Strategy for improved analysis of peptides by surface‐enhanced Raman spectroscopy (SERS) involving positively charged nanoparticles

A strategy for improved surface‐enhanced Raman spectroscopy (SERS) measurements that extends the variety of analytes accessible to SERS analysis is developed. The strategy involves inducing aggregation by mixing positively charged nanoparticles which form SERS‐active clusters when mixed with negatively charged silver nanoparticles fabricated using the Lee–Meisel process. To make positively charged nanoparticles, silver nanoparticles using the traditional Lee–Meisel process are fabricated and coated with a thin layer of silica and the silica modified with silane chemistry. Analytes with a significant amount of negative charge exhibit strong Raman bands when the strategy using these fabricated, positively charged nanoparticles for inducing cluster formation is used, enabling their detection and analysis. We envision the use of positively charged nanoparticles in cluster formation for expanding the range of analytes that can be detected using SERS and hence the range of applications SERS can play a role in. Copyright © 2008 John Wiley & Sons, Ltd.     

Gold and Silver Nanomaterial‐Based Optical Sensing Systems

Gold and silver nanomaterials (NMs) such as nanoparticles (NPs) and nanoclusters (NCs) possessing interesting optical properties have become popular sensing materials. With strong surface plasmon resonance (SPR) absorption, extraordinary stability, ease in preparation, conjugation, and biocompatibility, Au NPs are employed to develop sensitive and selective sensing systems for a variety of analytes. However, small sizes of Au and Ag NCs with interesting photoluminescence (PL) properties are used in many PL‐based sensing systems for the detection of important analytes. In addition, many bimetallic AuM NMs possessing strong catalytic activity are used to develop highly sensitive fluorescent sensors. This review article is categorized in four sections based on the NMs used in the sensing systems, including Au NPs, bimetallic AuM NMs, Au NCs, and DNA–Ag NCs. In each section, synthetic strategies and optical properties of the NMs are provided briefly, followed by emphasis on their analytical applications in the detection of small molecules, metal ions, DNA, proteins, and cells. Current challenges and future prospects of these NMs‐based sensing systems will be addressed.     

Wide range bilayer aluminum nanowire grating sensors with robust reflective peaks

A grating-coupled surface plasmon resonance sensor based on bilayer aluminum nanowire arrays is fabricated by laser interference lithography. The device presents impressive reflective sharp peaks by lateral surface plasmon resonances even for aluminum thicknesses of merely several nanometers. Distinct reflective peaks and dramatic color shifts under different analytes are observed within a wide range of incident angle, metal thickness, and refractive index. The sensitivity of 307 nm per refractive index unit is experimentally obtained.The reflective-peak-type surface plasmon resonance sensors are suitable for practical applications because of easy fabrication, low cost, wide range, and high signal visibility.     

表面增强拉曼光谱(SERS)技术对非标记蛋白质的研究进展

基于表面增强拉曼光谱(SERS)技术在非标记蛋白质研究方面的最新进展。SERS是一个特殊的拉曼光谱现象,对于众多被吸附到粗糙金属表面上的拉曼活性分析物,可以提供增强拉曼信号(通常可以增强几个数量级)。SERS是一个灵敏的,选择性的,和通用的技术,并且可以实时、快速的对数据进行采集。因此,在基于仪器仪表技术和数据分析方法以及SERS在生物体系中的诸多优势,SERS经历了快速的发展阶段。重点介绍几个采用SERS技术对生物体系的代表性研究。某些SERS的生物应用发展比较成熟,并已经可以小范围临床应用,而有些还停留在发展的初始阶段(实验室研究阶段)。讨论了最近发展起来的几种基于SERS技术定量分析的方法, 选择不同SERS活性基底和技术(如生物分子在电极上,胶体纳米粒子,周期性图案结构和基于针尖拉曼技术)对蛋白质进行直接研究。此外,根据SERS指纹信息的变化可以用来研究蛋白质-蛋白质,蛋白质-配体间的相互作用。基于SERS技术对生物分子进行定性和/或定量分析方面显示出了相当大的优势。     

Chiral Ag and Au Nanomaterials Based Optical Approaches for Analytical Applications

Sensing of chiral compounds has gained great attentions for many decades. Chiral nanomaterials with a greater surface area, optical properties, and stability have however not been well realized in this field. Herein, strategies for the preparation of chiral Ag and Au nanomaterials are focused upon, including Ag and Au nanoparticles conjugated with chiral molecules with/without containing fluorophores, chiral nanoassemblies of Ag and Au nanoparticles, and chiral Ag and Au nanoclusters. The chirality of nanomaterials originates from their core and/or ligand, meanwhile that for nanoassemblies results from their complex spatial configuration. An emphasis is given to circular dichroism, colorimetry/UV–vis absorption, and fluorescence detection modes for sensing enantiomers and achiral analytes using the chiral Ag and Au nanomaterials. Several interesting examples for quantitation of DNA, proteins, peptides, drugs, and pollutants are provided to highlight their potential as sensitive and selective nanomaterials for enantiomer recognition and sensing of achiral analytes. Several important issues to be solved when using chiral nanomaterials for chiral recognition are specified. Some strategies for improving the sensitivity and selectivity of chiral nanomaterials for chiral recognition are suggested. The aim is to bring more attention to the potential of chiral nanomaterials for sensing important analytes such as chiral drugs.     

A tunable gas sensor using an acoustic waveguide

A tunable gas sensor using surface acoustic waves (SAW) is described. It is designed on the basis of a waveguide delay line fabricated on a piezoelectric substrate made of 128° Y-cut LiNbO₃. A voltage applied between the waveguide and two electrodes causes a local change in the properties of the substrate near the waveguide and differently affects the sensor’s response to the vapors of various analytes. Some results of the experimental study of the sensor, which show the change in the selectivity under the effect of voltage, are presented. The analytes used for testing include a number of alcohols and deionized water. The possibilities for employing such a sensor in the sensor arrays of gas analyzers of the electronic nose type are discussed.     

电极表面特性对甘油介质击穿特性的影响

基于几种常见的电极表面处理工艺,制作了外形一致、表面不同的砂纸打磨、羊毛抛光、金属电镀和非金属电镀四种同轴电极,对比了电极在微观下的形貌特点,通过实验研究了不同电极表面特性与甘油介质耐压的关系。搭建了基于晶闸管控制的空心脉冲变压器升压实验平台,最大输出电压500 kV,上升时间26 s。实验结果表明:四种电极的微观形貌存在较大差异,并引起了甘油击穿特性的不同,在相同充电电压条件下,甘油的平均击穿场强为210~260 kV/cm;与使用常规的砂纸打磨电极相比,使用羊毛抛光、金属电镀、非金属电镀电极可分别使击穿场强提高14.51%,11.60%,19.67%,其中非金属电镀电极表面均匀程度远高于其他电极,最高击穿场强可达288 kV/cm,比对照组平均击穿场强提高33.09%。     

Design considerations for SERS detection in colloidal solution: reduce spectral intensity fluctuation

The intensity fluctuation of surface‐enhanced Raman scattering (SERS) has seriously hampered its practical applications. The previous studies that involved SERS intensity fluctuation mostly focus on the assembled substrates or single molecule and single nanoparticle but have few attention on colloidal solutions containing numerous molecules and/or nanoparticles. Here, we studied the time‐elapsed SERS spectra of three different analytes in colloidal solution. Their peak intensities fluctuated simultaneously and uniformly throughout the acquisition process and had no correlation with their wavenumber wandering. Gravity‐induced inhomogeneous distributions of Ag nanocubes in solution led to the spatial and temporal variations of peak intensities, which could be reduced by altering the integration time, particle concentration, and solvent viscosity and density. Furthermore, the dissimilar interactions between analytes and Ag nanocubes showed non‐detectable influence over their intensity fluctuations. This investigation gives out the significant guidance for SERS detection in colloidal solution. Copyright © 2015 John Wiley & Sons, Ltd.     

Nanostructures and nanostructured substrates for surface—enhanced Raman scattering (SERS)

We review the performance of various nanoscaled structures needed to support the propagation of the surface plasmons responsible for surface‐enhanced Raman scattering (SERS), and assess the potential for the optimisation of the compromise between enhancement and reproducibility that they provide, and hence their utility for relevant applications. We divide these nanostructures into those comprising structured arrays of discrete nanoparticles in two or three dimensions, and those comprising structured or regularly patterned surfaces in two or three dimensions. The most promising in terms of this compromise are those that involve the tethering of functionalised metal nanoparticles to surfaces. They are not only reproducible, but the functionalisation provides a measure of selectivity to relevant target analytes that the majority of SERS applications require. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of electrode surface topology on charge injection characteristics in dielectric liquids: An experimental study

Micro/nano scale features are incorporated on an electrode surface to study its effect on the charge injection characteristics in HFE7100. These features are generated on a smooth surface by chemical etching of the electrodes or through electrophoretic deposition of single walled carbon nanotubes (SWCNT). The threshold voltage for charge injection was reduced by a factor of 5 and 2 for the SWCNT and etched electrodes respectively, when compared to the smooth electrode configuration. The presence of sharp features on the surface with high aspect ratio had a more dominant effect on enhancing the charge injection than the roughness.     

Contact interference in molecular junctions

We highlight a new manifestation of quantum interference in transport through single-molecule junctions, owing to different charge transport pathways from the molecule through the contacts into the three-dimensional electrode. Such contact interference can be identified with characteristic features of the current–voltage curve, as dramatic as closing an otherwise open transport channel. Based on analysis of the necessary conditions for observation of this phenomenon, we conclude that this effect should be detectable in relatively small molecules, where a molecular site shares coupling to two electrodes, and an electrode surface site shares coupling to different molecular sites. The importance of the surface-molecule connectivity scheme implies that commonly used reduced models which couple different molecular sites to effectively independent electrodes, fail to account for this effect and must be corrected in order to properly capture contact interference.     

Thickness shear mode quartz crystal resonators with optimized elliptical electrodes

Quartz crystal resonators (QCRs) with circular electrodes have been widely used for various liquid and gas sensing applications. In this work,quartz crystal resonators with elliptical electrodes were studied and tested for liquid property measurement. Mindlin’s theory was used to optimize the dimension and geometry of the electrodes and a 5-MHz QCR with minimum series resistance and without any spurious modes was obtained. A series of AT-cut QCRs with elliptical electrodes of different sizes were fabricated and their sensing performances were compared to devices with circular electrodes. The experimental result shows that the device with elliptical electrodes can obtain lower resonance impedance and a higher Q factor,which results in a better loading capability. Even though the sensitivities of devices with elliptical and circular electrodes are found to be similar,the sensor with elliptical electrodes has much higher resolution due to a better frequency stability. The study indicates that the performance of QCRs with elliptical electrodes is superior to that of traditional QCRs with circular electrodes.     

纳米结构中的量子问题

文章讨论了纳米器件发展方向和近期的研究成果，指出是子效应和纳米结构是将来的纳米器件的两大基础，以碳纳米管和各种电极组成的纳米结构为代表，论述了不同的量子效应及其在纳米器件中的可能应用。     

Effect of electrodeposition modes on ruthenium oxide electrodes for supercapacitors

With developments in energy storage devices, supercapacitors are gaining more attraction because of their potential to excel batteries shortly. In this work, ruthenium oxide (RuO₂) has been deposited on stainless steel and studied the influence of surface modification of solid electrodes on capacitance properties. Hydrous ruthenium oxide was plated by different modes such as potential sweep method (cyclic voltammetric), constant potential method (chronoamperometry) and optimised potential pulse method using a recently reported precursor material namely ruthenium nitrosylsulfate (RuNS). The structural information and morphology of electrodeposits were characterised by X-ray diffractometer and scanning electron microscope respectively. The XRD studies indicate a poor crystalline state for RuO₂ in all the modes of deposition but can contribute to a higher surface area when compared to a highly crystalline form. The SEM analysis revealed the formation of surface modification concerning the change of potential mode. Mud-cracked morphology, spherical particles and dendrimeric morphology observed on chronoamperometry, potential pulse and cyclic voltammetry respectively. Electrochemical studies were also conducted on the samples to assess their performance for supercapacitor applications. The spherical particles of hydrous RuO₂ show high performance of capacitance behaviour 1180 F/g in 0.5 M H₂SO₄ at the scan rate of 5 mV/s. Dendrimeric morphology and mud-cracked morphology shows 573 F/g and 546 F/g respectively in same 0.5 M H₂SO₄ at the scan rate of 5 mV/s. The studies reveal that RuO₂ electrodes can be exploited for their outstanding capacitive behaviour by properly controlling the morphology of the deposits.     

Combined ellipsometric and reflectometric measurements of surface processes on noble metal electrodes

Linear approximation expressions for the optical effects due to the growth of very thin films on metal electrodes are discussed. It is concluded that the combined results of electromodulated reflectometric and ellipsometric measurements may provide better diagnostic criteria in the analysis of this type of surface processes. Transient measurements of the small changes in Δ may be performed with an off-null ellipsometric technique. Results of such experiments are discussed for three different surface processes: the early stage in the surface electro-oxidation of gold in acid solution, anionic electrosorption on platinum and hydrogen ad- and absorption on platinum and palladium. Variation of the modulation frequency allows to resolve surface processes which occur simultaneously, according to their characteristic relaxation times.     

准分子激光取样与电感耦合等离子体质谱和光谱联用分析仪器研究进展

将准分子激光剥蚀取样后的产物经由电感耦合等离子质谱与光谱分析,从而获得被激光剥蚀样品的元素与同位素含量信息,是迄今为止适应于表面原位微区分析最为重要的分析科学技术手段之一.基于准分子激光剥蚀取样技术分别与电感耦合等离子体质谱或发射光谱技术联用的分析手段,已经被广泛应用于地质学、材料学、环境科学,甚至生命科学领域的原位微...     

Sensitivity enhancement in membrane separation flow injection analysis by ultrasound

The effect of ultrasound on gas-diffusion and pervaporation flow injection separation was investigated. Ammonia and three aliphatic amines (propylamine, tri-ethylamine and di-n-butylamine) with different volatility and surface activity were used as model analytes. Under the experimental conditions used, sonication did not enhance gas-diffusion separation efficiency and resulted in up to 62% improvement in pervaporation mass transfer. Based on these findings and taking into account the surface activity of the analytes studied which decreased with their molecular mass it was postulated that ultrasound-induced surface rippling was primarily responsible for the enhanced evaporation in the donor chamber of the pervaporation cell. The results reported in this paper suggest that ultrasonic pervaporation separation could extend the applicability of this on-line flow injection separation technique to the direct determination of higher molecular mass volatile and semi-volatile analytes in 'dirty' samples.     

Some regularity on how to locate electrodes for higher fECG SNRs

The electrocardiogram(ECG) recorded from the abdominal surface of a pregnant woman is a composite of maternal ECG, fetal ECG(f ECG) and other noises, while only the f ECG component is always needed by us. With different locations of electrode pairs on the maternal abdominal surface to measure f ECGs, the signal-to-noise ratios(SNRs) of the recorded abdominal ECGs are also correspondingly different. Some regularity on how to locate electrodes to obtain higher f ECG SNRs is needed practically. In this paper, 343 groups of abdominal ECG records were acquired from 78 pregnant women with different electrode pairs locating, and an appropriate extended research database is formed. Then the regularity on f ECG SNRs corresponding to different electrode pairs locating was studied. Based on statistical analysis, it is shown that the f ECG SNRs are significantly higher in certain locations than others. Reasonable explanation is also provided to the statistical result using the theories of the fetal cardiac electrical axis and the signal phase delay.     

Equipment for continuous measurement of cathodic hydrogen diffusion through metal membranes

An equipment is described which enables to measure sensitively and during long time the quantity of hydrogen diffusion through a metal sample saturated electrolytically under defined conditions of current density, temperature, and stirring while the electrodes potentials, voltage etc. are measured simultaneously.The arrangement makes possible to transfer the measuring equipment with the sample from one used solution into another in 2 sec which enables to apply different electrochemical processing of the sample surface.Some examples of applications of the equipment for measurement of hydrogen diffusion in nickel are presented.     

甘油介质在同轴形成线中的击穿特性研究

针对甘油介质在形成线中的应用,总结了甘油作为储能介质已开展的相关研究工作,并在缩比的同轴电极试件中进行了电极表面、磁场、耐压极性、含气量等条件对甘油介质击穿特性影响的实验研究。搭建了基于晶闸管控制的空心脉冲变压器升压实验平台,设计了浸没于脉冲磁场中的同轴电极击穿试件,实验平台最大输出电压500 kV,上升时间26 s,最大磁场1 T,可通过控制晶闸管的先后触发使击穿过程发生于准稳衡磁场中,并制作了外形一致、表面不同的砂纸打磨、羊毛抛光、金属电镀和非金属电镀四种电极。实验结果表明:甘油的击穿是没有极性的;1 T量级磁场对甘油介质的击穿特性无影响;不同电极表面微观形貌差异较大,使甘油介质具有不同的击穿特性,说明甘油击穿在电极表面的过程具有较大影响;充分的排气能减少甘油中直径较大的气泡,减少概率性的低击穿场强,击穿后产生的大量微小气泡会整体降低甘油的击穿阈值,使甘油的平均击穿场强降低。