苯甲酸、邻羟基苯甲酸和对羟基苯甲酸在银胶粒中的表面增强喇曼散射

在银胶体中进行了苯甲酸、邻羟基苯甲酸(又名水扬酸)和对羟基苯甲酸的表面增强喇曼散射。得到并分析了这三种分子的增强喇曼谱。这三个分子都含有ν(C—CO₂^-)伸缩振动。水扬酸和对羟基苯甲酸是同分异构体,都含有ν(C—OH)伸缩振动,但处于不同位置上。借此我们分析了相对于表面不同距离和不同取向下的增强因子变化,并与纯电磁理论的球形颗粒模型进行了比较。发现了明显的分歧,讨论了可能的原因。还讨论了凝聚对增强因子的影响,并提出了控制胶体凝聚的可能途径。 关键词：     

KCl对表面增强喇曼光谱系统中分子吸附取向的影响

本文从实验上测量表面增强喇曼光谱(SERS)系统中掺入KCl后分子特征喇曼峰相对强度的变化,由此进一步分析分子在表面上吸附取向的变化。 关键词：     

氯离子对银胶中表面增强喇曼散射效应的影响

讨论氯离子对银胶体系中对氨基苯甲酸(PABA)和吡啶(pyr)的表面增强喇曼散射(SERS)效应的影响。观察PABA在银胶中的SERS,氯离子的影响以及SERS强度-时间关系。发现氯离子的竞争吸附破坏PABA分子的类固相吸附并伴随着分子吸附状态的改变,从而导致SERS强度的减弱。研究PABA/银胶与pyr/银胶混合后添加氯离子的影响。同时观察氯离子对银胶中PABA和pyr光吸收的影响。发现氯离子对银胶中SERS的影响主要是化学增强。     

KCl中FH(CN)-的吸收、发射光谱及e-v能量转换机理研究

以扩展离子处理方法(SLC)从理论上研究了KCl中F_H(CN)^-缺陷中心的基态和激发态的特性,理论计算值与F_H(CN)^-在KCl中的吸收、发射光谱的实验值符合得很好。计算了(CN)^-分子在KCl中的本征振动频率,解释了F_H(CN)^-的振动荧光光谱及相应的Raman谱,指出Raman振动谱中峰的劈裂应该来源于(CN)^-分子在KCl中的 关键词：     

草酰氯的激光诱导荧光激发谱

本文报道草酰氯C₂O₂Cl₂在358—372.5nm范围的激光诱导荧光(LIF)激发谱。对60多条振动谱带进行了归属,其中24条是吸收光谱中没有的。由振动结构得到C₂O₂Cl₂分子在X基态和?激发态的部分振动频率,其中v＂₇=84cm^-1和v＇₇=164cm^-1是新的数据。对4₀¹振动带的转动结构的分析给出转动常数A=0.190cm^-1,B=0.114cm^-1,C=0.048cm^-1。 关键词：     

TiO2几何和电子结构调制用于超灵敏SERS传感

半导体表面增强拉曼散射(SERS)材料由于其低成本、高化学稳定性、生物相容性、结构多样性和可控性而备受关注。它们被认为是在实际应用中替代贵金属SERS基板的良好候选者。然而,半导体SERS基底的实际应用受到其低灵敏度和发展滞后的极大阻碍。最近我们研究小组提出了一种利用稀土元素镱(Yb)掺杂制备半导体TiO₂基底材料,这种方法可以实现对二氧化钛的几何和电子结构调制,并且获得了对4-巯基苯甲酸(4-MBA)分子极大的SERS增强。相较于未掺杂的TiO₂, Yb-TiO₂表现出更加优良的SERS增强效果,根据Lombardi等提出的半导体SERS增强理论,增强是通过PICT机制中的Herzberg-Teller耦合,取决于吸附分子和基底能级匹配的程度。     

吡啶,苯甲酸共存体系在Ag溶胶表面上的SERS研究

本文研究了吡啶、苯甲酸共吸附在Ag溶胶表面上的SERS谱,发现吡啶、苯甲酸加入顺序的不同对体系的SERS谱的影响不大,且苯甲酸的SERS谱相对强度大于吡啶的相对强度,说明苯甲酸的吸附能力强于吡啶。SERS谱中吡啶的环呼吸振动谱带从正常拉曼谱中的991cm~(-1)位移至1008cm~(-1),并且少量加入苯甲酸对环呼吸振动有进一步的影响,据此定性地讨论了吡啶的吸附取向。     

苯甲酸和对羟基苯甲酸与Cl~-在银表面上吸附竞争的SERS研究

对Cl~-在银胶体系中与苯甲酸(C_6H,COOH)和对羟基苯甲酸(HOC_6H_4COOH)在银表面上的相互作用和吸附竞争进行了研究,证实了Cl~-对上述两类分子的SERS信号增强具有明显的淬灭效应.1640cm~(-1)振动所反映的Cl~-存在前后—COO~-与银表面相互作用强弱的变化,证实了Cl~-促使分子从银表面脱附这一过程的存在.同时对—OH在其中的影响作了讨论.     

固-液系统中表面增强喇曼散射强度ISERS对浓度c的依赖关系及水杨酸分子的吸附等温特性研究

在恒定温度下,通过测量不同浓度溶液中吸附在Ag镜表面水杨酸分子(SA)的表面增强喇曼散射(SEKS)强度(I_SERS,对固-液系统中吸附在Ag镜表面上SA分子的I_SERS对溶液浓度的依赖关系进行实验研究,并对I_SERS与吸附分子数N^s的关系进行分析讨论。实验研究和理论分析的结果表明:利用SERS技术通过测量I_SERS与溶液浓度c的依赖关系,可为固-液系统中分子在固体表面的吸附过程及吸附特性研究提供 关键词：     

n-羟基苯甲酸(n=p,m,o)在一种新的活性基底上的SERS研究(英文)

将银纳米颗粒覆盖在覆有铟锡氧化物的导电玻璃上,可以将其作为一种新型的表面增强拉曼散射(SERS)活性基底。将三种羟基苯甲酸分子作为探针分子在这种新的基底上进行检测,得到了很好的SERS信号,从中可反映出大量分子振动信息     

SURFACE-ENHANCED RAMAN SCATTERING STUDY ON NON-ACTIVITY OF Ag-Cl CLUSTERS

The non-active mechanism of Ag-Cl clusters in surface-enhanced Raman scattering (SERS) was discussed on the basis of the study of the interaction and adsorption competition of chlorions with a series of compounds: benzoic acid, p-hydroxybenzoic acid, and m-hydroxybenzoic acid on silver surface. As a result of the addition of chlorions, the SERS signals of these molecules were sharply and rapidly reduced and quenched in intensity. The change of Raman bands at 1644 cm^-1 for benzoic acid, and at 1636 cm^-1 for p-hydroxybenzoic acid and m-hydroxybenzoic acid, before and after the addition of chlorions, indicated the desorption process of these adsorbed molecules, and the adsorption behavior of the molecules remaining adsorbed on the silver surface.     

Quenching and enhancing of SERS of methyl orange after the addition of chlorine and nitrate anions

The influence of Cl⁻ and NO₃⁻ anions on surface enhanced Raman scattering (SERS) of methyl orange adsorbed on “chemical pure” silver colloids was studied. It was found that NO₃⁻ could give rise to a large enhancement of SERS of methyl orange, while Cl⁻ could obviously weaken the SERS intensity of this molecule. Both quenching and enhancing effects were discussed and compared with each other. It indicated the coadsorbed process of these adsorbed species, and different adsorption behaviors of the molecules on silver surface directly resulted in the difference. In addition, the results of TEM pictures and UV-visible spectral experiments have also confirmed the conclusion above.     

温度对苯甲酸衍生物在银胶体系中的SERS的影响

本文报道了温度对银胶体系中的苯甲酸衍生物(PHBA,MHBA,SA)水溶液的表面增强拉曼散射(SERS)的影响。将苯甲酸衍生物水溶液与银溶胶混合后加热至沸腾,再冷却至室温(20℃左右)后测得SERS谱。将其与未加热混合液的SERS谱相比较发现这些分子加热前后的SERS谱中存在许多明显的差异。这种差异可能来自于苯甲酸衍生物在银胶颗粒表面的吸附方式的变化以及吸附的分子与溶液中残留的柠檬酸根在加热作用下发生的相互影响共同作用的结果。     

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.     

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：     

Adjustment and control of SERS activity of metal substrates by pressure

Metal pellets of silver and copper for surface‐enhanced Raman scattering (SERS) spectroscopy were prepared by compression with different pressures. It was found that the SERS activity of the pellet could be controlled by pressure. Enhanced Raman scattering properties of the metal pellets in the presence of adsorbed 4‐mercaptobenzoic acid (4‐MBA) with excitation at 632.8 or 514 nm could be obtained by choosing proper pressure of pellatization. The SERS peak intensity of the band at ∼1584 cm⁻¹ of 4‐MBA adsorbed on the metal pellets varies as a function of applied pressure, and which is about 1.2–32 times greater than when it is adsorbed on silver and copper particles. The calculated results of three‐dimensional finite‐difference time‐domain method (3D‐FDTD) are in good agreement with the experimental data. Moreover, no spurious peaks appear in the SERS spectra of the samples because no other chemicals are involved in the simple preparation process of the metal pellets, which will facilitate its use as an SERS‐active substrate for analytical purposes. In summary, SERS‐active metal pellets can be produced simply and cost effectively by the method reported here, and this method is expected to be utilized in the development of SERS‐based analytical devices. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of indium–silver bimetallic nanocomposites for surface-enhanced Raman scattering

We report on the synthesis of indium–silver bimetallic nanocomposites by chemical reduction method under atmospheric condition and their activity for surface-enhanced Raman scattering (SERS). It is found that the indium–silver bimetallic nanocomposites have better SERS activity with larger enhancement factors (EF) than pure silver nanoparticles with similar size. The SERS EF can reach 10⁷ for 4-mercaptobenzoic acid and 10⁹ for crystal violet and rhodamine 6G adsorbed on the nanocomposites and the detection limits can be at least down to 10^?7 and 10^?10 M, respectively. The results demonstrate that the indium–silver bimetallic nanocomposites are promising as SERS substrate for a myriad of chemical and biological sensing applications.     

负电性纳米银溶胶SERS活性及稳定性的比较研究

用单宁还原硝酸银可制得表面带负电的、对阳离子型分子具有较强SERS效应的纳米银。为了进一步测试负电性纳米银溶胶的SERS活性及稳定性,在室温下用制针剂的封装机将样品(old NCS)封装并保存。两年后与新制备的负电性纳米银溶胶(new NCS)比较,用透射电镜观测发现old NCS与new NCS相比银粒子尺寸增大;用紫外可见吸收光谱测定old NCS的吸收峰为431 nm,new NCS的吸收峰为418 nm,old NCS与new NCS相比吸收峰发生红移。为比较old NCS及new NCS的SERS活性选取阳离子型分子、中性分子及阴离子型分子作为测试分子,用拉曼光谱仪测试这些分子在两种纳米银上的SERS谱,结果发现,阳离子型分子碱性品红、中性分子吖啶橙在old NCS及new NCS上SERS较强,阳离子型分子亚甲基蓝在old NCS上与在new NCS上相比SERS较弱,阴离子型分子苯甲酸在old NCS及new NCS均未观察到SERS信号。     

Application of calixarene to high active surface‐enhanced Raman scattering (SERS) substrates suitable for in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater

The characteristics of the sol–gel matrix embedding Ag nanoparticles functionalized with 25,27‐dimercaptoacetic acid‐26,28‐dihydroxy‐4‐tert‐butylcalix[4]arene (DMCX) suitable for the in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater is presented. The DMCX‐functionalized silver nanoparticles were produced by the thermal reduction method in xerogel film. The silver colloid blocks were formed in the sol–gel matrix, with a diameter ranging from 50 to 120 nm. DMCX forming the monolayer on the silver nanoparticle surface contributes to the surface‐enhanced Raman scattering (SERS) activity due to the aggregation of silver nanoparticles and the preconcentration of PAH molecules within the zone of electromagnetic enhancement. When selected, PAH molecules e.g. pyrene and naphthalene were adsorbed onto the SERS substrate; Raman band positions of PAH were slightly shifted. A calibration procedure reveals that this type of SERS substrate has a limit of detection of 3 × 10⁻¹⁰ mol/l for pyrene and 13 × 10⁻⁹ mol/l for naphthalene in artificial seawater. The Raman signal response on a pyrene concentration change in artificial seawater was evaluated using a 671‐nm Raman setup with a flow‐through cell. This type of SERS substrate will be suitable for the in situ trace detection of pollutant chemicals in seawater. Copyright © 2012 John Wiley & Sons, Ltd.