自组装银纳米粒子及其SERS增强效应

采用柠檬酸三钠还原硝酸银方法制备出银纳米粒子, 并通过在玻璃表面修饰3-氨基丙基-三乙氧基硅烷( APTES)对银纳米粒子进行自组装。利用紫外-可见(UV-Vis)吸收光谱和扫描电子显微镜(SEM)测试手段对样品进行分析和表征。由测试结果可知银纳米粒子的尺寸比较均匀, 组装致密度较高, 基本以亚单层的形式分布于基底表面。进一步研究了以结晶紫(CV)为探针分子的自组装基底的表面增强拉曼光谱(SERS), 计算发现该基底的拉曼增强因子数量级达106。结果表明: 银纳米粒子自组装基底具有良好的SERS增强效应, 为痕量CV的检测提供了有效的方法。     

偶联分子对金纳米粒子在玻片上组装的影响

将金纳米粒子组装在用3-氨基丙基-三乙氧基硅烷(APES)修饰的普通玻片上,再分别用偶联分子对巯基苯胺、1,4-二巯基苯在该基底上再次组装金纳米粒子,结果表明用对巯基苯胺作为组装的偶联分子得到双层金纳米粒子结构,对巯基苯胺的表面增强拉曼光谱信号得到增强,而用1,4-二巯基苯作为组装的偶联分子得到单层金纳米粒子结构。     

微波合成银包覆金纳米粒子膜的拉曼散射活性研究

采用微波加热加压法和静电吸附自组装法在石英玻璃表面制备了银包覆金纳米粒子薄膜,利用原子力显微镜分析了薄膜的表面形态和结构,测定结晶紫分子在薄膜表面的拉曼光谱。结果表明,银包覆金纳米粒子薄膜具有很强的表面增强拉曼散射效应(SERS)活性和稳定性。     

DNA诱导金纳米粒子自组装及其SERS表征

首先将巯基DNA分子与金纳米粒子偶联,并用琼脂糖凝胶电泳分离出含不同DNA分子数目的金纳米粒子,最后将修饰有互补DNA链的Au纳米粒子进行组装,得到组装体(五聚体)。透射电子显微镜(TEM)研究表明,DNA-Au纳米组装体被成功地获得;表面增强拉曼光谱(SERS)研究表明,与未组装的金纳米粒子相比,DNA-Au纳米组装体具有更强的SERS活性。     

金属纳米粒子自组装多层结构的光谱特征

分别以对巯基苯胺和1,4-二巯基苯为偶联分子,采用自组装方法,在功能化玻片上组装了二层和三层银纳米粒子有序结构.实验发现,耦联于一、二层组装体中的对巯基苯胺的拉曼散射可由粒子间电磁偶合和电荷转移而显著增强.但第二层组装银纳米粒子上1,4-二巯基苯的吸附可导致组装体中对巯基苯胺的拉曼散射强度显著减弱,这与分子吸附导致的粒子中电荷分布的改变密切相关.纳米粒子的进一步组装使得1,4-二巯基苯的拉曼光谱有所增强.     

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。     

金纳米粒子自组装薄膜的光谱学研究

采用柠檬酸钠还原氯金酸制备了金胶体，通过静电自组装制备了金纳米粒子薄膜，利用紫外-可见光吸收光谱等对金纳米粒子薄膜进行了光谱学研究，紫外-可见光吸收光谱表明所制备的金溶胶为单分散体系，根据自组装薄膜的X-射线衍射谱，由谢乐公式估算金纳米粒子的粒径约为21nm；X-射线光电子能谱显示氯金酸的还原反应比较完全，金主要以Au^0的价态存在，金胶体粒子通过静电吸引机制组装到PDDA改性的衬底表面；紫外-可见光吸收光谱和表面增强拉曼光谱显示，由于粒子间的电磁耦合，自组装金纳米粒子薄膜表现出协同等离子体共振吸收行为和表面增强拉曼散射效应。     

金纳米粒子组装体系的表面增强拉曼光谱特性研究——表面粒子密度与拉曼光谱强度的关系

利用纳米粒子组装制备了金基底———巯基苯胺自组装膜偶联层———金纳米粒子的“三明治”结构,研究了表面粒子密度与偶连层分子的拉曼光谱强度的关系。实验结果显示,该结构对偶连层分子的拉曼光谱有很好的增强效应,增强因子可达１０５。在表面粒子密度较低时,拉曼光谱强度与表面粒子密度曲线呈线形,随着表面粒子密度的增加,曲线出现负偏差并在粒子密度较高区域出现一个平台。     

组装阵列中耦联剂对表面增强拉曼光谱的影响

利用自组装技术,将不同浓度比例的对巯基苯胺和N,N'-二苯基硫脲为功能耦联分子,在光滑银基底表面组装不同表面密度的二维银纳米粒子阵列。通过对组装阵列和粗糙银表面耦联剂分子的表面增强拉曼光谱比较,阵列中对巯基苯胺分子拉曼信号得到了明显的增强,但只有微弱的N,N'-二苯基硫脲的拉曼增强信号,说明在这种组装阵列中得到的拉曼散射增强主要来自于银纳米粒子和光滑银表面之间。     

金纳米粒子组装体系的表面增强拉曼光谱特性研究：表面粒子密度与？…

利用纳米粒子组装制备了金基底－－巯基苯胺自组装膜偶联层－－金纳米粒子的“三明治”结构,研究了表面粒子粒子密度与偶连层分子的拉曼光谱强度的关系。结果 偶连层分子的拉曼光谱有很好的增强效应,增强因子可达１０＾５。在表面粒子密度较低时,拉曼光谱强讧民表面粒子密度曲线呈线形,随着表面粒子密度的增加,曲线出现偏差并在粒子密度较高区域出现一个平台。     

新型C60衍生物／Ag复合纳米材料的制备及光谱性质

利用1,3-偶极环加成反应合成了联吡啶基C60单加成衍生物N-甲基-2-[4′-(4″-甲基-2′,2″-联吡啶基)]-3,4-C60吡咯烷(C60BPY),并用NaBH4还原法和银溶胶直接组装法制备了C60BPY/Ag复合纳米结构。透射电子显微镜(TEM)表明,两种复合纳米结构的粒子粒径分别在30~45nm和40~55nm之间,粒子形状较规则,且分散性较好。在复合纳米结构形成过程中,C60BPY分子有效地控制了银粒子的生长和团聚,起到了很好的稳定和分散作用。紫外-可见吸收光谱中,两种复合纳米结构分别在430和490nm处出现了银纳米粒子的表面等离子体共振吸收峰,说明随着粒径的增大,吸收峰发生了红移。荧光发射光谱显示,C60BPY/Ag复合纳米体系猝灭了C60BPY在720和805nm处的发射峰,并对其机理进行了探讨。这种复合纳米体系有望在光电器件、传感器及催化领域有潜在的应用前景。     

Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of ?41.98 mV for the gold nanoparticles and ?53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.     

Optical properties of monodispersed silver nanoparticles produced via reverse micelle microemulsion

Silver nanoparticles produced by the sodium borohydride reduction of silver nitrate were stabilized by means of 1-dodecanethiol providing sulfur atom. (n-Dodecyl) trimethylammonium bromide (DTAB), which was used as a phase transfer agent in two-phase system involving water and toluene, played a significant role in the formation of monolayer-protected silver nanoparticles. These nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible absorption spectroscopy (UV-vis), FT-IR spectra and fluorescence. The results indicate that the system is monodispersed and leads to the self-assembly of silver nanoparticles into 0-D quanta-dot arrays.     

SERS of plant material

Colloidal gold and silver were formed by the spontaneous reduction of metal salts by plant tissue—alfalfa seeds, green tea leaves, carrots and red cabbage. The colloids were analyzed using electron microscopy and spectroscopic tools. The reduction process yielded stable gold colloids, but for silver the colloidal particles were bigger and less stable, tending to form aggregates. The formation of metal colloids enabled surface‐enhanced Raman spectra (SERS) measurements, yielding specific vibrational signatures for the plant components in the proximity of the colloids. The main SERS peaks were attributed to nicotinamide adenine dinucleotide (NAD) and other adenine‐containing materials. Other peaks were assigned to flavins [e.g. flavin adenine dinucleotide (FAD)], chlorophyll, lipids and other biocomponents. Since the SERS spectra did not show any antioxidants common to all four different types of plant tissue, it is proposed that NAD and FAD compounds that play an important role in the respiration process may be involved in the metal reduction process. Copyright © 2007 John Wiley & Sons, Ltd.     

The Effect of L-Cysteine on Surface-Enhanced Raman Scattering of Malachite Green in Silver Colloids

ABSTRACT

Colloidal silver nanoparticles were prepared by a simple chemical reduction method. The effect of L-cysteine on the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was investigated by using malachite green as a probe molecule. It was found that the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was improved tremendously with the help of L-cysteine. The possible reasons for this enhancement effect were given. Specifically, in silver colloidal solution, no surface-enhanced Raman scattering spectrum of malachite green was observed at a relatively low concentration (≤2.5 × 10^?5 mol/L). However, well-resolved and high-quality surface-enhanced Raman scattering spectra of malachite green were successfully obtained after the addition of L-cysteine to silver colloids, and the minimum detection limit for malachite green was down to 10^?8 mol/L.     

Self Assembly of the Metal Nanoparticles: Formation of the Highly Oriented,Core-Shell Type,Bimetallic Gold–Silver Film

A synthetic route is presented for the preparation of a bimetallic gold–silver film under UV-irradiation. Methoxy polyethylene glycol, a water soluble polymer, is used as the reducing agent for the gold and silver ions in the presence of a ultra-violet source that results in the formation of gold and silver bimetallic nanoparticles. During stirring a centrifugal force is generated at the center of the solution, which results in a coalescence of the nanoparticles and forms a self-assembly of small subunits that ultimately produces a film-like network. UV–vis spectra and scanning electron microscopy were used to determine, respectively, the configuration of the gold and the silver in the nanoparticles, a Au_core–Ag_shell structure, and the thickness of the film.     

银纳米粒子对组装阵列中耦联分子拉曼散射的影响

分别用硼氢化钠和氢气还原法制备了两种不同的银溶胶(I和II),并采用自组装技术将银纳米粒子组装到对巯基苯胺(PATP)修饰的光滑银基底表面,形成银纳米粒子亚单层二维阵列。比较两种阵列中PATP的表面增强拉曼光谱发现,溶胶II所得阵列中的PATP的b2振动得到了较大的增强,即存在较大程度的电荷转移,说明银纳米粒子的性质直接影响了耦联分子的光谱特征。对溶胶Ⅰ进行离心处理,组装,得到的拉曼特征与阵列II类似。就溶胶II的银纳米粒子而言,组装结构中可能形成Ag-N化学键,从而导致更强的氨基与银粒子的相互作用。     

金纳米粒子掺杂DNA-CTMA-DPFP薄膜的表面增强拉曼散射特性

采用柠檬酸三钠还原氯金酸和离子交换法制备金纳米粒子掺杂DNA-CTMA材料,利用钯催化反应合成9,9-二乙基-2,7-二-(4-吡啶)芴荧光染料(DPFP),将DPFP与DNA-CTMA混合后,旋凃制备金纳米粒子掺杂的DNA-CTMA-DPFP薄膜样品。通过吸收光谱、荧光光谱和拉曼光谱的测量,研究了薄膜样品的光学特性和表面增强拉曼散射(SERS)特性。实验结果表明,薄膜样品在300～360 nm的吸收主要来自DPFP,在500～700 nm的吸收来自样品中金纳米粒子的局域表面等离子共振;样品在370,386,408 nm处的荧光峰分别对应DPFP的S₁₀-S₀₀、S₁₀-S₀₁和S₁₀-S₀₂能级的电子振动跃迁;在785 nm激光激发下,薄膜样品的拉曼散射主要来自DPFP分子,随着金纳米粒子掺杂比的增大,DPFP分子的拉曼散射峰强度逐渐增强。因此,金纳米粒子掺杂DNA-CTMA薄膜适合作为多种染料分子的SERS基底。     

Seedless synthesis of gold nanorods with longitudinal surface plasmon resonance wavelength of 1200 nm

Gold nanorods with the longitudinal plasmonic resonance peak position up to 1200?nm are prepared using an improved seedless synthetic technique. In this method, dopamine is employed as the weak reducer, whereas cetyltrimethylammonium bromide and sodium oleate are used as the binary surfactant mixture. Gold nanorods produced at various amounts of silver nitrate and hydrochloric acid were characterized by visible-near-infrared spectroscopy and scanning electron microscopy. Results show that the sizes, length-to-width aspect ratios, and the corresponding longitudinal surface plasmon resonance peaks of the synthesized gold nanorods can be tuned by altering the silver nitrate and hydrochloric acid amounts. The present method provides a new procedure for fabrication of gold nanorods with a broad range of plasmonic resonance peaks, which has a great potential for applications such as photothermal therapy and sensing.