一种新型银溶胶的制备、表征及其SERS活性的研究

报道了用一种化学还原方法制备银溶胶的新方法。用紫外-可见光谱和透射电镜研究银纳米粒子的形成过程,粒子形状及粒径分布。结果表明,在反应初期形成球形和棒状两种形状的银纳米粒子,随着反应的进行,大部分的棒状粒子逐渐变为球形粒子,最终棒状粒子少于银纳米粒子总数的3%。因此,最终得到了一种形状均一的,平均粒径为17nm银纳米粒子。同时也用紫外-可见光谱研究了Cl-的加入对这种银纳米粒子光谱性质的影响,结果表明Cl-加速了银纳米粒子的聚集。这种银溶胶有着较高的SERS活性。     

聚丙烯胺稳定铜纳米粒子的制备及其SERS活性研究

报道了聚丙烯胺稳定的球形和棒状铜纳米粒子的制备方法。在水溶液中空气条件下,通过水合肼还原二价铜离子到铜纳米粒子。聚丙烯胺的作用除稳定粒子防止聚集外,也可使粒子分散在水溶液中。该法的优点是在室温下,无需惰性气体保护,即可制备水溶液中分散的铜纳米粒子。紫外光谱和透射电镜监测了铜纳米粒子的生长过程。发现氢氧化钠的用量,聚丙烯胺浓度,反应时间等因素都影响到铜纳米粒子的组成,尺寸,形貌和聚集程度。氢氧化钠用量决定了制备粒子的组成成分是铜或氧化亚铜。所制备的球形铜纳米粒子表现出优良的表面增强拉曼散射活性。     

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.     

绿色合成银纳米粒子及其在SERS中的应用

采用无毒、绿色的酪氨酸作为还原剂和稳定剂,在碱性条件下还原硝酸银,经60 ℃恒温水浴处理20 min,成功地合成了银纳米粒子。混合溶液颜色由淡黄色变为棕黄色直观地呈现了银纳米粒子的生成。利用紫外可见吸收光谱(UV-Vis)和透射电子显微镜(TEM)对制备样品进行分析和表征。粒子的UV-Vis吸收在412 nm附近。TEM图像显示,银纳米粒子的形状近似球形,粒子直径在15～25 nm。分别以结晶紫(CV)和叶酸(FA)为探测分子,进一步研究了该银纳米粒子的表面增强拉曼散射(SERS)效应。实验结果表明,该合成方法不仅方便、快速、绿色环保,而且合成的银纳米粒子对CV和FA分子有很好的SERS效应。     

玻璃基底上不规则银纳米结构的生长及其光学性质的研究

以经过硅烷化后玻璃片为基底,之后吸附金纳米种子,采用柠檬酸钠为还原剂,在荧光灯照射条件下还原硝酸银,制备出基底表面具有银纳米粒子聚集结构的材料。采用透射电镜、扫描电镜和紫外可见分光光度计对产物的形貌和性质进行了表征,并考察银纳米粒子的形貌对其薄膜基底SERS活性的影响。结果表明：随着光照时间增加至16 h,金种子长大为平均粒径110 nm的不规则状多晶银纳米粒子,且出现双层粒子堆积。基底上纳米粒子的吸收光谱上出现了由银粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰：随着光照时间的变化,耦合峰在600～813 nm波段内移动。光照时间为12 h后得到的SERS活性基底具有最强的SERS信号。     

银纳米粒子自组装复合LB膜的结构与性质

纳米粒子的自组装和有序组装膜的结构与性质近年来受到了人们的广泛关注,纳米粒子的表面结构与性质对由其组装成的有序膜的结构与性质有直接的影响。文章报道了利用自组装技术制备的银纳米粒子与双亲有机分子的单层和多层复合LB膜,通过吸收光谱和表面增强拉曼光谱研究了银纳米粒子与吸附分子间的相互作用,探讨了复合膜的成膜特性及银纳米粒子的拉曼增强特性。十八胺/银粒子复合LB膜的吸收光谱及拉曼光谱显示,十八胺分子与银纳米粒子表面的活位通过NH₂中的氮原子以复合体的形式结合;同时,在激发光的作用下复合体可能存在光催化过程。根据银粒子复合LB膜的实验结果,十八胺和十八酸之间的反应产物在复合膜中起空间位阻作用,与银粒子表面的相互作用较弱。     

金属铁纳米粒子的液相制备表面修饰及其结构表征

报道在知性剂存大的条件下于乙醇／水的简单液相体系中以ＫＢＨ４还原制备金属铁纳米粒子,然后再用含镍盐修饰溶液进行原位粒子的表面修饰,并通过Ｘ射线衍射（ＸＲＤ）、光电子能谱分析（ＸＰＳ）、透射电子显微分析（ＴＥＭ）、选区电子衍射（ＥＤ）表征和讨论所得产物粒子的形貌结构特征和粒子大小。结果表明,初始生成的金属铁纳米粒子与修饰溶液的电化学反应形成以金属纳米铁核为中心的具有较好稳定性的多层复合结构。     

银纳米粒子自组织二维有序阵列

采用液液二相转移方法合成出颗粒直径为(4.18±0.5)nm的银纳米粒子溶胶,并用紫外可见光谱对所制得的银纳米粒子溶胶的单分散性和稳定性进行了研究.结果表明,所得到的溶胶相为稳定的、粒径分布窄的单分散体系.红外光谱的分析结果表明,稳定剂1壬基硫醇包缚在银纳米粒子表面.并且,通过自组织方法获得了二维有序的银纳米粒子阵列 关键词： 银纳米粒子 液液二相转移方法 自组织 二维有序阵列     

三元复合材料PANI/Ag/MWNT的电化学行为和比电容

通过原位聚合的方式在银纳米粒子/多壁碳纳米管(Ag/MWCNT)复合材料的表面成功聚合苯胺单体制备了聚苯胺/银纳米粒子/多壁碳纳米管(PANI/Ag/MWCNT)三元复合材料苯．通过对三元复合材料的结构以及表面形貌进行分析,表明聚苯胺层完全包覆了Ag/MWCNT复合材料,形成了核壳式结构．同时银纳米粒子则以单质晶体的形态存在于多壁碳纳米管与聚苯胺层之间．三元复合材料电极在1 mol/L的KOH溶液中具有极低的阻抗,而与聚苯胺电极相比,这些复合材料电极则表现出更低的电阻、更高的电化学活性和更好的循环稳定性．尤其是当苯胺和Ag:MWCNTs质量比为5:5时,该复合材料电极在0.25 A/g的电流密度下表现出最大的比电容值为160 F/g．     

玻璃基底上不规则银纳米结构的生长及其光学性质的研究

以经过硅烷化后玻璃片为基底，之后吸附金纳米种子，采用柠檬酸钠为还原剂，在荧光灯照射条件下还原硝酸银，制备出基底表面具有银纳米粒子聚集结构的材料。采用透射电镜、扫描电镜和紫外可见分光光度计对产物的形貌和性质进行了表征，并考察银纳米粒子的形貌对其薄膜基底SERS活性的影响。结果表明：随着光照时间增加至16 h，金种子长大为平均粒径110 nm的不规则状多晶银纳米粒子，且出现双层粒子堆积。基底上纳米粒子的吸收光谱上出现了由银粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰：随着光照时间的变化，耦合峰在600～813 nm波段内移动。光照时间为12 h后得到的SERS活性基底具有最强的SERS信号。     

Silver nanoplates: controlled preparation, self-assembly, and applications in surface-enhanced Raman scattering

Silver nanoplates were prepared in a dual reduction system with NaBH₄ and sodium citrate both as reducing agents. And then the as-prepared nanoplates could be growing up through multistage growth methodology. The average edge length of Ag nanoplates can be tailored from 40 nm to 260 nm without changing their shape, crystallinity, and the average thickness. Furthermore, the effectiveness of these silver nanoplates as substrates prepared by the silanization self-assembly method toward surface-enhanced Raman scattering (SERS) detection was evaluated by using 4-aminothiophenol (4-ATP) and rhodamine 6G (R6G) as probe molecules. It was found that the enhancement ability of the silver nanoplates film is remarkable lower than that of the spherical silver nanoparticle film. The reason is attributed to the electromagnetic mechanism and chemical mechanism. This work will be of great significance in understanding the SERS enhancement mechanism and in the fabrication of nanoparticle films for biosensing.     

对痕量羊角材料降解产物的表面增强拉曼光谱研究

将一定浓度的硝酸银与柠檬酸三钠混合后,利用微波加热法制备纳米银溶胶,该方法加热速度快、温度分布均匀、反应条件易控制。采用准弹性激光散射技术检测其粒度大小及分布状态的信息,测得其平均粒度为(53.27±2.65)nm,粒度大小集中分布在56 nm左右。然后以之作为表面增强拉曼光谱(SERS)的活性基底,研究测定羊角痕量降解产物的SERS光谱。结果发现,羊角降解产物的表面增强拉曼效应显著,尤其在659,830,850,929,999,1 028,1 280,1 439,1 599 cm-1等多处出现了明显的拉曼振动峰,这些谱峰反映了羊角降解产物的生化成分信息。并且通过对所获得的羊角降解产物SERS信号进行的谱峰归属分析表明,羊角降解产物主要为氨基酸与多肽类物质。运用表面增强拉曼光谱检测角材料的降解产物,获得较高的灵敏度,可测定浓度低至ppm水平的痕量降解产物,本研究表明,SERS可能为羊角等角材料降解产物的检测提供一种快速、直观、准确的新方法。     

Influence of several factors on the growth of selenium nanowires induced by silver nanoparticles

This paper presents a study on the crystallization and growth mechanism of selenium nanowires induced by silver nanoparticles at ambient conditions with special reference to the effects of factors such as the shapes and size of silver nanoparticles, the induced reaction time, and the molar ratio of Ag⁰ to SeO₃²⁻ ions. The synthesis approach is conducted with no need of any stabilizers, and with no sonochemical process and/or templates. It is found that whether silver spherical particles or colloids can lead to the formation of nanowires with average diameter of 25 nm and lengths up to a few micrometers, and silver nanoplates lead to the formation of flat Se nanostructures. In particular, Au, Cu, Pt, and Pd particles cannot induce the growth of selenium nanowires in aqueous solution at room temperature. The results indicate that silver particles play a critical role in determining the growth of selenium nanowires. The lattice match between hexagonal-Se and orthorhombic- or trigonal-Ag₂Se particles is the major driving force in the growth of such nanostructures. The findings would be useful for design and construction of heterogeneous nanostructures with similar lattice parameter(s).     

正电性胶态纳米银中加入凝聚剂后的表面增强拉曼光谱

在柠檬酸还原制备的正电性胶态纳米银中加入凝聚剂HNO₃和NaNO₃后,用波长为633 nm的激光激发,获得了较强的表面增强拉曼散射光谱(SERS谱),通过讨论及实验明确该SERS谱是来自于还原剂中的柠檬酸根离子,并说明该方法制备的纳米银的吸附层是带正电的银离子,扩散层是带负电的柠檬酸根离子。     

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。     

Surface‐enhanced Raman scattering (SERS) spectra of hemoglobin on nano silver film prepared by electrolysis method

Nano silver films were prepared by the electrolysis method. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were employed to detect the morphology of the silver particles. The surface‐enhanced Raman scattering (SERS) spectra of the hemoglobin on nano silver film were recorded. It is seen from the SERS spectra that the nano silver films can enhance the Raman signals of the hemoglobin efficiently, and sodium citrate and phosphate buffered saline have no influence on the SERS spectra of hemoglobin. The electrolysis technique to fabricate this highly bioactive, stable, reusable, and low‐cost SERS substrate will be useful in the development of hemoglobin detection methods. Copyright © 2009 John Wiley & Sons, Ltd.     

Synergistic effect of silver seeds and organic modifiers on the morphology evolution mechanism of silver nanoparticles

Triangular, truncated triangular, quadrangular, hexagonal, and net-structured silver nanoplates as well as decahedral silver nanoparticles were manipulatively prepared starting from silver nitrate and silver seeds in the presence of poly(ethylene glycol) (PEG), poly(N-vinyl pyrrolidone) (PVP), and Tween 80 at room temperature, respectively. UV-vis spectroscopy, XRD, HRTEM, SAED, and FTIR were used to illustrate the crystal growth process and to characterize the resultant silver nanoparticles. It was found that the silver seeds and organic modifiers synergistically affected the morphology evolution of the silver nanoparticles. The co-presence of silver seeds and PEG was beneficial to the formation of triangular and truncated triangular silver nanoplates; the silver seeds and PVP favored the formation of polygonal silver nanoplates; the silver seeds and Tween 80 preferred to the formation of net-structured silver plates. The morphology evolution of the resultant silver nanoparticles was correlated with the crystallinity of the silver seeds and the adsorption ability of the organic modifiers on the crystal surfaces.     

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。     

Nanoplates controlled synthesis and catalytic activities of silver nanocrystals

The silver nanostructures, from nanoparticles (NPs) to nanorod and nanoplate, can be synthesized quantitatively with DMF (N,N^′$N,N^{\prime }$-dimethyl formamide) and PVA (Polyvinyl alcohol). Due to the anisotropic shape feature, the absorption spectra of the nanoplates prove to be quite different from that of spherical NPs. It may be due to the specific interaction between OH groups and Ag+ ions, which affect selective growth of various planes of silver nanocrystals. In addition, the catalytic activity of the obtained different shaped silver nanocrystals for hydrogen production has also been investigated. The silver nanoplates exhibit higher catalytic activities than silver NPs.     

电解法制备纳米溴化银溶胶及其SERS活性研究

将一定量的十六烷基三甲基溴化铵溶于500 mL去离子水中作为电解液,用直径为1.0 cm、长为10.0 cm银棒分别作为阴及阳电极,加上7 V直流电压,通电 3 h,用电解方法得到了乳白色的纳米溴化银溶胶。用吸收光谱、对该进行研究。其吸收峰为292.5 nm, 透射式电镜表明纳米溴化银粒径分布在一个较大的范围,既有大小不一的球形粒子,也有大小不一的椭球形粒子,部分粒子产生了凝聚。为测试该纳米溴化银溶胶是否具有表面增强拉曼散射(SERS)活性,选用了阳离子型分子甲基橙(Methyl orange)、中性分子苏丹红(Sudan red)及吡啶(Pyridine)作为测试分子,用二次去离子水配成适当浓度后,与纳米溴化银溶胶按1∶1的比例混合后,置入毛细管样品池中用Renishaw 2000测定,激发波长514.5 nm。结果发现电解法制备的纳米溴化银对这三种分子都具有较强的SERS活性,甲基橙中明显增强的峰是1 123,1 146,1 392,1 448,1 594 cm-1;苏丹红中明显增强的峰是1 141,1 179,1 433,1 590 cm-1;吡啶中明显增强的峰是1 003,1 034,1 121 cm-1。值得注意的是在该方法制备的纳米溴化银上,得到了在常规方法制备的黄银胶、灰银胶上得不到的甲基橙分子的SERS谱,对可能的原因进行了讨论。