a surface and must surface diffuse to reactive sites (the sinks). We find that surface diffusion can be an important factor contributing to the rate of reaction; especially when surface diffusion is rapid relative to the adsorption/desorption rate. Third, we discuss diffusion influenced reactions with sinks which are long ellipsoids. Dilute long ellipsoids provide a large rate enhancement relative to a spherical sink; we show that this rate enhancement survives when nondilute ellipsoids are considered.     

L-天冬氨酸在银胶体中吸附状态的表面增强拉曼光谱研究

利用表面增强拉曼光谱 (Surface EnhancedRamanScattering,SERS)研究了L 天冬氨酸在银溶胶体中的吸附状态及其浓度变化对表面增强拉曼散射效应的影响 ,并探讨了L 天冬氨酸在银溶胶表面的吸附作用特点和规律。实验结果表明 ,L 天冬氨酸在银溶胶中有明显的SERS信号 ,经过分析表明 ,该化合物能够吸附在银表面 ,这种吸附是通过羧基和氨基中的氮原子与银结合来实现的 ,L 天冬氨酸分子中带有负电荷的羧基和氨基中带有孤对电子的氮原子都能与银原子配位 ,其中羧基在银表面的增强为电荷转移机制增强 ,具有化学吸附的特征 ;氨基在银表面的增强为电磁场增强机制 ,为物理吸附。而且SERS强度随着L 天冬氨酸浓度的变化而改变 ,当其浓度为 10 - 3mol·L- 1 时增强效果较好 ,当浓度降低 ,增强作用也逐步变弱