利用聚碳酸酯模板制备的金纳米棒的表面增强Raman散射效应研究

采用聚碳酸酯模板和电化学沉积法制备基于金纳米棒的Raman场增强衬底, 制备的金纳米棒直径大约36 nm, 长约1 μm, 测试结果显示其共振吸收峰的位置约为540 nm. 比较了谐振和非谐振条件下的场增强情况, 并确定了场增益系数, 结果显示谐振激光激发下的增益比非谐振情况下提高了7.36倍. 本研究相对于前人的工作取得了如下进展: 一是讨论了谐振模式与非谐振模式下的金纳米棒的场增益系数, 利用谐振波长的激光激发金纳米棒, 进一步提高了场增益; 二是消除了聚碳酸酯模板分子的荧光背底, 使其在表面增强 Raman 散射方面的应用进一步变得可行. 关键词： 金纳米棒 表面增强Raman散射 聚碳酸酯模板     

银纳米颗粒阵列的表面增强拉曼散射效应研究

利用具有高密度拉曼热点的金属纳米结构作为表面增强拉曼散射(SERS)基底,可以显著增强吸附分子的拉曼信号.本文通过阳极氧化铝模板辅助电化学法沉积制备了高密度银(Ag)纳米颗粒阵列;利用扫描电子显微镜和反射谱表征了样品的结构形貌和表面等离激元特性;用1, 4-苯二硫醇(1, 4-BDT)为拉曼探针分子,研究了Ag纳米颗粒阵列的SERS效应.通过优化沉积时间,制备出高SERS探测灵敏度的Ag纳米颗粒阵列,检测极限可达10~(-13)mol/L;时域有限差分法模拟结果证实了纳米颗粒间存在强的等离激元耦合作用,且发现纳米颗粒底端的局域场增强更大.研究结果表明Ag纳米颗粒阵列可作为高效的SERS基底.     

超声提取防风多糖的抗氧化活性研究

采用不同电功率和频率的超声波辅助提取防风多糖,通过体外抗氧化实验,研究了多糖抗氧化活性与超声电功率及频率的变化规律。实验结果表明:超声频率为135kHz、电功率为290W时,提取的防风多糖得率最高,达到7.12%。超声频率在80kHz和135kHz,电功率范围在150W～220W时提取的防风多糖抗氧化活性较高。超声提取防风多糖能够提高提取效率,选择适当的电功率和频率能达到较好的抗氧化活性效果。     

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.     

Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ``breathing' of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.     

基于单个花状银纳米颗粒的表面增强拉曼散射效应研究

在室温下,以硝酸银为银源,抗坏血酸为还原剂,通过调节表面活性剂聚乙烯吡络烷酮的浓度,实现对花状银纳米颗粒的可控制备。利用扫描电子显微镜、原子力显微镜、X射线衍射和X射线能谱等手段检测并分析了材料的形貌结构和成分组成。实验结果表明,当聚乙烯吡络烷酮的浓度为0.1 mol/L时,所制备花状银纳米颗粒的表面结构达到最精细的状态且颗粒的尺寸达到微米量级,适合对单颗粒进行定位与光学性质研究。以结构最优化的花状银纳米颗粒为表面增强拉曼散射基底材料,以羟基苯甲酸为探针,对单个和少数颗粒的表面增强拉曼散射效应进行了研究,并借助暗场散射光谱分析了基底的表面增强拉曼散射机理。结果显示,该花状银纳米颗粒因其独特的表面结构为拉曼信号增强提供了大量“热点”。良好的拉曼性能以及较低的制备成本表明,该新型表面增强拉曼散射基底具有很大的应用前景。     

Raman scattering from microcrystals

This review discusses the size effects on Raman scattering from microcrystals. For ionic microcrystals, the existence of surface phonon modes is predicted from electromagnetic theories. It is shown that Raman spectroscopy is very effective to detect the surface phonon modes. The size effects on nonpolar phonons in covalent microcrystals can also be studied by Raman spectroscopy. However, the relaxation of the wave-vector selection rule or the phonon confinement explains only some of the experimental data. Development of lattice dynamical theories of Raman scattering from microcrystals including surface effects is highly required. Enhancement of Raman intensities arising from the excitation of electromagnetic normal modes of microcrystals is also discussed.     

A facile synthesis of branched silver nanowire structures and its applications in surface-enhanced Raman scattering

We report a facile method of preparing novel branched silvernanowire structures such as Y-shaped, K-shaped and other multi-branchednanowires. These branched nanostructures are synthesized by reducingsilver nitrate (AgNO₃) in polyethylene glycol(PEG) with polyvinglpyrrolidone (PVP) as capping agent. Statisticaldata indicate that for the “y” typed branched nanowire,the branches grow out from the side of the trunk nanowire in a preferentialorientation with an angle of 55? between the branch and the trunk.Transmission electron microscopy (TEM) studies indicate that the defectson silver nanowires could support the growth of branched nanowires.Conditions such as the molar ratio of PVP/AgNO₃, the reaction temperature, and the degree of polymerization of reducingagent and PVP play important roles in determining the yield of thesilver branches. Due to the rough surface, these branched nanostructurescan be used as efficient substrates for surface-enhanced Raman scatteringapplications.     

DFT理论探讨银电极表面吸附吡啶和水分子的表面增强拉曼光谱

本文利用密度泛函方法计算了吡啶和水分子分别吸附于粗糙银电极表面的拉曼光谱强度。结果表明,在不发生共振拉曼散射情况下,拉曼强度随电极表面负电荷量的增加而显著增大。理论预测与实验结果一致。     

聚甲基丙烯酸甲酯间隔的金纳米立方体与金膜复合结构的表面增强拉曼散射研究

金属纳米颗粒与金属薄膜的复合结构由于其局域表面等离子体和传播表面等离子体间的强共振耦合作用,可作为表面增强拉曼散射(SERS)基底,显著增强吸附分子的拉曼信号.本文提出了一种聚甲基丙烯酸甲酯(PMMA)间隔的90 nm金纳米立方体与50 nm金膜复合结构的SERS基底,通过有限元方法数值模拟,得到PMMA的最优化厚度为15 nm.实验制备了PMMA间隔层厚度为14 nm的复合结构,利用罗丹明6G (R6G)为拉曼探针分子, 633 nm的氦氖激光器作为激发光源,研究了复合结构和单一金纳米立方体的SERS效应,发现复合结构可以使探针分子产生比单一结构更强的拉曼信号.在此基础上,研究了不同浓度金纳米立方体水溶液条件下复合结构中R6G的拉曼光谱.结果表明,当金纳米立方体水溶液浓度为5.625μg/mL的条件下复合结构中R6G的拉曼信号最强,且可测量R6G的最低浓度达10~(–11) mol/L.     

界面自组装的金/氧化石墨烯复合材料的表面增强拉曼散射行为研究

采用Frens法制备金纳米粒子溶胶,通过界面自组装技术在掺磷的非晶碳衬底表面构筑三维的金/氧化石墨烯/金复合结构.以罗丹明B为探针分子,考察金/氧化石墨烯/金复合材料的表面增强拉曼散射活性.结果表明,由于氧化石墨烯的化学增强和金纳米粒子的电磁场增强的协同作用,在该三维复合材料上获得了很强的罗丹明B拉曼信号.所设计的三维金/氧化石墨烯/金复合材料在生物分析、环境监测、疾病防控、食品安全等领域具有潜在的应用价值.     

Surface-enhanced Raman scattering from the individual metallic single-walled carbon nanotubes

A new experimental technique has been presented to investigate the surface-enhanced Raman scattering (SERS) on “individual and untouched” single-walled carbon nanotubes (SWNTs) deposited onto gold or silver film-covered substrate through a direct CVD method. It was found that the radial breathing mode for SERS shows a narrower linewidth than the normal Raman spectroscopy (NRS). Relative to NRS, the SERS spectra also revealed a preferable contribution to some metallic component of the G line. However no obvious difference for D and G′ between SERS and NRS has been revealed, which is different from the previous results on bulk SWNT samples.     

Surface enhanced Raman scattering of 2-cyanopyridine adsorbed on silver colloidal particles

Surface-enhanced Raman scattering (SERS) spectra of 2-cyanopyridine (2 CP) adsorbed on silver colloidal particles have been investigated. The prominent SERS bands are observed at 556, 612, 778, 1002, 1060, 1072, 1150 and 1240 cm⁻¹. The absolute enhancement factor of the Raman signals in SERS studies has been estimated to be of the order of 10²–10⁵ for various bands. The 2CP molecules have been ascribed to adsorb on colloidal particles in standing up fashion.     

纳米结构Si表面增强拉曼散射特性研究

为了实现低成本高灵敏度的表面增强拉曼散射效应,制备了一种基于硅表面纳米结构的表面增强拉曼散射效应（SERS）衬底。首先利用低能反应离子注入的方法对单晶硅进行表面处理,制作高陡值度的墙壁结构。然后采用电子束蒸发的方式在硅片表面蒸镀银膜,高密度的银纳米点阵列出现在侧壁表面,形成大量的热点。实验采用罗丹明6G（R6G）作为探针分子进行表征,发现获得最强拉曼信号的银膜厚度为40 nm,R6G的探测极限能达到10^-14 mol/L;同时分析衬底的重复性和稳定性,发现在614 cm^-1和1 650 cm^-1处的拉曼信号特征峰的相对标准偏差分别达到12.3%和14.3%,保存一个月的衬底测得的拉曼信号强度保持不变。本研究提供了一种操作简单、成本低的制备高灵敏度增强拉曼效应衬底的方法,制备的衬底具有高信号可重复性和高稳定性的优点。     

Surface-enhanced Raman on gold nanoparticles for the identification of the most common adulterant of Astragali Radix

Adulterant is a common problem in Astragali Radix (a widely used Chinese herbal medicine). In this study, the surface-enhanced Raman technique was used to identify the authentic Astragali Radix and the most common adulterant with the aim to develop a convenient and sensitive method for the adulterant identification. Surface-enhanced Raman spectra combined with multivariate diagnostic algorithm differentiated the authentic Astragali Radix from the adulterant with high sensitivity (100%) and specificity (97.6%). This exploratory work demonstrates that surface-enhanced Raman technology can be used for the rapid and label-free screening of adulterant and has great potential for the quality control of Chinese herbal.     

Propagating surface plasmon polaritons for remote excitation surface-enhanced Raman scattering spectroscopy

To illustrate the attractive potentials of remote-excitation surface enhanced Raman scattering (RE-SERS), we review the fundamental concepts and typical applications of propagating surface plasmon polaritons (PSPPs). Based on the RE-SERS technic, the adsorbed molecules are protected from being directly illuminated, while the merits of SERS still remained. However, the critical limitations of applying RE-SERS hinder its rapid development. Hence, drawing an overview about the PSPPs would be beneficial for further promoting the significance of RE-SERS in biological application and investigating the mechanism of surface catalytic reactions.     

低维光电材料缺陷与界面增强拉曼散射

近年来,一系列新型低维光电材料相继涌现,展现出优异的性能.这些光电材料与表面增强拉曼散射(SERS)技术相结合,显示出巨大的应用潜力,有望成为高灵敏SERS活性基底.缺陷与界面调控是低维光电材料SERS应用的重要策略,本文将重点介绍新型低维光电材料缺陷与界面增强拉曼散射的种类和增强机理.通过对缺陷与界面增强拉曼散射的应...     

沉积铁钝化膜的傅立叶变换表面增强拉曼光谱

利用恒电流沉积技术、傅立叶变换表面增强拉曼散射技术现场研究了0 1mol/LNaOH溶液中铁金属电极在不同电位下的表面氧化物的组成。结果表明,在电极预钝化区,表面首先生成的Fe(OH)2可由拉曼谱图中出现的550cm-1表征,证实了以往的研究结果。进入钝化区,表面二价氧化物逐步转化为高价氧化物Fe3O4及α 、δ 和γ FeOOH。在电位回扫的过程中,各氧化产物的还原以及铁表面SERS活性的逐渐消失导致谱峰强度降低。     

An effective surface-enhanced Raman scattering template based on gold nanoparticle/silicon nanowire arrays

A large-scale Si nanowire array （SiNWA） is fabricated with gold （Au） nanoparticles by simple metal-assisted chemical etching and metal reduction processes. The three-dimensional nanostructured Au/SiNWA is evaluated as an active substrate for surface-enhanced Raman scattering （SERS）. The results show that the detection limit for rhodamine 6G is as low as 10-7 M, and the Raman enhancement factor is as large as 105 with a relative standard deviation of less than 25%. After the calibration of the Raman peak intensifies of rhodamine 6G and thiram, organic molecules could be quantitatively detected. These results indicate that Au/SiNWA is a promising SERS-active substrate for the detection of biomolecules present in low concentrations. Our findings are an important advance in SERS substrates to allow fast and quantitative detection of trace organic contaminants.     

不同Ag壳厚度Au@Ag纳米粒子的调控制备表征及表面增强拉曼光谱的效应

采用化学还原法制备了以Au为核、包覆Ag的双金属核壳Au@Ag纳米粒子,并成功地用于表面增强拉曼光谱(SERS)分析测试。通过改变制备液中Ag/Au的量比来调控Ag壳包覆厚度。采用透射电子显微镜(TEM)和紫外-可见光谱仪(UV-Vis)对Au@Ag纳米粒子的构貌进行表征。TEM显示明显存在核壳结构,且Ag壳层随Ag/Au的量比的增加而逐渐变厚;UV-Vis表明随着Ag/Au的量比的增加,Au@Ag纳米粒子出现了Au核与Ag壳吸收峰的2个等离子体共振峰,同时伴随着Au峰的蓝移和Ag峰的红移。以双甲脒为分析物,考察了不同Ag/Au的量比时的Au@Ag纳米粒子的SERS活性。结果表明,SERS活性随Ag/Au的量比的增加先增大后减小,在6∶5时其SERS增强效应最佳,此时Ag壳厚度约为6 nm。以对巯基苯胺(4-ATP)、结晶紫(CV)和双甲脒为分析测试对象,对比了Au@Ag、Ag、Au 3种基底的SERS活性。结果表明,所制备的Au@Ag纳米粒子的SERS活性要明显优于单纯的Au、Ag纳米粒子。