二维银球腔阵列的制备及其在SERS检测中的应用

以密堆积的700 nm单分散聚苯乙烯微球为模板,采用多电流阶跃方法制备了不同深度的二维有序微/纳尺度银球腔阵列。通过扫描电子显微镜,反射紫外对球腔形貌及表面等离子体共振进行了表征,以对氨基苯硫酚及罗丹明6G为探针分子进行了表面增强拉曼光谱(SERS)的研究。结果表明,通过控制电化学沉积的条件可以实现对球腔形貌的控制。以该种球腔阵列作为SERS基底,其增强因子可达107,并具有良好的信号重现性,信号间相对标准偏差小于8%。该基底用于对罗丹明6G的定量检测,检测限可达0.1 ng·mL-1。     

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.     

Distinguishable behavior of multiple and individual rhodamine‐6G molecules on spherical Ag nanoparticles examined via time dependence of the SERS spectra

We report a surface‐enhanced Raman spectroscopy (SERS) investigation to probe the adsorption and dynamic behavior of rhodamine 6 G (Rh6G) molecules on spherical Ag nanoparticles which were produced via laser ablation in liquid. Assembly of the colloidal Ag nanoparticles on a cover glass was used to work as SERS substrates on which high‐quality SERS spectra of Rh6G were obtained with interesting time dependence when using low and ultralow concentrations, respectively. The variation of SERS spectra over time was identified with the adsorption behavior of multiple and individual molecules on the Ag nanoparticles. Analysis indicates that the adsorbed Rh6G molecules can desorb away from the initial locations on the substrate under continuous laser excitation; simultaneously, some individual molecules can move and become trapped in the gap between the aggregated Ag nanoparticles. These investigations help to clarify the origins of forming ‘hot‐spots’ which host probe molecules and hence improve the understanding of mechanisms for single‐molecule SERS spectroscopy. Copyright © 2012 John Wiley & Sons, Ltd.     

Comparison of Surface-Enhanced Raman Scattering Spectra of Azo Dye Sudan III on Several Substrates

On several substrates, including dried silver-coated filter paper, electro-polishing aluminum foils, and anodic aluminum oxide (AAO) nanometer array templates, surface-enhanced Raman scattering (SERS) spectra of Azo Dye Sudan III molecules were studied, and high-quality SERS spectra were obtained, which indicated that electro-polishing aluminum foils and AAO nanometer array templates were also active SERS substrates. A number of additional modes were presented, as well as some split peaks, which were especially obvious on electro-polishing aluminum foil and AAO nanometer array template. The enhancement mechanisms were discussed and the enhancement factors G were calculated as 10⁴, 10⁶, and 10⁵, respectively.     

Polymer optical fiber SERS sensor with gold nanorods

A surface-enhanced Raman scattering sensor is developed by etching polymer optical fiber and coating with gold nanorods. The SERS sensing experiments are demonstrated with the analyte molecules of rhodamine 6G (R6G) at 514.5 nm laser excitation. The results show that a strong fiber Raman background scattering overwhelm the R6G molecule Raman signal in common optrod configuration, but a distinct R6G SERS spectrum with 9 order magnitude enhancement can be observed while directly focusing light on the probe. Further modeling indicates the enhancement is attributed to both nanorods local field and their coupling.     

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.     

基于纳米锥森林结构的表面增强拉曼散射透明器件研究

具有无损、超灵敏和实时检测优点的表面增强拉曼散射(SERS)器件具有重要研究意义。目前,针对SERS器件的大部分研究都围绕着非透明的器件展开。使用此类器件检测高浓度试剂时,激光只能从正面入射。这意味着入射激光需要穿透被测试剂分子层才能到达位于其下方的金属纳米结构表面,因此用于激发金属纳米结构表面等离子体共振(SPR)的激光能量被减弱,相应地,SERS光谱信号也被减弱;此外,SERS光谱信号因被测试剂分子层的遮挡,无法高效返回到电荷耦合元件(CCD)中,再次被大幅度减弱,甚至有可能完全无法被检测到。相比之下,如果使用透明SERS器件,检测过程中将被测试剂分子置于器件正面,激光从器件背面入射,此时高浓度被测试剂分子层对入射激光和SERS光谱信号的干扰最小。这种情况下,可以得到较好的光谱信号。通过在石英基底上旋涂聚酰亚胺(PI)层,然后通过氧等离子体对PI层进行无掩模轰击,在石英基底上自行生成纳米纤维掩模,配合反应离子刻蚀工艺(RIE)制备了石英纳米锥森林结构。之后,通过金属纳米颗粒溅射工艺,得到SERS透明器件。对于该SERS透明器件,在测试过程中,拉曼激光可从器件的正面以及背面分别入射。初步的测试结果表明,对于罗丹明6G(R6G)在10^-3~10^-6 mol·L^-1这一浓度范围内,背面入射方式收集的SERS光谱信号强度高于正面入射方式。另外,进一步研究了该SERS透明器件背面检测的一致性,得到了良好的结果,证明了其在实际生化检测中的可行性。这一工作有望扩展SERS在分析物检测领域中的应用。     

Protein adsorption drastically reduces surface‐enhanced Raman signal of dye molecules

There is an increasing interest in developing surface enhancement Raman spectroscopy methods for intracellular biomolecule and for in vitro protein detection that involve dye or protein–dye conjugates. In this work, we have demonstrated that protein adsorption on silver nanoparticle (AgNP) can significantly attenuate the surface‐enhanced Raman spectroscopy (SERS) signal of dye molecules in both protein/dye mixtures and protein/dye conjugates. SERS spectra of 12 protein/dye mixtures were acquired using 4 proteins [bovine serum albumin (BSA), lysozyme, trypsin, and concanavalin A] and three dyes [Rhodamine 6G, adenine, and fluorescein isothiocyanate (FITC)]. Besides the protein/dye mixtures, spectra were also obtained for the free dyes and four FITC‐conjugated proteins. While no SERS signal was observed in protein/FITC mixtures or conjugates, a significantly reduced SERS intensity (up to 3 orders of magnitude) was observed for both R6G and adenine in their respective protein mixtures. Quantitative estimation of the number of dye molecules absorbed onto AgNP implied that the degree of R6G SERS signal reduction in the R6G/BSA sample is 2 to 3 orders of magnitude higher than what could be accounted for by the difference in the amount of the absorbed dyes. This finding has significant implications for both intracellular SERS analyses and in vitro protein detection using SERS tagging strategies that rely on Raman dyes as reporter molecules. Copyright © 2009 John Wiley & Sons, Ltd.     

银纳米粒子与R6G分子间的电荷转移

本文通过吸收光谱、表面增强垃曼光谱、荧光光谱等手段研究了银纳米粒子与罗丹明6G（R6G）分子之间的相互作用,结果表明：银纳米粒子表面与R6G分子之间存在电荷转移效应。表现为吸收谱长波方向出现银粒子－R6G复合体的吸收带,R6G分子的拉曼振动模得到显著增强,而其荧光得到明显猝灭;AgN特征拉曼振动带的出现服银米粒子与R6G分子是通过银粒表面的活位与R6G分子中的氮原子配位形成复合体而发生电荷转移的。     

利用高活性和重复性的银薄膜衬底SERS检测芥子气及其水解产物

通过化学浴沉积的方法制备了一种高SERS活性和重复性的银薄膜衬底。分别采用扫描电子显微镜和拉曼光谱研究了沉积时间对银薄膜微观形貌和SERS活性的影响, 优化的沉积时间为120分钟。利用优化的银薄膜衬底, 可以检测到10-9 M 的罗丹明分子的SERS谱图, 表明该银薄膜衬底具有很高的SERS活性。相同实验条件下, 在一片银薄膜衬底上任意选择16个点测试R6G的SERS谱图。分别计算了R6G的8个特征峰16次检测的相对标准偏差, 最大相对标准偏差小于13% 。实验结果表明, 该衬底具有很好的重复性, 可应用于SERS 的定量分析。采用优化的银薄膜衬底检测了不同浓度的芥子气及其水解产物硫二甘醇。分别结合芥子气和硫二甘醇的常规拉曼光谱和文献报道, 对它们的SERS谱图进行了指认和归属。20分钟内, 对芥子气和硫二甘醇的检测限可分别达到320 ppm和1 ppm (g/g)。     

Vibrational spectroscopic studies and computational study of methyl(2‐methyl‐4,6–dinitrophenylsulfanyl)ethanoate

FT‐IR and FT‐Raman spectra of methyl(2‐methyl‐4,6–dinitrophenylsulfanyl)ethanoate (MDIE) were recorded and analyzed. Surface‐enhanced Raman scattering (SERS) spectra were recorded in silver colloid and silver electrode. The vibrational wavenumbers were computed using HF/6‐31G* and B3LYP/6‐31G* basis. The data obtained from vibrational wavenumber calculations are used to assign vibrational bands obtained in infrared and Raman spectroscopies as well as in SERS of the studied molecule. The first hyperpolarizability and infrared intensities are reported. The geometrical parameters of the title compound are in agreement with the reported similar derivatives. The presence of new bands at 1045 and 948 cm⁻¹ in the SERS spectrum in silver electrode is related to the change in orientation of the molecule with respect to the metal surface. In silver colloid SERS spectrum, the methyl group attached to the methoxy carbonyl group is close to the metal surface, whereas on silver electrode the methyl group attached to the phenyl ring is close to the metal surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Facile synthesis of gelatin‐protected silver nanoparticles for SERS applications

Gelatin‐protected silver nanoparticles have been synthesized by a one‐pot, green method for surface‐enhanced Raman scattering (SERS) applications using gelatin as the reducing and stabilizing agent. The gelatin protection on silver nanoparticle surface helps improve its stability greatly and water dispersibility, while retaining high SERS activity of silver nanoparticles. The gelatin‐protected silver nanoparticles showed SERS signals as low as 100 nM of the typical Raman reporter molecules, RuBPY and R6G and 10 μM of other molecules of interest, melamine and folic acid. Copyright © 2013 John Wiley & Sons, Ltd.     

SERS activity of Au nanoparticles coated on an array of carbon nanotube nested into silicon nanoporous pillar

A novel composite structure, Au nanoparticles coated on a nest-shaped array of carbon nanotube nested into a silicon nanoporous pillar array (Au/NACNT/Si-NPA), was fabricated for surface-enhanced Raman scattering (SERS). The morphology of the Au/NACNT/Si-NPA composite structure was characterized with the aid of scanning electron microscopy, X-ray diffraction instrumentation and Transmission electron microscopy. Compared with SERS of rhodamine 6G (R6G) adsorbed on SERS-active Au substrate reported, the SERS signals of R6G adsorbed on these gold nanoparticles were obviously improved. This was attributed to the enlarged specific surface area for adsorption of target molecules brought by the nest-shaped CNTs structure.     

Surface-enhanced Raman scattering of λ -DNA

By using the molecular combing method, we stretched DNA molecules with colloidal silver nanoparticles adsorbed on them. Surface-enhanced Raman scattering (SERS) spectra were recorded in this particular DNA/Ag system. We also studied SERS spectra of DNA molecules in solution. The spectra of DNA in different concentration solution show distinct differences, and we speculate that the coiling states of DNA molecules are different in different concentrations, leading to the spectral differences. PACS 33.20.Fb; 42.62.Fi; 78.67.-n; 73.20.Mf; 87.64.-t     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.     

树枝状银微米材料的制备及其表面增强拉曼光谱研究

为使表面增量拉曼散射(SERS)衬底的制备方法简单快速且提高的基底增强效果,采用置换反应的制备方法,用锌片和硝酸银反应制备出微米银结构SERS活性基底,其具有稳定性好,易保存,制备方法简单,过程快速等特点。用扫描电子显微镜观察得银微米材料表面形貌呈均匀对称的树枝状结构。实验中控制置换反应的时间分别为40,50,60 s时,得到的树枝状银微米材料的长度分别为3,5,10 μm左右,分支分别为700 nm,2 μm,3 μm,发现随着置换反应的时间的增长,微米银树枝及分枝的长度越长,且树枝分枝上逐渐长出纳米级“树叶”结构, 使得微米级银树枝表面具有纳米结构。并且将微米银材料置于硅片上作为SERS衬底,并以罗丹明6G为探针分子,用激发波长为1 064 nm的傅里叶变换拉曼光谱仪检测,研究其在表面增强拉曼光谱中的应用,结果表明树枝状银微米材料有很好的SERS特性,其中置换反应时间为40 s时制备的微米银树枝的增强效果最佳,其增强因子可达到103左右,并且采用用表面活性剂PVP处理硅片的方法后,保持其他条件不变,微米银衬底的SERS增强效果得到进一步加强,增强因子达到104左右。此外,将树枝状银微米材料用水可封存数月,且实验结果的重复性较好。     

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.     

水溶液银纳米晶聚集对表面增强拉曼散射的影响

由于贵金属纳米粒子独特的光学性质,基于衬底的贵金属纳米粒子薄膜表面增强拉曼散射技术在分子生物学和医学免疫分析等研究领域中显现出非常好的应用优势和潜力。本项研究工作应用柠檬酸纳作聚集剂诱导水溶液中对巯基苯甲酸修饰的Ag纳米粒子聚集,并应用以此形成的"热点"增强SERS光谱,获得了对巯基苯甲酸修饰的Ag纳米粒子聚集非常有效的4-MBA分子的SERS信号,为未来建立生物待测物的分析检测奠定前期基础。结果证明,水溶液中的Ag纳米粒子的聚集形成的"热点"具有非常好的SERS光谱增强效应。     

在银、金和铂基底上银纳米粒子诱导的单层有机分子的表面增强拉曼散射(英文)

Noble metallic nanostructures exhibit a phenomenon known as surface-enhanced Raman scattering （SERS） in which the scattering cross sections are dramatically enhanced for molecules adsorbed thereon. Thanks to the enormously large enhancement factor on the order of 106～1015, one can readily acquire thevibrational spectra from adsorbates on roughened surfaces of Ag, Au, and Cu. However, SERS has not developed to be as powerful a surface technique as many people had hoped initially because of two specific obstacles.     

Self‐assembled silver nanoparticle monolayer on glassy carbon: an approach to SERS substrate

In this paper, the fabrication of an active surface‐enhanced Raman scattering (SERS) substrate by self‐assembled silver nanoparticles on a monolayer of 4‐aminophenyl‐group‐modified glassy carbon (GC) is reported. Silver nanoparticles are attached to the substrate through the electrostatic force between the negatively charged silver nanoparticles and the positively charged 4‐aminophenyl groups on GC. The active SERS substrate has been characterized by means of tapping‐mode atomic force microscopy (AFM), indicating that large quantities of silver nanoparticles are uniformly coated on the substrate. Rhodamine 6G (R6G) and p‐aminothiophenol (p‐ATP) are used as the probe molecules for SERS, resulting in high sensitivity to the SERS response, with the detection limit reaching as low as 10⁻⁹ M . This approach is easily controlled and reproducible, and more importantly, can extend the range of usable substrates to carbon‐based materials for SERS with high sensitivity. Copyright © 2007 John Wiley & Sons, Ltd.