锌的表面增强喇曼散射效应

本文从莫育俊等人提出的天线共振子模型理论出发,计算了金属锌的SERS增强特性。天线共振子模型预言,在可见光区,锌的增强因子最大为10,而在红外则会达到很大的增强(10⁵以上).同时,我们通过实验分析了金属锌的SERS增强特性,得到了在可见光区锌的增强因子约为230.在考虑化学增强的情况下,理论计算结果同实验基本一致。     

LB膜隔离层对表面增强喇曼散射的影响

本文首次利用LB膜作为分子—金属间的隔离层,考察了表面增强喇曼散射的电磁增强机理,监测了表面增强喇曼散射信号随隔离层厚度的变化。在银膜/LB膜/吡啶+氯化钾系中,实验结果表明,隔离层厚度为5nm时,表面增强喇曼散射效应仍然存在,但在15nm时已测不到其信号,实验支持了电磁增强机理。     

银分子中电荷转移效应及其对喇曼信号的增强研究

本文从观察光的吸收谱变化觉察到分子吸附在银胶、银镜上所出现的电荷转移跃迁;同时测量了电荷转移对吸附分子喇曼信号的增强.并且对其机理进行了初步分析.     

金属光栅表面增强喇曼散射TE模的计算分析

以纳米量级金属履带矩形光栅为模型,研究了表面增强喇曼散射的特性.针对TE模的入射光,采用耦合波原理对金属表面的衍射场进行了讨论,并用数值计算方法讨论了光栅周期、光栅深度等参量对表面增强的影响以及增强因子随第一级瑞利系数的变化关系.结果表明：在入射光波长为700 nm、光栅周期p=400 nm、 光栅深度d=150 nm、占空比为1/3、入射角度为10°时,获得最大增强,增强因子G可达102.     

钴钯铂的表面增强喇曼散射效应研究

利用天线共振子模型对钴钯铂的表面增强喇曼散射特性进行了计算和分析, 计算结果表明钴钯铂的增强分别为1、≤4、2～4, 实验测量的最大增强分别为≤5、105和140, 在考虑化学增强的情况下, 理论同实验是一致的; 在经氧化还原过程处理的钴钯铂片上做了核酸碱基胞嘧啶的SERS谱, 结果反映三种衬底上的SERS谱强弱不同, 以铂最大, 钴最小, 而且, 三种衬底对于胞嘧啶各振动模式的增强基本一致.     

银片上茜素的表面增强共振喇曼散射效应及模式标识

本文对吸附在经连续的氧化 还原循环(ORC)过程处理的银片衬底上的茜素的表面增强共振喇曼散射(SERRS)特性进行了研究,并对茜素SERRS谱中的振动模式做了标识.结果表明,吸附在经氧化.还原循环(ORC)处理的银片衬底上的茜素分子,其表面增强喇曼散射的强度,主要是由于最靠近银片的一层分子的增强,而第一层以外的分子贡献很小.也就是说,表面增强喇曼散射具有单层饱和效应.茜素在经ORC处理的银片上和在银镜上所显示的SERRS特征基本一致,其中有些振动模式存在小的频移,这与银片、银镜各自的表面特性有关.     

一种具有较强表面增强喇曼散射效应的纳米银粒子

制备出一种新的纳米银溶胶,与传统银溶胶相比,不仅可见光透过率高,而且还有较强的表面增强喇曼散射(SERS)效应.当阴、阳离子型分子分别吸附于其表面上时,喇曼与传统银胶相比表观增强分别约为400倍、70倍.     

光诱导转化法制备片状三角形银纳米粒子的表面增强喇曼散射

采用柠檬酸三钠化学还原法制备球形Ag纳米粒子溶胶,并用高压球形氙灯对球形Ag纳米粒子溶胶进行光诱导实验.利用透射电子显微镜、紫外-可见吸收光谱研究了不同光照时间下的银胶纳米粒子的光谱特性和表面形貌,并以结晶紫为探针分子测量了银胶纳米粒子的表面增强喇曼散射光谱.实验结果表明:随着光照时间的增多,Ag纳米粒子溶胶颜色变化显著;紫外-可见吸收光谱吸收峰从单一峰渐渐显示出多个峰;透射电子显微镜图显示Ag纳米粒子由球形逐渐转变成片状三角形银纳米粒子、截角的片状三角形银纳米粒子;表面增强喇曼散射的增强效应随着光照时间的变化先逐渐增大,然后逐渐减小.     

表面增强喇曼散射(SERS)光谱中影响增强效应因素的实验研究(Ⅲ)

本文研究了苯甲酸水溶液的pH值,电极外加电位对银电极表面吸附苯甲酸SERS光谱表面增强效应的影响。实验结果表明,苯甲酸以—COO~-根负离子吸附于银电极表面。通过改变溶液的pH值,使苯甲酸吸附于粗糙银电极表面,溶液pH值影响电极表面吸附苯甲酸的面密度,电极外加电位影响—COO~-根离子与银电极间的电荷迁移,电极外加电位也影响苯甲酸在粗糙银电极表面的吸附。     

Surface enhanced Raman scattering of 2-cyanopyridine adsorbed on silver colloidal particles

Surface-enhanced Raman scattering (SERS) spectra of 2-cyanopyridine (2 CP) adsorbed on silver colloidal particles have been investigated. The prominent SERS bands are observed at 556, 612, 778, 1002, 1060, 1072, 1150 and 1240 cm⁻¹. The absolute enhancement factor of the Raman signals in SERS studies has been estimated to be of the order of 10²–10⁵ for various bands. The 2CP molecules have been ascribed to adsorb on colloidal particles in standing up fashion.     

表面等离子激元非线性表面增强拉曼散射效应

本文采用热蒸发法制备得到纳米Ag颗粒作为增强拉曼衬底, 利用入射光子与纳米颗粒表面价电子的相互作用机理, 激发出高能表面等离子激元, 其表面等离子形成的高能"热点"起到表面增强拉曼散射效果. 通过比较不同入射光强下的拉曼峰强, 指出纳米Ag颗粒的增强拉曼散射效果可以实现低探测光强下的高散射强度, 即纳米Ag颗粒的表面等离子激元具有非线性的表面增强拉曼散射效果, 可降低对样品的光、热损伤, 以利于拓展拉曼散射光谱的应用范围. 同时比较不同纳米Ag颗粒衬底的表面增强拉曼散射效果表明, 采用的热蒸发工艺具有较大的工艺域度, 具有较强的工艺兼容性.     

Surface‐enhanced Raman scattering assessment of DNA from leaf tissues adsorbed on silver colloidal nanoparticles

In this work, the surface‐enhanced Raman scattering (SERS) spectra of seven genomic DNAs from leaves of chrysanthemum (Dendranthema grandiflora Ramat.), common sundew (Drosera rotundifolia L.), edelweiss (Leontopodium alpinum Cass), Epilobium hirsutum L., Hypericum richeri ssp. transsilvanicum (Čelak) Ciocârlan, rose (Rosa x hybrida L.) and redwood (Sequoia sempervirens D. Don. Endl.), respectively, have been analyzed in the wavenumber range 200–1800 cm⁻¹. The surface‐enhanced Raman vibrational modes for each of these cases, spectroscopic band assignments and structural interpretations of genomic DNAs are reported. A high molecular structural information content can be found in the SERS spectra of these DNAs from leaf tissues. Based on this work, specific plant DNA–ligand interactions or accurate local structure of DNA might be further investigated using surface‐enhanced Raman spectroscopy. Besides, this study will generate information which is valuable in the development of label‐free DNA detection for chemical probing in living cell. Copyright © 2013 John Wiley & Sons, Ltd.     

纳米Ag材料表面等离子体激元引起的表面增强拉曼散射光谱研究

用热蒸发的方法制备了纳米Ag材料,并用扫描电子显微镜对纳米粒子进行了形貌的表征,通过紫外—可见分光光度计得到Ag纳米粒子的透过谱,得到了Ag纳米粒子的表面等离子体共振的峰值位置.以罗丹明6G为探针分子测定Ag纳米粒子衬底的表面增强拉曼散射效应,通过拉曼散射光谱与透过谱研究了由表面等离子体激元的强极化场引起的表面增强拉曼散射效应,结合透过谱与拉曼增益因子提出了一种描述表面等离子体光学和电学特性的方法,并结合扫描电镜的结果给出了不同结构的纳米Ag材料对表面等离子体激元强度的影响. 关键词： 热蒸发 纳米Ag材料 表面等离子体 表面增强拉曼散射     

Darling–Dennison resonance of thiourea adsorbed on the silver electrode revealed by surface enhanced Raman spectroscopy

We report surface enhanced Raman spectroscopy (SERS) of Darling–Dennison resonance of thiourea on Ag electrode excited at 514.5 nm laser excitation. Darling–Dennison resonance indicates that two degenerate Raman modes interact with each other and their degenerate first‐order overtone modes obtain energy and appear in Raman spectra. Our study showed that the ratio of intensity of the Darling–Dennison resonance is up to 0.24 of its fundamental Raman intensity, when the applied electrode voltage is at –0.4 V versus the saturated calomel electrode. This phenomenon was also observed on the Ag island film surface at ambient condition. These observations demonstrated strong evidence for Darling–Dennison resonance band in SERS. The implications of these observations are also discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering on silver dendrite with different growth directions

A simple and cost‐effective strategy was developed to synthesize Ag dendrites via an aqueous chemical route based on spontaneous galvanic displacement between silver (I) ions and copper foil under hydrothermal condition. Ag dendrites with [100], [110], and [111] growth direction can be prepared by adjusting the content of polyvinyl pyrrolidone. The Ag dendrites exhibited fine and well reproducible surface‐enhanced Raman scattering effect using Rhodamine 6G as model molecule. There is a corresponding relation between the false color plot of Raman intensity and the dendrite morphology. Among the products, the Ag dendrites growing along [100] direction have the best surface enhancement ability, and a possible explanation was proposed. The results might open up new thinking on surface‐enhanced Raman scattering by proper crystal growth and design. Copyright © 2011 John Wiley & Sons, Ltd.     

Piperidine adsorption on two different silver electrodes: A combined surface enhanced Raman spectroscopy and density functional theory study

The surface enhanced Raman scattering (SERS) spectra of piperidine in silver colloid solution, on roughened silver electrode and on roughened silver electrode modified with silver nanoparticles were studied, and the high-quality SERS spectra of piperidine on roughened silver electrode modified with silver nanoparticles were obtained for the first time. Surface selection rules derived from the EM enhancement model were employed to deduce piperidine orientations on the different surfaces. On the basis of this, two models of piperidine adsorbed on the surface of the silver nanoparticles were built, and DFT-B3PW91/LanL2dz was applied to calculate the Raman frequencies. It proves that, at higher potential values, the piperidine is perpendicularly standing on the roughened silver electrode surface though its lone-electron pair, but in silver colloid solution and on the silver nanoparticles modified silver electrode the piperidine molecular lies flat on the silver surface. In the meantime, the potential dependent SERS of piperidine on the modified electrode were studied.     

Surface‐enhanced Raman spectroscopy of 4‐tert‐butylpyridine on a silver electrode

We report the observation of large surface‐enhanced Raman scattering (SERS) (10⁶) for 4‐tert‐butylpyridine molecules adsorbed on a silver electrode surface in an electrochemical cell with electrode potential set at − 0.5 V. A decrease in electrode potential to − 0.3 V was accompanied by a decrease in relative intensities of the vibrational modes. However, there were no changes in vibrational wavenumbers. Comparison of both normal solution Raman and SERS spectra shows very large enhancement of the intensities of a₁, a₂, and b₂ modes at laser excitation of 488 nm. Enhancement of the non‐totally symmetric modes indicates the presence of charge transfer as a contributor to the enhancement. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering of N‐acetylneuraminic acid on silver nanoparticle surface

N‐Acetylneuraminic acid (sialic acid, Neu5Ac) has recently gained interest as a potential marker for a variety of pathophysiological processes, although no Raman study has been reported for this important biomolecule. In this paper, the vibrational properties of Neu5Ac were studied by means of Raman, surface‐enhanced Raman scattering (SERS), and density functional theory calculations. By adsorption of Neu5Ac on silver nanoparticle surface, strongly enhanced Raman intensities are obtained, allowing easy measurement of small amounts of aqueous Neu5Ac (10 µl of a 10⁻⁷ m solution) utilizing low laser power and short exposure time. The mechanism of adsorption of Neu5Ac on the silver surface is discussed on the basis of the experimental and theoretical results. This study demonstrates that SERS can provide an effective tool for development of a label‐free, rapid, and sensitive optical platform for identification of Neu5Ac. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman scattering of L‐tryptophan enhanced by surface plasmon of silver nanoparticles: vibrational assignment and structural determination

Vibrational bands of L ‐tryptophan which was adsorbed on Ag nanoparticles (∼10 nm in diameter) have been investigated in the spectral range of 200–1700 cm⁻¹ using surface‐enhanced Raman scattering (SERS) spectroscopy. Compared with the normal Raman scattering (NRS) of L ‐tryptophan in either 0.5 M aqueous solution (NRS‐AS) or solid powder (NRS‐SP), the intensified signals by SERS have made the SERS investigation at a lower molecular concentration (5 × 10⁻⁴ M ) possible. Ab initio calculations at the B3LYP/6‐311G level have been carried out to predict the optimal structure and vibrational wavenumbers for the zwitterionic form of L ‐tryptophan. Facilitated with the theoretical prediction, the observed vibrational modes of L ‐tryptophan in the NRS‐AS, NRS‐SP, and SERS spectra have been analyzed. In the spectroscopic observations, there are no significant changes for the vibrational bands of the indole ring in either NRS‐AS, NRS‐SP, or SERS. In contrast, spectral intensities involving the vibrations of carboxylate and amino groups are weak in NRS‐AS and NRS‐SP, but strong in SERS. The intensity enhancement in the SERS spectrum can reach 10³–10⁴‐fold magnification. On the basis of spectroscopic analysis, the carboxylate and amino groups of L ‐tryptophan are determined to be the preferential terminal groups to attach onto the surfaces of Ag nanoparticles in the SERS measurement. Copyright © 2008 John Wiley & Sons, Ltd.