ZnO/Au纳米复合物的制备及光学性质的研究简

摘要：采用ZnO纳米晶表面还原Au＋的方法合成了ZnO／Au纳米复合物,研究了其光学性质。     

Incorporation of Ag nanoparticles into membrane mimetic systems composed by phospholipid layer‐by‐layer (LbL) films to achieve surface‐enhanced Raman scattering as a tool in drug interaction studies

The synergistic effect produced by nanoparticles when incorporated into different systems used as analytical tools represents a growing research field nowadays. On the other hand, the study of interactions involving pharmacological drugs and biological membranes using phospholipids as mimetic systems is a research field already well established. Here, we combine both the anionic phospholipid dipalmitoyl phosphatidyl glycerol (DPPG) and negative Ag nanoparticles (AgNP) to form layer‐by‐layer (LbL) multilayered films using the cationic polymer poly(allylamine hydrochloride) (PAH) as the supporting polyelectrolyte, which were further investigated in the presence of a phenothiazine compound (methylene blue—MB). The molecular architecture of the LbL films in terms of controlled growth, morphology with micro and nanometer spatial resolutions, and dispersion of both AgNP and MB within the DPPG matrix was determined combining spectroscopy [ultraviolet–visible (UV–Vis) absorption and micro‐Raman spectroscopy] and microscopy [scanning electron microscopy (SEM) and atomic force microscopy (AFM)]. The results showed that the LbL films can be grown in a controlled way at nanometer thickness scale with the surface morphology susceptible to the presence of both AgNP and MB. The surface‐enhanced phenomenon was applied to investigate the LbL films taking the advantage of the strong surface‐enhanced resonance Raman scattering (SERRS) signal presented by the MB molecules. Besides, as MB is a pharmacological drug of interest, its molecular arrangements when dispersed in LbL films containing DPPG, which is the biological membrane mimetic system here, were investigated. In this case, the AgNP played a key role in achieving the MB SERRS signal. Copyright © 2009 John Wiley & Sons, Ltd.     

Minireview: Recent Advances in Surface-Enhanced Raman Scattering-Based Nucleic Acid Detection with Application to Pathogen Diagnosis

Surface-enhanced Raman scattering (SERS) is a promising analytical tool in nanoscale detection because of its high sensitivity and selectivity. This review focuses on recent advances in SERS-based detection of DNA and RNA. First, nanostructure-based SERS-active substrates are introduced. Using label-free and labeled SERS, target biomolecules such DNA, RNA and microRNA have been successfully detected. Finally, applications in pathogen diagnosis are discussed. The prospects and challenges of SERS-based bioanalysis are highlighted.     

Interfacing capillary electrophoresis and surface-enhanced resonance Raman spectroscopy for the determination of dye compounds

The at-line coupling of capillary electrophoresis (CE) and surface-enhanced resonance Raman spectroscopy (SERRS) was optimized for the separation and subsequent spectroscopic identification of charged analytes (dye compounds). Raman spectra were recorded following deposition of the electropherogram onto a moving substrate. To this end a new interface was developed using a stainless steel needle as a (grounded) cathode. The outlet end of the CE capillary was inserted into this metal needle; CE buffer touching the needle tip served as the electrical connection for the CE separation. A translation table was used to move the TLC plate at a constant speed during the deposition. The distance between the tip of the fused silica column and the TLC plate was kept as small as possible in order to establish a constant bridge-flow, while avoiding direct contact. The dyes Basic Red 9 (BR9), Acid Orange 7 (AO7) and Food Yellow 3 (FY3) were used as test compounds. After CE separation in a 20 mM borate buffer at pH 10, after deposition, concentrated silver colloid was added to each analyte spot, followed by irradiation with 514.5 nm light from an argon ion laser to record the SERRS signal using a Raman microscope. Different types of silver colloids were tested: Lee–Meisel type (citrate), borate, and gold-coated silver. BR9 (positively charged) gave much more intense SERRS spectra than the two negatively charged dyes. For BR9 and AO7 the citrate-coated Lee–Meisel colloid yielded the most intense SERRS spectra. The CE–SERRS system was used to separate and detect the negatively charged dyes. Silver colloid and nitric acid (to improve adsorption) were added post-deposition. Even though their chemical structures are very similar, AO7 and FY3 could be readily distinguished based on their SERRS spectra. The limits of detection (S/N=3) of the CE–SERRS system ranged from 6.7×10^–5 M (2.6×10^–12 mol injected) for FY3 down to 1.8×10^–6 M (7.0×10^–14 mol injected) for BR9.D. Arráez Román and E. Efremov contributed equally to this work.     

Multiplexed concentration quantification using isotopic surface‐enhanced resonance Raman scattering

The recently developed isotopically edited internal standard approach for surface‐enhanced resonance Raman scattering (SERRS) based chemical quantification is extended to demonstrate multiplexed detection of four different isotopic variants of a single chromophore. More specifically, it is shown that rhodamine‐6G (R6G) with 0, 2, 4, or 6 deuterium substitutions may be reliably quantified in either two‐ or three‐component mixtures. Thus, one isotopic species of known concentration may be used as an internal standard to determine the concentrations of two other isotopic components in a mixture. The concentrations of isotopic R6G SERRS chromophores are determined using partial least squares calibration and shown to yield a predictive accuracy of about ± 10% of the total R6G concentration (over 1–50 nM concentration range). These results set the stage for the use of such isotopic variants as tags for the SERRS/SERS quantitation of mixtures containing proteins, peptides, and other compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical study on SERRS of rhodamine 6G adsorbed on Ag2 cluster: chemical mechanism via intermolecular or intramolecular charge transfer

The problem of the chemical enhancement of rhodamine 6G (R6G) adsorbed on silver cluster has been theoretically investigated by charge difference densities (CDDs) to show the direct charge transfer (CT) evidence. For surface‐enhanced resonance Raman scattering (SERRS) of R6G excited at 514.5 nm, the enhancements of v(151) and v(154) result from weak intermolecular (from Ag to R6G) CT and the strong intramolecular CT [similar to that of resonance Raman scattering (RRS) of R6G], respectively. The possibility of the SERRS of R6G contributed from pure intermolecular CT is also discussed, when the incident light is close to the new metal–R6G CT excited state at 1571.4 nm. Meanwhile compared with the absorption process the fluorescence yield of R6G is investigated by transition densities and CCDs. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of indigo carmine with surface‐enhanced resonance Raman spectroscopy (SERRS) using silver colloids and island films,and theoretical calculations

The application of resonance Raman (RR) and surface‐enhanced resonance Raman (SERR) spectroscopies to the qualitative and semiquantitative analysis of the artificial dye indigo carmine has been examined using sodium‐citrate‐reduced silver colloid and island films with various roughnesses. Additional, the Raman spectrum of the solid state and density functional theory (DFT) calculations helped to a better understanding of the fully optimized geometry and of the vibrational wavenumbers of the dye. A strong chemical interaction of indigo carmine with the silver colloidal particles was observed mainly at very low concentration of 0.03 × 10⁻⁹ M and with silver film surfaces at a concentration of 10⁻⁴ M . The indigo carmine orientation possibilities while going to different metallic substrates are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

荧光素钠互变异构体的表面增强共振喇曼散射光谱

本文报导了不同pH值下荧光素钠吸附于银岛膜的表面增强共振喇曼散射(SERRS)光谱。由于在不同pH值的溶液中荧光素钠具有不同的离子构型, 其SERRS光谱也有所不同, 其差异主要表现在谱线强度的变化而不是频率变化。谱线强度随pH值的变化形式可分为两种类型, 这与其相对应的振动模的性质有关。利用“四级能模型”和共振喇曼理论对实验结果进行了分析。     

银片上茜素的表面增强共振喇曼散射效应及模式标识

本文对吸附在经连续的氧化 还原循环(ORC)过程处理的银片衬底上的茜素的表面增强共振喇曼散射(SERRS)特性进行了研究,并对茜素SERRS谱中的振动模式做了标识.结果表明,吸附在经氧化.还原循环(ORC)处理的银片衬底上的茜素分子,其表面增强喇曼散射的强度,主要是由于最靠近银片的一层分子的增强,而第一层以外的分子贡献很小.也就是说,表面增强喇曼散射具有单层饱和效应.茜素在经ORC处理的银片上和在银镜上所显示的SERRS特征基本一致,其中有些振动模式存在小的频移,这与银片、银镜各自的表面特性有关.     

Direct visual evidence for chemical mechanism of SERRS of pyrazine adsorbed on Ag nanoparticle via charge transfer

In this paper, the chemical enhancement of surface-enhanced resonance Raman scattering (SERRS) of pyrazine adsorbed on Ag nanoparticles through charge transfer was experimentally and theoretically investigated. Based on the calculations by density functional theory (DFT) and time-dependent DFT (TD-DFT), we theoretically analyzed the absorption spectra and SERS spectrum of the S-complex of pyrazine–Ag₂₀. The charge transfer in the process of resonant electronic transitions between adsorbed molecule and metal cluster can be visualized by the method of charge difference density. It is a direct evidence for the chemical enhancement mechanism of SERRS of pyrazine molecule adsorbed on Ag nanoparticle via charge transfer between molecule and metal. Additionally, the intracluster charge redistribution was also considered as an evidence for the electromagnetic enhancement. By comparing the experimental and theoretical results, it was demonstrated that the SERRS of the pyrazine molecule absorbed on silver clusters in different incident wavelength regions is dominated by different enhancement mechanisms via the chemical and electromagnetic enhancements.