金银纳米粒子的电化学性质及联苯胺的SERS研究

采用柠檬酸钠还原氯金酸,硼氢化钠还原硝酸银分别制备了较小粒径的金、银纳米粒子。运用紫外可见吸收光谱(UV-Vis)、扫描电子显微镜(SEM)、循环伏安法(CV)对金、银纳米粒子进行了表征。结果表明：所得金、银纳米粒子粒径分别约为16和10 nm,并能以亚单层形式组装于导电玻璃(ITO)表面;CV图显示金、银纳米粒子分别有一对不对称的氧化还原峰,而且纳米粒子的浓度对其氧化还原电位存在一定的影响。采用自组装方法,以联苯胺为偶联分子, 在粗糙金基底表面构筑了金/银纳米粒子的双层有序结构。表面增强拉曼光谱研究表明, 在有序金银纳米粒子组装体中偶联分子的拉曼散射得到了增强。     

Co掺杂ZnO纳米棒的共振拉曼光谱和发光特性

采用X射线衍射(XRD)和透射电子显微镜(TEM)手段对微乳液法合成的Zn0.9Co0.1O纳米棒进行了表征.通过室温下的共振拉曼光谱和光致发光光谱手段,研究了所合成纳米材料的共振拉曼光谱和发光特性,并与体相ZnO的研究结果对比,发现合成的材料具有四阶声子紫外共振拉曼散射,而体相材料只有两阶,并观察到在紫外和可见区域所...     

电荷转移对纳米金属吸附分子拉曼光谱影响

在金,银纳米粒子表面修饰对巯基苯胺(PATP)分子,对其进行紫外及拉曼光谱性质表征。紫外吸收光谱显示修饰了单分子层的纳米粒子表面等离子体共振发生较大的红移,银粒子位移程度大于金粒子的。其拉曼散射增强效应研究表明,对巯基苯胺b2振动模式的极大增强是由电磁增强和化学增强效应共同决定的。金、银粒子上对巯基苯胺单分子层拉曼散射增强效应的差异主要来自金属与对巯基苯胺之间电荷转移能力的不同。     

巯基乙胺的表面增强拉曼光谱研究

拉曼光谱用于检测物质。但由于物质的普通拉曼信号较弱,因此在微量检测应用中受到限制。本文通过尝试获得了巯基乙胺(C_2H_7NS)粉末、巯基乙胺在纳米银溶胶中的表面增强,巯基乙胺与纳米银粒子在载玻片上自组装纳米银膜的表面增强等的拉曼光谱。应用紫外-可见吸收光谱仪、电子扫描显微镜、电子透射显微镜来对纳米银胶、纳米银膜进行形貌表征。应用Guassian03软件计算出巯基乙胺的拉曼峰,对实验得到的拉曼峰进行对比和归属。对实验得到的拉曼峰比较,巯基乙胺与纳米银粒子在载玻片上自组装纳米银膜获得的表面增强拉曼光谱较好。通过改变巯基乙胺与纳米银粒子在载玻片上自组装时间长短来对该方法进一步优化。     

一种制备金纳米粒子的新方法

报道了一种温和的、低成本、有效制备高纯度单分散金纳米粒子的新方法.采用种子生长法,在表面活性剂十八烷基苄基二甲基氯化铵(BDAC)体系下液相合成金纳米粒子.通过改变实验中反应温度和反应时间等条件,制备了粒径为25-50nm的金纳米粒子,运用透射电子显微镜(TEM)对纳米粒子的形貌进行分析,利用紫外可见光谱(UV-Vis)对产物进行光谱表征,并讨论了金纳米粒子的形成机制.结果表明,金纳米粒子的粒径随反应温度的升高及反应时间的加长有增大的趋势.     

不同粒径、超均匀球形金纳米粒子合成及其表面增强拉曼散射效应研究

以氯金酸为原料,抗坏血酸为还原剂,柠檬酸钠为保护剂,用化学还原(种子生长)法制备了不同粒径、超均匀的球形金纳米粒子溶胶,并通过紫外可见吸收光谱(UV-Vis)和扫描电子显微镜(SEM)进行表征。结果表明,随着金纳米粒子粒径的增大,其UV-Vis光谱中的吸收峰发生红移并出现四极峰。为进一步研究金纳米粒子表面增强拉曼散射(SERS)效应的作用机理并优化其灵敏度,我们以罗丹明6G(R6G)为探针分子,对不同粒径的金纳米粒子进行SERS表征,发现R6G的SERS信号随着金纳米粒子的增大先增强后减弱。当金纳米粒子的平均粒径达到120 nm时,产生最强SERS信号增强,增强因子约为1.1×107。三维时域有限差分法(3D-FDTD)理论模拟纳米粒子阵列电磁场分布结果与实验数据的趋势一致。     

银纳米粒子阵列的自组装及其表面增强拉曼光谱应用

在以聚赖氨酸为表面耦联层分子的玻片基底制备了银纳米粒子阵列。ＳＥＭ表征结果表明,银粒子以亚单层的形式排列在基底表面。比较银溶胶和纳米粒子阵列的紫外可见光谱可见聚赖氨酸耦联层对银纳米粒子的粒径具有一定的选择性,甲基紫精在银纳米粒子阵列上的表面增强ＦＴ拉曼光谱表明在近红外区拉曼散射的表面增强主要来自于化学增强效应。     

半胱氨酸修饰金纳米棒光学性质的研究

采用种子生长法制备了不同长径比的金纳米棒,并通过金硫键的结合在其表面包覆半胱氨酸分子。利用紫外-可见吸收光谱仪,扫描电子显微镜以及拉曼光谱仪等对样品进行分析和表征。实验结果表明金纳米棒产率较高,且一致性较好。表面修饰后的金纳米棒的纵向吸收峰发生蓝移,表明半胱氨酸分子与金纳米棒的结合有助于溶液分散性的提升。以结晶紫为探针分子,随着金纳米棒长径比的增加其拉曼增强效果变强。进一步分析发现,修饰后的金纳米棒的表面增强拉曼光谱的增强效果并未受到影响。通过金纳米棒与半胱氨酸分子牢固的结合,一方面可以提高金纳米棒溶液的分散性与稳定性;另一方面半胱氨酸分子可为金纳米棒修饰其它有机官能团提供了一个牢固的桥梁,有效地拓展了金纳米棒的应用方向。     

不同形貌金纳米粒子的制备及其表面增强拉曼散射效应的研究

不同形状的金纳米粒子在表面增强拉曼散射(surface enhanced Raman scattering,SERS)中有不同的增强效果,多面体金纳米粒子具有多角结构,显示出比金纳米板更为明显的增强效果,近年来对其合成和性质的研究备受关注。该研究探究了十二面体,二十面体,三角板,球形四种形状的金纳米粒子在SERS中不同的增强效果。分别采用硼氢化钠还原法和以N,N-二甲基甲酰胺(DMF)为还原剂制备金三角纳米片和二十面体金纳米粒子,又以二十面体金纳米粒子为种子制备出十二面体金纳米粒子,并分别以以上三种不同形貌的金纳米粒子及球形金溶胶为基底,4-巯基吡啶,对巯基苯甲酸为探针分子检测了其在不同激发波长下的增强效果。透射电子显微镜结果表明金三角纳米板的平均边长为130nm,二十面体和十二面体金纳米粒子的粒径分别为100和120nm。三者的紫外可见吸收峰分别在589,598和544nm处。表面增强拉曼散射结果表明金多面体比金三角纳米板表现出更好的增强效果。     

金纳米粒子聚集体系的制备及其SERS效应表征

以Na2S作为金纳米粒子的还原制备与聚集剂制备了金纳米粒子聚集体系。在制备过程中通过紫外可见光谱对制备条件进行了优化。TEM表征显示聚集体系中的金纳米粒子均为球形,且聚集状态呈现出较好的均匀性。将这一聚集体系作为SERS基底应用于若干氨基酸分子的SERS光谱表征与分析。初步的研究表明Na2S-金纳米粒子聚集体系可有效地应用于生物分子的SERS光谱表征与分析。     

SERS detection of polychlorinated biphenyls using β‐cyclodextrin functionalized gold nanoparticles on agriculture land soil

A highly sensitive surface‐enhanced Raman scattering (SERS) platform for the selective trace analysis of persistent organic pollutant (POP) such as polychlorinated biphenyl (PCBs) was reported based on β‐CD modified gold nanoparticles (AuNPs) with the real environmental sample of polluted soil. The synthesized gold nanoparticles were characterized using UV–vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and transmission electron microscopy (TEM). In polluted soil the presentation of PCB is confirmed by using GC‐MS. It is further verified and confirmed by using SERS. When the contaminated soil was added to the system, the binding of soil with β‐CD resulted in the aggregation of AuNPs, and excellent Raman signal was obtained which can reflect the isomers of polychlorinated biphenyls. Copyright © 2015 John Wiley & Sons, Ltd.     

电解法制备纳米银溶胶及其SERS活性研究

分别用柠檬酸三钠溶液、硝酸银和聚乙烯醇混合液作为电解液,用银棒作为电极,加上7 V直流电压,通电1 h,用电解方法得到了纳米银溶胶。为测试该纳米银溶胶是否具有表面增强拉曼散射1(SERS)活性,选用了阳离子型分子碱性品红(Fuchsine basic)、亚甲基蓝(Methylene blue),阴离子型分子苯甲酸(Benzoic acid),甲基橙(Methyl orange)、中性分子吖啶橙(Alcidine orange)、苏丹红(Sudan red)作为测试分子,进行SERS研究,结果发现用两种电解液制备的纳米银都具有很强的SERS活性,但用硝酸银和聚乙烯醇混合液作为电解液制备的纳米银溶胶具有更广泛的SERS 活性。在该方法制备的纳米银上,得到了在常规方法制备的胶态纳米银上及用柠檬酸三钠溶液作为电解液制备的纳米银上得不到的甲基橙分子的SERS谱,对可能的原因进行了讨论。     

Characterization and optimization of AuNPs labeled by Raman reporters on glass based on silver enhancement

In this report, gold nanoparticles (AuNPs) labeled by Raman reporters (AuNPs‐R6G) were assembled on glass and used as the seeds to in situ grow silver‐coated nanostructures based on silver enhancer solution, forming the nanostructures of AuNPs‐R6G@Ag, which were characterized by scanning electron microscopy (SEM) and UV‐visible spectroscopy. More importantly, the obtained silver‐coated nanostructures can be used as a surface enhancement Raman scattering (SERS) substrate. The different SERS activities can be controlled by the silver deposition time and assembly time of AuNPs‐R6G on glass. The results indicate that the maximum SERS activity could be obtained on AuNPs‐R6G when these nanostructures were assembled on glass for 2 h with silver deposition for 2 min. In addition, the reproducibility of SERS signal on the fabricated nanostructures is very high with the intensity error lower than 15%, which has great promise as a probe for application in bioanalysis. Copyright © 2008 John Wiley & Sons, Ltd.     

Selective SERS detection of each polycyclic aromatic hydrocarbon (PAH) in a mixture of five kinds of PAHs

This paper reports the qualitative analysis and quantitative detection of polycyclic aromatic hydrocarbon (PAH) molecules with per‐6‐deoxy‐(6‐thio)‐β‐cyclodextrin (CD‐SH) modified gold nanoparticles (AuNPs) by surface‐enhanced Raman scattering (SERS) spectroscopy. For the selective sensing of PAHs, which are environmental pollutants with very low affinity to metallic surfaces, by SERS, a stable substrate with AuNPs and CD‐SH was utilized by supramolecular interaction. Quantitative detection of each PAH was carried out by SERS on inclusion complexes with different concentrations. From the SERS spectra of a mixture of five different PAHs, we could easily distinguish each PAH by its discriminant peaks. In addition, quantitative analysis of one component in a mixture of five PAHs was also investigated. This sensing platform revealed matching relationship between the host and the guest and the host–guest interaction mechanism. The proposed approach for the selective detection of PAHs holds great potential in the detection of environmental organic pollutants. Copyright © 2010 John Wiley & Sons, Ltd.     

Portable smart films for ultrasensitive detection and chemical analysis using SERS and SERRS

Metallic nanostructures, much smaller than the wavelength of visible light, which support localized surface plasmon resonances, are central to the giant signal enhancement achieved in surface‐enhanced Raman scattering (SERS) and surface‐enhanced resonance Raman scattering (SERRS). Plasmonic driven SERS and SERRS is a powerful analytical tool for ultrasensitive detection down to single molecule detection. For all practical SERS applications a key issue is the development of reproducible and portable SERS‐active substrates, where the most widely used metals for nanostructure fabrication are silver and gold. Here, we report the fabrication of a ‘smart film’, containing gold nanoparticles (AuNPs), produced by in situ reduction of gold chloride III (Au⁺³) in natural rubber (NR) membranes for SERS and SERRS applications. The composite films (NR/AuNP membranes) show characteristic plasmon absorption of Au nanostructures, which notably do not influence the mechanical properties of the NR membranes. The term ‘smart film’ has to do with the fact that the SERS substrate (smart film) is flexible and standalone, which allows one to take it anywhere and to dip it into solutions containing the analyte to be characterized by SERS or SERRS technique. Besides, the synthesis of the AuNPs at the surface of NR films is much simpler than making an Au colloid and cast it onto a substrate surface or preparing an Au evaporated film. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Raman and SERS study of metoclopramide at different pH values

Conjugate acid–base forms of the drug metoclopramide were investigated by Raman spectroscopy in aqueous solutions and by surface‐enhanced Raman scattering (SERS), when the molecules were adsorbed on colloidal silver surfaces. Raman spectra were recorded at pH values below 8, metoclopramide being poorly water soluble at higher pH values. The SERS spectra of metoclopramide were recorded in the 3–11 pH range, even in spite of its low solubility at basic pH values. The Raman and SERS spectra were assigned by means of density functional theory (DFT) calculations. By monitoring several SERS marker bands, the protonated, neutral or the coexistence of both molecular species adsorbed on the colloidal silver particles could be evidenced. The adsorbate orientation was deduced to be perpendicular to the metal surface for the protonated molecular species and tilted for the neutral metoclopramide molecular species. Copyright © 2009 John Wiley & Sons, Ltd.     

Steric hindrance in cationic and neutral rhodamine 6 G molecules adsorbed on Au nanoparticles

The adsorption of cationic and neutral R6G molecules on Au nanoparticles was elucidated by surface enhanced Raman scattering (SERS). The steric hindrance at hydroethyl amino (‐N(H)Et) groups in R6G was evidenced by the observation that R6G⁺ adsorb on as‐prepared gold nanoparticles (AuNPs) only with electrostatic forces, in contrast to the electrostatic and chemical adsorption of R123⁺ with dihydro amino (‐NH₂) groups on as‐prepared AuNPs. Large steric hindrance at the amino groups in R6G yielded saturated coverage of 700 molecules/AuNP for R6G⁺ significantly fewer than 1000 molecules/AuNP for R123⁺. In addition, neutral R6G⁰ on AuNPs showed markedly enhanced peaks at 1200–1600 cm⁻¹, which were not observed in Raman spectra of R6G⁰ in bulk solution, and also in SERS of R6G⁺ on AuNPs. These bands are attributed to vibrational modes of an outer phenyl ring and ethyl amino groups, which are vertical to a xanthene plane, on the basis of theoretical analysis of molecular vibrations. Thus, Raman scattering of these bands is enhanced under an inclined orientation of R6G⁰ molecules chemisorbed on AuNPs via lone pair electrons at amino groups. Copyright © 2013 John Wiley & Sons, Ltd.     

SERS的煎炸食品中丙烯酰胺速测方法研究

丙烯酰胺是一种具有神经毒性、生殖毒性,遗传毒性及免疫毒性的化合物,被列为2A级致癌物。富含碳水化合物的食物经高温烹饪后,丙烯酰胺暴露风险极大,建立对丙烯酰胺的速测方法具有重要的意义和实用价值。表面增强拉曼光谱技术(SERS)近年来发展迅速,利用高SERS活性纳米结构基底可实现对目标物拉曼"指纹"信号的高灵敏增强。复杂基质中目标物的SERS快速分析需要高活性的基底和高效的净化技术。建立了一种基于复合纳米结构的煎炸食品中丙烯酰胺的SERS快速分析方法。利用纳米银阵列负载纳米金粒子(AgNR@AuNPs)作为增强基底,一是该基底基于AgNR纳米棒之间以及AuNPs纳米粒子之间双重"热点"增强作用,对丙烯酰胺具有较高的SERS增强活性;二是该基底中AgNR为固相基底,每次使用前,利用稀硝酸除去表面氧化物,大大提高了SERS分析稳定性。还研究了AuNPs粒径和样品添加顺序对分析灵敏度的影响。煎炸食品中基质干扰严重,结合QuECHERS快速净化技术,在优化除脂、萃取溶剂及净化材料的用量比例、种类的基础上,选择正己烷为除脂溶剂,水∶乙腈(V/V=1∶1)为提取溶剂, MgSO4+NaCl为净化材料, 5 min内完成检测。分析灵敏度1μg·kg-1,在5~100μg·kg-1内以Δν=1 482 cm^-1为定量峰,实现定量分析,线性相关系数r=0.985, 5个添加浓度下回收率为77.1%~93.6%,相对标准偏差小于4.0%。所建立的方法有望用于食品安全现场检测中。     

Synthesis of gelatin-capped gold nanoparticles with variable gelatin concentration

Gelatin-stabilized gold nanoparticles (AuNPs-gelatin) with controlled particle size were synthesized with simple variation of concentration of gelatin by reducing in situ tetrachloroauric acid with sodium citrate. The nanoparticles showed excellent colloidal stability. Transmission electron microscopy (TEM) revealed the formation of well-dispersed gold nanoparticles (AuNPs) with different sizes. The methodology produces particles 10–15 nm in size depending on the concentration of gelatin used. The measured AuNPs are 10, 11, 12, 13, 14, and 15 nm for AuNPs-gelatin 1, 0.5, 0.25, 0.1 and 0.05%, and pure AuNPs, respectively. The AuNPs-gelatin exhibit size-dependent localized surface plasmon resonance behavior as measured by UV–visible spectroscopy. UV–vis spectroscopy and TEM results suggest that higher concentration of gelatin favor smaller particle size and vice versa. FTIR spectroscopy analysis of AuNPs-gelatin revealed the amino bands and carboxyl peak of gelatin. The crystalline nature of AuNPs was investigated by X-ray diffraction.