银溶胶SERS光谱在分析方面的应用研究

本文利用乙醇作为内标对结晶紫进行了定量分析,对最佳溶胶粒度进行了选择,并使结晶紫的检测限降至5×10~(-12)mol/l,实验中还对 KCl、乙醇等对溶胶粒度的影响进行了研究,并讨论了溶剂极性对 SERS 谱带频率的影响。通过1620cm~(-1)苯环伸缩振动频率的位移现象对结晶紫的吸附取向进行了初步探讨。     

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。     

银纳米有序阵列SERS活性基底的制备及在膀胱肿瘤细胞检测中的应用

以多孔阳极氧化铝(porous anodic alumina,PAA)膜为模板,采用真空电子束蒸镀技术,分别在PAA多孔层以及阻挡层表面形成了银纳米孔和银纳米帽有序阵列表面增强拉曼散射(surface-enhancedRaman scattering,SERS)活性基底,并以膀胱肿瘤细胞作为分子探针,测试和分析了这两种SERS活性基底的表面增强拉曼光谱的特性。结果表明,两种SERS活性基底对膀胱肿瘤细胞的拉曼散射信号均有很好的增强作用。银纳米帽有序阵列SERS活性基底不仅具有较高的SERS增强和荧光猝灭效应,而且不存在与PAA膜中草酸根杂质相关的干扰峰,可获得膀胱肿瘤细胞拉曼散射光谱的更多细节信息。     

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。     

银纳米阵列直径对SERS增强效果的影响

采用电化学沉积法分别在不同孔径的阳极氧化铝(AAO)模板上沉积一系列直径不同,排列规则的银纳米阵列。以对氨基苯甲酸(PABA)和三聚氰胺两种分子分别作为探针分子, 研究了银纳米阵列的直径大小对其表面增强拉曼散射(SERS)效果的影响。结果表明, 在波长为514.5 nm的激光激发下, 探针分子的SERS信号强度随银纳米阵列直径的改变而明显变化, 并在银纳米阵列直径约为53 nm时, SERS强度达到最大。利用电磁增强机制对此实验结果进行了分析和解释。     

一类菁染料的SERS光谱研究

本文报导了一类菁染料在银溶胶中和吸附在硝酸刻蚀的银和铜箔上的SERS 光谱以及两种方式的比较。对硝酸刻蚀粗化银和铜箔表面的最佳条件进行了讨论,区别于银溶胶,用粗化银和铜箔测得了共振 SERS 光谱。提出了菁染料分子在铜、银表面吸附的可能方式。     

温度对银基底表面增强拉曼散射效应的影响

利用电沉积法制备了银基底,考察了焙烧温度对基底形貌和表面增强拉曼散射效应的影响.研究结果表明,制备的电沉积银基底呈主干及两侧分支组成的枝晶状,分支均具有高曲率的尖端,可以产生避雷针效应,增强基底的表面增强拉曼散射性能;对基底进行焙烧处理,在300℃时分支尖端开始消失并出现团聚现象,400℃时枝晶变得粗大,但有新的球状纳...     

银纳米线表面增强拉曼散射的偏振依赖性研究

近年来,一系列新型低维金属纳米材料相继涌现,展现出优异的性能。这些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。形貌与取向调控是低维金属纳米材料SERS应用的重要策略。主要采用多元醇还原法制备了高质量、各向异性的银纳米线结构,进一步以罗丹明6G分子作为探针,来研究入射光偏振方向对银纳米线拉曼信号的影响。结果表明,由于纳米线具有各向异性,所以当入射光方向与纳米线长轴近乎垂直时,获得的SERS信号最强。反之,当入射光方向与纳米线长轴成0°夹角时,得到的SERS信号最弱。通过对基于各向异性基底SERS光谱的偏振依赖性研究,有利于更深入地理解SERS机理,同时也有利于人们在不利用任何外部装置的情况下更好的调控SERS强度。     

基于纳米多孔银的磺胺类药物SERS光谱检测

抗生素和磺胺类药物在预防感染,治疗疾病方面起到巨大作用,从而被广泛使用。由于这些药物在生物体中无法完全代谢,随着食物链循环造成环境污染并对人类形成持续危害。近年来对于这些药物的监管逐渐被人们所重视。基于局域表面等离子体共振的表面增强拉曼光谱法(SERS)可以将吸附在粗化的金属表面分子的拉曼信号进行增强,检测极限可达单分子量级,因此,SERS相关技术被广泛用于痕量物质检测,检测极限主要决定于SERS基底的活性。本研究工作采用脱合金方法,制备出了均匀、孔径可调纳米多孔银基底,并用于磺胺嘧啶和磺胺醋酰检测,检测极限达到了0.25μg/kg和2μg/kg,远远低于我国农业部规定的磺胺类药物最大残余量100μg/kg。且拉曼特征峰峰强与药物的浓度表现出良好的线性关系,检测动态监测范围高达6个量级。研究所得纳米多孔银可推广用于其他物质检测,具有潜在的应用价值。     

银纳米粒子修饰三维碳纳米管阵列SERS实验

为了使表面增强拉曼散射(SERS)基底的三维聚焦体积内包含更多的“热点”,能吸附更多探针分子和金属纳米颗粒,以便获得更强的拉曼光谱信号,提出了银纳米粒子修饰垂直排列的碳纳米管阵列三维复合结构作为SERS基底,并对其进行了实验研究。利用化学气相沉积(CVD)方法制备了垂直排列的碳纳米管阵列;采用磁控溅射镀膜方法先在碳纳米管阵列上形成一层银膜,再通过设置不同的高温退火温度,使不同粒径的银纳米粒子沉积在垂直有序排列碳纳米管阵列的表面和外壁。SEM结果表明：在有序碳纳米管阵列的表面和外壁都均匀地负载了大量银纳米粒子,并且银纳米颗粒的粒径、形貌及颗粒间的间距随退火温度的不同而不同。采用罗丹明6G(R6G)分子作为探针分子,拉曼实验结果表明：R6G浓度越高,拉曼强度越强,但是R6G浓度的增加与拉曼强度增强并不呈线性变化;退火温度为450 ℃,银纳米颗粒平均粒径在100～120 nm左右,退火温度为400 ℃,银纳米颗粒平均粒径在70 nm左右,退火温度为450 ℃的拉曼信号强度优于退火温度400和350 ℃。     

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.     

Surface-enhanced Raman scattering of silicon evaporated on Ag island films

Enhanced Raman scattering of Si films from 1 to 25 Å thick deposited on Ag island films is presented. It is found that Raman spectra of Si deposits have a spectral shape similar to those of amorphous Si.     

Surface-enhanced Raman scattering of 4-mercaptobenzoic acid and hemoglobin adsorbed on self-assembled Ag monolayer films with different shapes

Polyvinylpyrrolidone (PVP)-protected silver nanostructures of various shapes, including nanocubes, nanospheres, and hybrid shapes with nanospheres and nanorods, on the surface of glass or Si substrates (PVP-Ag films) are prepared by using electrostatic self-assembly. With 4-mercaptobenzoic acid (4-MBA) as a probe molecule, it is demonstrated that the PVP-protected silver nanocubes films (PVP-Ag NCs) have better surface-enhanced Raman scattering (SERS) activity with an order of magnitude larger enhancement factors (EF) than the PVP-protected silver nanospheres films and the PVP-protected silver hybrid shapes films, which is confirmed by our numerical simulations. The EF of 4-MBA on the PVP-Ag NCs film are up to ~5.38 × 10⁶, and the detection limit is at least down to ~10^?8 M. The uniformity and reproducibility of the SERS signals on PVP-Ag NCs film are tested by point-to-point and batch-to-batch measurements. Meanwhile, the PVP-Ag films are also shown to be an excellent SERS substrate with good biocompatibility for hemoglobin detection. It is shown that the PVP-Ag NCs films can be used as excellent SERS substrate with good activity, uniformity, reproducibility, and biocompatibility and are promising for a myriad of chemical and biochemical sensing applications.     

Surface-enhanced Raman scattering (SERS) spectra of Methyl Orange in Ag colloids prepared by electrolysis method

Polyvinyl alcohol (PVA)-protected Ag colloids were prepared by an electrolysis method. The surface-enhanced Raman scattering (SERS) spectra of Methyl Orange (MO), one of the Azo-dye molecules, in Ag colloids were successfully recorded with good concordance comparing to the theoretical results calculated by the Gaussian’98 program. The MO was adsorbed on the surface of Ag nanoparticles by trans-form which plays an important role for the SERS effect. However, the SERS spectra of MO in Ag colloids prepared by chemical reduction method did not appear which may be because of the competition of the borate or citrate ions with the MO. In order to test the applicability of these colloids, the SERS spectra of Sudan red (III) (SR), another of Azo-dye molecules, were measured and the result was good.     

Surface-enhanced Raman spectroscopy based on ordered nanocap arrays

We fabricated the Ag cap array for surface-enhanced Raman scattering (SERS) by Ag deposition onto two dimensional polystyrene colloid sphere templates, and 4-mercaptopyridine (4-MPy) was used as the probing molecule. When the colloids with different size were chosen as the substrate for 20 nm Ag deposition, the film on 100 nm colloids gave the significant enhancement. SERS intensity increased with the increase of Ag thickness. When 20 nm Ag film was coated by Ta, the SERS signals decreased with the increase of Ta thickness, indicating the main effect from the top of cap structure. When Co layer was added under the Ag film, the SERS intensity decreased with the increase of Co thickness because the Co layer affects electromagnetic and plasmon resonance.     

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.     

Fabrication of silver-coated silicon nanowire arrays for surface-enhanced Raman scattering by galvanic displacement processes

Silver-coated silicon nanowire (SiNW) arrays were prepared utilizing galvanic displacement processes consisting of three steps: galvanic displacement deposition of silver particles using a HF-AgNO₃ or NH₄F-AgNO₃ aqueous solution; formation of SiNW arrays by a silver-assisted chemical etching process conducted in the HF-H₂O₂ aqueous solution; deposition of silver particles on the SiNW arrays from the NH₄F-AgNO₃ aqueous solution. The effects of the morphology of pre-deposited silver particles and deposition solution on the formation of silver-coated SiNW arrays were discussed. Surface-enhanced Raman scattering (SERS) performances have been studied using Rhodamine 6G (R6G) probe molecules on the silver-coated SiNW substrates.     

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.