纳米银溶胶和微腔型光纤SERS基底的制备及其性能比较

通过化学法制备了纳米银溶胶基底和微腔型光纤表面增强拉曼散射(SERS)基底,其中光纤SERS基底的微腔结构是通过氢氟酸(H F)腐蚀得到的.实验采用湿法检测,首先将纳米银溶胶基底与罗丹明6G(R6 G)混合,找到增强效果最强时的裸光纤微腔结构,在此结构的基础上采用溶胶自组装法制备银纳米颗粒包覆的光纤SERS基底,通过控...     

R6G单分子表面增强共振拉曼散射光谱探测研究

以共焦显微系统为平台,研究了不同浓度的R6G银溶胶的表面增强共振拉曼散射(SERRS)光谱, 结果表明不同浓度溶液中的R6G分子表现出了不同的光谱特性。在浓度为10-13mol·L-1的R6G银溶胶中 得到了R6G单分子的表面增强共振拉曼散射光谱,观察到了一些光谱非均匀变化现象,如谱色散、谱线的 强度起伏、拉曼谱的偏振化以及分子的闪烁等,并对这些现象进行了分析,证明得到的是R6G单分子的 SERRS光谱。文章还对单分子检测中的一些关键问题进行了分析与讨论,确定了单分子SERRS光谱检测的 适当条件。     

微波法制备银胶体及其在表面增强拉曼散射中的应用

本文提出了一种利用微波加热的原理,合成一种新型的银胶体溶液。该银胶具有高效的表面增强拉曼活性。以这种新型银胶体粒子作为活性衬底,测得的强荧光物质R6G的表面增强拉曼光谱,体现出荧光背景低,信噪比高的特点。通过两种不同方法制备的银胶体粒子的表面增强拉曼散射效果的比较,发现这种新型银胶纳米粒子通过聚集,形成更多的具有很强的提高样品表面增强拉曼散射强度作用的“热点”,从实验的角度验证了表面增强拉曼中的“热点”理论。     

金纳米粒子的制备及其表面增强拉曼散射效应的研究

采用多巴胺化学还原法制备了分散性良好的纳米金溶胶,并检测了其作为表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)基底的性质。粒度和透射电子显微镜测试结果表明金溶胶为平均粒径30nm左右的球形颗粒,并且紫外-可见特征吸收峰出现在520nm,为典型的金纳米颗粒特征吸收峰。以罗丹明6G(R6G)为探针分子证明了金溶胶良好的SERS增强效果,用金溶胶对除草剂敌草快(DQ)进行检测,最低检测限可达1×10-7 mol/L。结果表明所制备的金溶胶具有良好的表面增强拉曼散射活性。     

噻菌灵在纳米银胶表面吸附的表面增强拉曼光谱研究

噻菌灵(TBZ)属苯并咪唑类杀菌剂,容易在水果、蔬菜及相应的果蔬饮品中形成有毒残留。基于密度泛函理论(DFT)的量子化学计算方法和表面增强拉曼光谱(SERS)技术,从理论和实验角度系统研究了噻菌灵在纳米银胶粒子表面的吸附行为和增强效应。采用柠檬酸钠还原法制备了具有表面增强拉曼散射活性的银纳米溶胶,并对水相的噻菌灵进行了SERS光谱研究。利用TBZ-Ag₄四种吸附模型对噻菌灵与银纳米溶胶的相互作用进行了理论分析。结合FT-Raman光谱和B3LYP/6-311G(d)理论计算的结果,借助Gaussian View5.0程序的图形化功能,对噻菌灵分子的振动模式、FT-Raman振动光谱和SERS光谱进行了系统的指认。研究结果表明：噻菌灵分子的所有原子在同一平面上,属于Cs对称性;其在银纳米溶胶表面具有十分显著的表面增强拉曼活性;分子中的S原子与银胶粒子发生吸附作用,并通过该分子的长轴方向垂直于银纳米银胶表面;可利用SERS光谱方法对痕量的噻菌灵进行快速检测。为研究噻菌灵的特性以及其快速检测提供了理论和实验依据。     

树枝状银纳米结构的可控电化学合成及其SPR/SERS性质

采用电化学沉积的方法在导电玻璃衬底上合成出树枝状的银纳米结构. 通过调控电位、表面活性剂、硝酸银浓度等参数控制树枝状银纳米结构的尺寸、直径、结晶性和分枝密度. 三种典型的树枝状银纳米结构被用来做表面增强拉曼散射衬底,其中的一种可以清楚的探测浓度低于0.1 nmol/L的若丹明6G分子. 不同树枝状银纳米结构表面增强拉曼效果相差比较大,说明了分枝颗粒形状,特别是颗粒间距对表面增强拉曼散射有非常重要的影响.     

六氢吡啶的表面增强拉曼散射研究

表面增强拉曼光谱在化学、生物及表面科学等领域都有广泛应用, 因此六氢吡啶的表面增强拉曼光谱的研究具有重要意义。实验用法国JOBIN YVON公司的光谱仪测定了六氢吡啶的正常拉曼光谱及其在银溶胶、银膜表面的表面增强拉曼光谱(SERS), 确保了实验结果的可靠性。利用表面增强拉曼散射技术研究了六氢吡啶的拉曼谱, 对它的拉曼峰进行了指认, 并得出了在银表面的吸附方式。同时分析了六氢吡啶在银溶胶及银膜表面拉曼散射光强增强程度不同的原因。     

以新型银胶为衬底的超低浓度R6G的拉曼光谱检测

利用柠檬酸钠还原硝酸银的原理,提出了一种微波加热制备银胶体粒子的新方法,得到了颗粒大小较均匀的灰色银胶体。以提纯后的银胶为表面增强拉曼散射衬底,研究了超低浓度染料大分子罗丹明6G分子的表面增强拉曼散射,得到浓度分别为10-12mol/L、10-13mol/L和10-14mol/L的罗丹明6G的表面增强拉曼散射光谱,初步实现了罗丹明6G的单分子检测,证明该新型银胶衬底有非常强的表面增强拉曼活性。同时根据表面增强拉曼散射“热点”的增强机理,分析了获得超低浓度R6G的表面增强拉曼光谱的原因。     

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     

银微聚集体上的表面增强拉曼研究

本文对柠檬酸钠方法还原的银溶胶形成的微聚集体进行了表面增强拉曼(SERS)研究。通过表面等离子体成像以及SERS成像对该聚集体上的表面增强拉曼活性进行讨论。实验证明该聚集体具有较强的拉曼增强能力。对探测分子1H-1,2,3-triazolo[4,5-b]pyridine(TzPy)的检测浓度达到10-6mol/L,信噪比(S/N)为6左右。     

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.     

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.     

A simple method for the preparation of ultrahigh sensitivity surface enhanced Raman scattering (SERS) active substrate

By immersing mica modified with cetyltrimethylammonium bromide (CTAB) into the silver colloid, a high efficient surface enhanced Raman scattering (SERS) active substrate was formed within 2 h at room temperature. The limit of detection of the substrate for Rhodamine 6G is up to 1×10⁻¹⁴ M. Changing the concentration of silver colloid and the treating time, various silver aggregates such as nanocrystals, clusters and films were found, and the SERS spectra of these aggregates were also obtained. The results of SERS revealed that CTAB could accelerate aggregation of the silver colloid and cause great Raman enhancement. Bilayer of CTAB is very important for aggregation of silver colloid and the aggregation extent is the main factor for the enormous enhancement on this substrate.     

IR,Raman and SERS spectra of ethyl salicylate

The IR and Raman spectra of ethyl salicylate were recorded and analyzed. The surface enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound have been computed using the Hartree‐Fock/6‐31G* basis. The direction of charge transfer contribution to SERS has been discussed from the frontier orbital theory. The presence of methyl modes in the SERS spectrum indicates the nearness of the methyl group to the metal surface and the presence of ring vibrations and out‐of‐plane ring modes in the SERS spectrum suggests a flat orientation of the molecule on the silver surface. The first hyperpolarizability is calculated and the calculated molecular geometry has been compared with the reported similar structures. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational spectroscopic studies and computational study of methyl(2‐methyl‐4,6–dinitrophenylsulfanyl)ethanoate

FT‐IR and FT‐Raman spectra of methyl(2‐methyl‐4,6–dinitrophenylsulfanyl)ethanoate (MDIE) were recorded and analyzed. Surface‐enhanced Raman scattering (SERS) spectra were recorded in silver colloid and silver electrode. The vibrational wavenumbers were computed using HF/6‐31G* and B3LYP/6‐31G* basis. The data obtained from vibrational wavenumber calculations are used to assign vibrational bands obtained in infrared and Raman spectroscopies as well as in SERS of the studied molecule. The first hyperpolarizability and infrared intensities are reported. The geometrical parameters of the title compound are in agreement with the reported similar derivatives. The presence of new bands at 1045 and 948 cm⁻¹ in the SERS spectrum in silver electrode is related to the change in orientation of the molecule with respect to the metal surface. In silver colloid SERS spectrum, the methyl group attached to the methoxy carbonyl group is close to the metal surface, whereas on silver electrode the methyl group attached to the phenyl ring is close to the metal surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational spectroscopic studies and ab initio calculations of phenyl phosphate disodium salt

The Fourier‐transform infrared and Fourier‐tranform Raman spectra of phenyl phosphate disodium salt were recorded and analyzed. The surface‐enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound were computed using the Hartree–Fock/6‐31G* basis and compared with the experimental values. The molecule is adsorbed on the silver surface with the benzene ring in a tilted orientation. The presence of the phenyl ring and the phosphate group vibrations in the SERS spectrum reveal the interactions between the phenyl ring and the phosphate group with the silver surface. The first hyperpolarizability is calculated, and the calculated molecular geometry is compared with those of similar reported structures. Copyright © 2009 John Wiley & Sons, Ltd.     

单分子水平罗丹明B吸附在银胶颗粒上的表面增强拉曼散射光谱研究(英文)

本文研究了单分子水平上银胶纳米体系中罗丹明B和罗丹明6G的拉曼光谱,研究结果显示单分子水平上罗丹明B的拉曼光谱作为探测试剂将可能提供更加丰富的分子信息。     

Surface-enhanced Raman scattering of methyl <Emphasis Type="Italic">p</Emphasis>-hydroxy benzoate: A molecular orientational study

The surface geometry of a methyl p-hydroxy benzoate (MPHB) molecule was studied by analysis of the SERS spectra adsorbed on silver colloid surfaces. For a reliable analysis of the SERS spectrum, we also performed density functional theoretical calculations. The large enhancement of the in-plane ring-stretching and ring-stretching modes in the surface-enhanced Raman scattering spectrum indicates that the molecule is adsorbed on the silver surface in a stand on orientation of MPHB on a silver surface.     

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