金属四苯基卟啉在氧化银和银胶体上的表面增强拉曼光谱研究(英文)

研究了四苯基卟啉金属配合物 (MTPP ;M =Ag ,Cu ,Pd ,Mg)和游离碱 (H2 TPP)在氧化银和银胶体中的表面增强拉曼光谱 (SERS) .在Ag2 O胶体中MTPP和H2 TPP的SERS谱与其普通拉曼谱明显不同 ,可知吸附分子在Ag2 O胶粒表面发生反应所引起 ,况且产物于 4 6 0nm附近有一强烈吸收 ,可知它含有共扼双吡咯发色团 .在OH- 修饰的银胶上也观察到类似的光谱变化 .     

基于银镜的高灵敏表面增强拉曼光谱基底制备及其用于呋喃唑酮检测

采用化学沉积法制备了表面增强拉曼散射光谱(SERS)银镜基底,用NaCl溶液与HCl溶液除去银镜表面杂质后,通过扫描电子显微镜对基底进行了表征,表明该基底表面的银纳米粒子平均粒径约为200 nm,以对巯基苯胺为探针分子测得其增强因子为4.6×105.利用表面增强拉曼光谱及表面吸附选择定律研究了广谱抗菌药呋喃唑酮在该基底表面的吸附状态,证明呋喃唑酮分子主要是通过CN吸附于银纳米粒子表面的.     

维生素PP的表面增强拉曼散射光谱研究

报道了维生素PP分子的常规拉曼光谱(NRS)及该分子在活性衬底银胶上的表面增强拉曼散射(SERS),并对它的拉曼特征峰进行了初步的指认和归属.维生素PP的常规拉曼光谱和SERS谱的对比表明,该分子吸附在银表面时,它的C‖O键与银粒子发生电荷转移,碳氧双键打开形成C-O 单键.通过分析可以推断维生素PP通过羰基和氨基垂直或斜立吸附在银表面上.     

一种新型表面增强拉曼活性基底的制备方法

表面增强拉曼光谱技术 (SERS)具有极高的灵敏度 ,对某些分子其灵敏度比常规拉曼光谱高一百万倍 ,能检测吸附在金属表面的单分子层和亚单分子层的分子 ,并提供丰富的分子结构信息 [1～ 5] .活性基底的制备是获得 SERS信号的前提 ,电化学粗糙化的电极、贵金属溶胶及真空蒸镀的金属岛膜是SERS分析中最常用的 3种活性基底 ,在实际应用中各有利弊 .本文报道一种新的制备银纳米粒子基底的方法 ,可使银纳米粒子生长到合适的尺寸 ,以达到最佳SERS增强效果 .利用紫外 -可见光谱和 AFM研究该 SERS基底纳米粒子的尺寸分布和形貌 ,以 1 ,4-(双…     

利用去湿现象制备具有SERS活性的银纳米粒子图案

构建了具有表面增强拉曼散射(SERS)活性的二维有序环状与盘状的银纳米粒子结构, 利用CTAB包覆银纳米粒子的氯仿溶液直接在图案化的金基底上进行去湿, 当改变银纳米粒子的浓度时可以得到不同的图案. 利用原子力显微镜(AFM)对其结构进行了表征, 以4-巯基吡啶作为探针分子, 采用表面增强拉曼成像技术研究了这种基底的SERS活性, 这将为SERS的研究开拓新的领域.     

银纳米粒子簇的设计、 制备和表面增强拉曼光谱

通过匹配激光光斑直径与胶体微球的尺寸, 设计制备了银纳米粒子的表面增强拉曼散射(SERS)基底, 并将其用于研究单个银纳米粒子簇的表面增强拉曼光谱. 在制备纳米粒子的过程中, 考察了等离子体刻蚀时间与银沉积厚度对“单”银纳米粒子结构与形貌的影响. 将吡啶、 巯基苯和罗丹明R6G作为SERS探针分子, 研究了其SERS效应, 通过荧光共振能量转移(FRET)机理, 实现了染料分子在单银纳米粒子簇上的SERS效应. SERS光谱测试与相关计算结果表明, 单个银纳米粒子簇的拉曼增强因子能够达到约10⁶.     

Au@SiO2膜/Ti电极吸附吡啶的表面增强拉曼光谱研究

基于壳层隔绝纳米粒子增强拉曼光谱技术,合成了Au@SiO₂纳米粒子,并对其进行了相关表征. 结果表明,包裹的二氧化硅层连续、致密,Au@SiO₂膜/Ti电极上可获得金属钛电极上吸附吡啶分子的高质量表面增强拉曼光谱（SERS）信号. 通过Pt、Ni电极的测试,证实该信号源于吸附在基底表面的吡啶分子. 此外,Au@SiO₂膜/Ti电极上吸附吡啶分子的现场SERS光谱研究表明,在-0.1 V ~ -0.6 V电位区间,吡啶分子平躺吸附,从-0.6 V起吸附的吡啶分子由平躺逐转变为垂直,而当电位为-1.2 V时,电极表面析氢,吡啶脱附.     

Ag_核Au_壳金属复合纳米粒子的制备及表面增强拉曼光谱研究

在已制备好的Ag纳米粒子表面,通过化学还原的方法沉积生长Au包裹层,制备了粒子尺寸为50-70nm的Ag核Au壳复合纳米粒子.通过改变AuCl₄^-量,使Ag_100-xAu_x中Au的含量由x=0变为x=30.用UV-Vis吸收光谱和透射电子显微镜(TEM)对该结构纳米粒子进行了表征,并以对巯基苯胺(PATP)为探针分子进行表面增强拉曼光谱(SERS)研究.表面拉曼光谱表明,该结构的纳米粒子具有比Ag更强的SERS活性,随着Au:Ag比例的逐渐增加,其活性呈现先增大后减小的趋势,其最大增强约为Ag纳米粒子的10倍.     

Ag/mSiO2空心微球的制备及SERS标记性能

以聚苯乙烯微球为模板, 经过原位还原和种子生长过程在聚苯乙烯微球表面包覆银(Ag)纳米粒子; 以正硅酸乙酯为硅源, 在十六烷基三甲基溴化铵的导向下实现介孔二氧化硅(mSiO₂)可控包覆, 去除模板得到Ag/mSiO₂空心微球. 透射电子显微镜(TEM)和氮气吸附-脱附分析结果表明, SiO₂壳层厚度约为20 nm, 介孔孔径为2.1 nm, 孔道分布均匀. 进一步利用虹吸作用使对巯基苯胺(4-ATP)分子进入微球内与Ag粒子结合, 构建表面增强拉曼散射(SERS)标记材料. SERS测试结果表明, 该标记材料检测限达到10^-7 mol/L, SERS增强因子达到3.7×10⁵.     

基于MOF@TiN-Ag/银溶胶复合基底的茶碱表面增强拉曼检测

以制备的MOF@TiN-Ag/银溶胶复合基底为表面增强拉曼光谱(SERS)活性基底，对茶碱进行SERS检测，探讨了基于该复合基底的表面增强拉曼技术在药物检测方面的应用。首先，利用电化学阳极氧化结合氨气还原氮化法制备了氮化钛纳米管阵列，随后通过电化学沉积法制备TiN-Ag复合基底，并在其表面原位生长金属有机框架(MOF)包覆层得到MOF@TiN-Ag复合基底，将茶碱与银溶胶混合后滴加在该复合基底上进行表面增强拉曼光谱检测。结果表明，MOF@TiN-Ag/银溶胶复合基底中存在面心立方晶型TiN、金属单质Ag和MOF钴基3种物相；扫描电镜结果显示，TiN纳米管排列整齐，Ag纳米结构呈树枝状均匀分散在其表面；作为隔绝层的MOF粒子形状规整，覆盖在TiN-Ag表面；银溶胶纳米粒子呈圆球状分布在MOF@TiN-Ag复合基底表面。由于银纳米粒子与TiN-Ag复合基底可发生协同增强作用，加之MOF的富集特性，使得该复合基底具有优异的SERS性能，其对茶碱溶液的SERS检出限为1×10^-5 mol/L，检测性能良好。所制备的MOF@TiNAg/银溶胶复合基底拓宽了SERS在药物检测...     

Photochemical Synthesis and Spectral-Optical Characteristics of ZnO/Cu and ZnO/Ag/Cu Nanoheterostructures

The photoreduction of Cu²⁺ at the surface of ZnO nanoparticles and ZnO/Ag nanostructures was investigated. The spectral characteristics of the obtained ZnO/Cu and ZnO/Ag/Cu composites were studied in relation to the reaction conditions. It was shown that the ZnO/Ag nanoparticles have higher photocatalytic activity in the reduction of Cu²⁺ ions than the individual ZnO particles.     

Fabrication and SERS properties of Ag/Cu2S composite micro-nanostructures over Cu foil

A new kind of Ag/Cu2S composite micro/nanostructures has been prepared via a convenient galvanic reduction method. SEM images of these micro/nanostructures showed that Ag nanoparticles with the size of around 50-100 nm were well deposited on the surface of Cu2S micro/nanostructures. The SEM images also indicated that the Ag nanoparticles were preferentially grown on the big polygonal Cu2S microstructures, which could be explained by a localization of the electrons on the surface of the polygonal Cu2S microstructures after the electron transfer step. Owing to the introduction of Ag nanoparticles on the surface of Cu2S micro/nanostructures, the resulting Ag/Cu2S composite micro-nanostructures could be used as a versatile substrate for surface enhanced Raman scattering.     

Effect of Ag and Au nanoparticles on the SERS of 4-aminobenzenethiol assembled on powdered copper

Raman scattering measurements were conducted for 4-aminobenzenethiol (4-ABT) assembled on powdered copper substrates. Initially, very weak Raman peaks were detected, but upon attaching Ag nanoparticles probably via NH2 groups onto 4-ABT/Cu, distinct Raman spectra were observed. Considering the fact that no Raman peak was identified when Ag nanoparticles were adsorbed on 4-aminophenyl-derivatized silane monolayers assembled on silica powders, the Raman spectra observed for Ag@4-ABT/Cu should be surface-enhanced Raman scattering (SERS) spectra, occurring by an electromagnetic coupling of the localized surface plasmon of Ag nanoparticles with the surface plasmon polariton of Cu powders. The extra enhancement factor attainable by the attachment of a single Ag nanoparticle is estimated to be as large as 1.4 x 10(5) in the case when 632.8-nm radiation is used as the excitation source. When Au nanoparticles were attached onto 4-ABT/Cu, at least an order of magnitude weaker Raman spectra were obtained at all excitation wavelengths, however, indicating that the Au-to-Cu coupling should be far less effective than the Ag-to-Cu coupling for the induction of SERS.     

Visual determination of Cu(2+) through copper-catalysed in situ formation of Ag nanoparticles

A new strategy was explored for the visual determination of Cu(2+) using copper-catalysed in situ formation of Ag nanoparticles. In this method, only common reagents were used and the pre-synthesis and modification of nanoparticles are avoided. Ag(+) can form a milk-white suspension (AgBr) with Br(-) in an aqueous solution composed of AgNO(3), cetyltrimethylammonium bromide, ascorbic acid, bovine serum albumin, and NaNO(3). The reaction will be stopped by addition of Cu(2+), accompanied by a colour change from milk-white to orange or brilliant yellow. Cu(+) (the reduction product of Cu(2+)) consumes the dissolved O(2) and prevents the O(2) from oxidizing the newly reduced Ag atoms (by ascorbic acid) back to Ag(+), facilitating the further aggregation of Ag atoms to become Ag nanoparticles. The visible colour change was shown to be specific towards Cu(2+) over most other metal ions. The limit of detection was 0.75 μM Cu(2+) by the naked eye and 0.25 μM by spectrometer. Quantitation of Cu(2+) was achieved in a linear range from 0.25 to 2.0 μM. This method was validated by measuring real water and serum samples, giving results agreeing well with the data reported and measured by inductively coupled plasma mass spectrometry. The recovery was 95.6-106% for untreated tap water and 96.0-100% for resin-pre-treated water and serum samples.     

Fabrication of Cu-Ag core-shell bimetallic superfine powders by eco-friendly reagents and structures characterization

Superfine bimetallic Cu-Ag core-shell powders were synthesized by reduction of copper sulfate pentahydrate and silver nitrate with eco-friendly ascorbic acid as a reducing agent and cyclodextrins as a protective agent in an aqueous system. The influence of Ag/Cu ratio on coatings was investigated. Ag was homogeneously distributed on the surface of Cu particles at a mole ratio of Ag/Cu=1. FE-SEM showed an uniformity of Ag coatings on Cu particles. Antioxidation of Cu particles was improved by increasing Ag/Cu ratio. TEM-EDX and UV-vis spectra also revealed that Cu cores were covered by Ag nanoshells on the whole. The surface composition analysis by XPS indicated that only small parts of Cu atoms in the surface were oxidized. It was noted that the hindrance of cyclodextrins chemisorbed on particles plays an important role in forming high quality and good dispersity Cu-Ag (Cu@Ag) core-shell powders.     

Preparation and study of polyacryamide-stabilized silver nanoparticles through a one-pot process

A one-pot route was illustrated to synthesize stable well-dispersed silver colloids stabilized by polyacrylamide on a large scale. Reduction of silver ions and polymerization of acrylamide occurred almost simultaneously in the absence of a commonly used reducing agent and initiator. A possible mechanism for the formation of silver nanoparticles with bimodal size distribution was proposed. The structure and composition of the obtained nanoparticles were characterized carefully. Furthermore, light scattering simulation and UV-vis absorption studies confirmed that the obtained colloids were the mixture of Ag and Ag2O nanoparticles. The presence of silver oxide layers on the nanoparticle surface should be responsible for the broadening of the surface plasmon band of silver nanoparticles. Ag2O layers could be added or removed from Ag nanoparticle surfaces by the addition of HNO3, HAc, or NaCl solution to the as-obtained silver colloids.     

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively.     

电极用纳米Ag~2O的电化学性能研究1: 纳米Ag~2O 的制备及表征

用化学方法首次成功地制备出了用于电极活性材料的纳米Ag~2O微粒,并通过TEM,XRD和XPS等测试技术进行了分析表征。同时,对每种方法纳米Ag~2O的生成机理进行了初步的探讨,表明这些方法具有一定的普适意义。     

Rapid transformation from spherical nanoparticles, nanorods, cubes, or bipyramids to triangular prisms of silver with PVP, citrate, and H2O2

Rapid sphere-to-prism (STP) transformation of silver was studied in aqueous AgNO(3)/NaBH(4)/polyvinylpyrrolidone (PVP)/trisodium citrate (Na(3)CA)/H(2)O(2) solutions by monitoring time-dependent surface plasmon resonance (SPR) bands in the UV-vis region, by examining transmission electron microscopic (TEM) images, and by analyzing emitted gases during fast reaction. Roles of PVP, Na(3)CA, and H(2)O(2) were studied without addition of a reagent, with different timing of each reagent's addition, and with addition of H(2)O(2) to mixtures of spheres and prisms. Results show that prisms can be prepared without addition of PVP, although it is useful to synthesize smaller monodispersed prisms. A new important role of citrate found in this study, besides a known role as a protecting agent of {111} facets of plates, is an assistive agent for shape-selective oxidative etching of Ag nanoparticles by H(2)O(2). The covering of Ag nanoparticles with carboxylate groups is necessary to initiate rapid STP transformation by premixing citrate before H(2)O(2) addition. Based on our data, rapid prism formation starts from the consumption of spherical Ag particles because of shape-selective oxidative etching by H(2)O(2). Oxidative etching of spherical particles by H(2)O(2) is faster than that of prisms. Therefore, spherical particles are selectively etched and dissolved, leaving only seeds of prisms to grow into triangular prisms. When pentagonal Ag nanorods and a mixture of cubes and bipyramids were used as sources of prisms, rod-to-prism (RTP), cube-to-prism (CTP), and bipyramid-to-prism (BTP) transformations were observed in Ag nanocrystals/NaBH(4)/PVP/Na(3)CA/H(2)O(2) solutions. Shape-selective oxidative etching of rods was confirmed using flag-type Ag nanostructures consisting of a triangular plate and a side rod. These data provide useful information for the size-controlled synthesis of triangular Ag prisms, from various Ag nanostructures and using a chemical reduction method, having surface plasmon resonance (SPR) bands at a desired wavelength.     

氧化银纳米线在官能化二氧化硅颗粒表面的自组装合成

在碱性水醇溶液中, 硝酸银与用3-(2-氨乙基氨丙基)三甲氧基硅烷[N-(2-aminoethyl)-3-aminopropyl-trimethoxy- silane, AMPTS]表面修饰后的二氧化硅胶体颗粒相互作用, 发现所生成的氧化银纳米颗粒可以在二氧化硅颗粒表面自组装为氧化银纳米线. 通过调变反应物中Ag/Si摩尔比, 可对氧化银纳米线的形貌进行调控. 在较小的Ag/Si摩尔比下, 可以得到结构均匀、直径约为50 nm、长度几十微米的氧化银纳米线. 随Ag/Si摩尔比增大, 得到的氧化银纳米线逐渐变短变粗, 且结构变得不均匀. 高分辨透射电镜(HRTEM)显示, 所有的氧化银纳米线均由直径10～20 nm的氧化银颗粒定向堆积而得. 利用透射电镜(TEM)对氧化银纳米线的形成过程进行了观察, 并对氧化银颗粒形成及组装机理进行了探讨.