粗糙镍电极上吡啶和二巯基嘧啶的表面拉曼光谱

粗糙镍电极上吡啶和二巯基嘧啶的表面拉曼光谱①黄群健高劲松蔡雄伟毛秉伟郑明森田中群＊（厦门大学化学系，固体表面物理化学国家重点实验室，厦门３６１００５）自从人们发现和认知表面增强拉曼散射（ＳＥＲＳ）效应以来［１］，ＳＥＲＳ技术以其极高的表面灵敏度为电极...     

烯丙基硫脲与支持电解质阴离子在银电极上共吸附的拉曼光谱

用表面增强拉曼散射光谱（ＳＥＲＳ）和时间分辨ＳＥＲＳ光谱（ＴＲＳＥＲＳ）等技术首次研究了烯丙基硫脲（ＡＴＵ）在ＨＣｌＯ４、Ｈ２ＳＯ４和ＨＮＯ３介质中与无机阴离子在银电极上的电化学共吸附行为．提出ＡＴＵ很可能以Ｓ端与银电极表面形成化学吸附键，仲氨基相对伯氨基距离表面较近，整个分子偏向烯丙基一侧倾斜吸附在表面上．ＣｌＯ－４、ＳＯ２－４和ＮＯ－３等弱吸附无机阴离子均能被ＡＴＵ诱导共吸附在其质子化了的仲氨基上，这３种无机阴离子被ＡＴＵ诱导共吸附的强弱顺序是ＣｌＯ－４＞ＳＯ２－４＞ＮＯ－３．被诱导共吸附的无机阴离子对ＡＴＵ在电极表面的化学吸附起到稳定剂的作用，有利于ＡＴＵ在电极表面形成致密的吸附层     

Ag2CO3溶胶中PABA表面增强拉曼光谱及增强机制的探讨

首次观测到Ａｇ２ＣＯ３溶胶体系中的吸附分子（对氨基苯甲酸ＰＡＢＡ）表面增强拉曼散射（ＳＥＲＳ）效应特强，该体系对ＰＡＢＡ的增强程度比Ａｇ胶还强。同时，分别向该体系加入少量的Ｓ２Ｏ３，Ｆｅ（ＣＮ）６，Ｈ２Ｏ２和ＮＯ３－溶液后，观测其对ＰＡＢＡ的ＳＥＲＳ谱带强度的影响，探讨该体系的增强机制。结果表明，胶体表面的Ａｇ＋或Ａｇδ＋是该体系的ＳＥＲＳ活位吸附点，而表面络合物对其ＳＥＲＳ起到一定的作用。     

D-氨基葡萄糖甘氨酸混配金属配合物与DNA作用的光谱研究

研究了４种Ｄ－氨基葡萄糖甘氨酸混配金属配合物的表面增强拉曼光谱（ＳＥＲＳ）,发现它们在银胶上的吸附方式基本相同,因而ＳＥＲＳ光谱相似,用电子光谱、荧光光谱、表面增强拉曼光谱研究了它们与ＤＮＡ的相互作用,发现这４种化合物与ＤＮＡ的作用能力有很大的不同,其中ＧｕＧｌｕＧ、Ｃｏ（Ⅲ）ＧｌｕＧ是值得进一步研究的可能抗癌的药物。     

拓宽银电极上SERS活性的研究电位范围

电极表面的粗糙化处理是进行表面增强拉曼光谱（ＳＥＲＳ）研究的重要前提，通过研究两种截然不同的氧化还原循环（ＯＲＣ）粗粗糙电极的方法，分析其ＳＥＲＳ活性稳定电位区间与ＯＲＣ还原电位之间的关系，发现高活性的ＳＥＲＳ位皆处于亚稳状态，易随电极电位趋近零电位（ＰＺＣ）而发生表面原子重排，以至推动活性，引入强吸附物种，可以使特殊ＯＲＣ得到的ＳＥＲＳ活性在ＰＺＣ以正电位区稳定存在，并可在ＰＺＣ以负一得到常规Ｏ     

ss—DNA在纳米金上固载和杂化的化学传感研究

将２－氨乙基硫醇（ＡＥＴ）固载到玻碳电极（ＧＣＥ）表面,进而化学吸附纳米金（ＮＧ）,并在纳米金上固载ss－ＤＮＡ得到ss－ＤＮＡ／ＮＧ／ＡＥＴ／ＧＣＥ,以Ｃo（ｂｐ ｙ）３＾３＋,但用pＨ７．０的磷酸缓冲液浸泡可基本上避免这种变性,并时显提高杂化反应的识别能力。结合在ds－ＤＮＡ／ＮＧ／ＡＥＴ／ＧＣＥ上的Ｃo（bpy）３＾３＋的峰电流与扫速的线性关系可保持到８０mＶ／s,与电沉积法固载纲米金相比较,本电极更稳定     

脱氧核糖核酸变性和损伤的吸附伏安法研究

本文用汞电极（ＨＭＤＥ）二次导数阴极吸附伏安（ＳＤ－ＡｄＣＳＶ）和碳电极（ＧＣＥ、ＣＰＥ）导数循环伏安（ＦＤ－ＣＶ）法研究了核酸受热、紫外线、超声波和丝裂霉素Ｃ（ＭＭＣ）作用下的变性作用。在０．１ｍｏｌ／Ｌ（Ｋ２ＨＰＯ４＋ＫＨ２ＰＯ４）－０．１ｍｏｌ．Ｌ ＮａＣｌ（ｐＨ７．０）底液中，吸附的单股（ｓｓ－）和双螺旋（ｄｓ－）ＤＮＡ分别在ＨＭＤＥ上得到特征还原峰Ｐ３和Ｐ２，和在碳电极上得到氧化峰Ａ。物     

高序热解石墨与玻碳电极上DNA的氧化和吸附行为

在高序热解石墨（ＨＯＰＧ）电极上,采用微分脉冲伏安法（ＤＰＶ）和电化学原子显微镜法（ＥＣＡＦＭ）探究小牛胸腺ＤＮＡ（ＣＴ ＤＮＡ）在电极表面的吸附。实验发现,控制电位下预极化对双链ＤＮＡ和ＨＯＰＧ电极上的吸附有很大的影响。而对单链ＤＮＡ影响不大。实验表明,在ＨＯＰＧ电极上ＥＡＦＭ是ＤＮＡ研究领域十分有用的技术,根据ＡＦＭ图象,结合文献上的ＤＮＡ吸附模型提出了ＣＴ ＤＮＡ研究领域十分有用的技术,根据     

用表面增强拉曼光谱研究BMAT对不锈钢的缓蚀机理

应用表面增强拉曼散射光谱（ＳＥＲＳ）技术，研究０．５％ＨＣｌ体系中缓蚀剂在１８－８不锈钢表面的吸附。谱图是在不锈钢表面电沉积不连续Ａｇ颗粒条件下测得的。缓蚀剂ＢＭＡＴ通过电极表面与缓蚀剂中的Ｎ原子，以及苯并咪唑环的共轭大π键形成化学吸附，ＢＭＡＴ斜卧于电极表面。其烯丙基起到空间的阻碍的作用。     

SYNTHESIS,CRYSTAL STRUCTURE AND MAGNETISM OF THE COMPLEX:GdFe(CN)_64H_2O

ＳＹＮＴＨＥＳＩＳ，ＣＲＹＳＴＡＬ　ＳＴＲＵＣＴＵＲＥ　ＡＮＤ　ＭＡＧＮＥＴＩＳＭ　ＯＦ　ＴＨＥ　ＣＯＭＰＬＥＸ：ＧｄＦｅ（ＣＮ）_６４Ｈ_２ＯＳＹＮＴＨＥＳＩＳ，ＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＡＮＤＭＡＧＮＥＴＩＳＭＯＦＴＨＥＣＯＭＰＬＥＸ：ＧｄＦ...     

A surface renewable iridium oxide-glass composite hydrogen ion electrode

A robust and surface renewable iridium oxide-based pH glass composite electrode was prepared by modifying glass matrix with iridium oxide particles. Fine glass powder coated with iridium oxide was prepared by pyrolyzing ammonium hexachloroiridate-coated glass powder under oxygen atmosphere. First the glass powder was molded into a disk, by using a press, then was sintered in high temperature, and was finally fabricated. The electrode showed linear response between pH 1 and 13 with close slopes to the theoretical value, − 59.2 mV/pH. The electrode showed low hysteresis upon sudden changes of pH from 2 to 6, but in extreme conditions, from pH 13 to 1, it showed values near 16 mV. The electrode maintained the pH response for 36 days, without a significant slope drift, in various storage conditions — deionized water, a pH 7 buffer solution, 4 M KCl, and even in the air. Most of the cations and anions, except electrochemically active compounds or ions, did not interfere with the electrodes seriously. The electrode surface can be renewed reproducibly, by a simple grinding process whenever it becomes fouled or deactivated. The electrode matrix was durable and showed extended lifetime although it was ground repeatedly with 2000 grit SiC emery paper for surface renewal.     

AB5型球形合金粉的表面处理研究

由雾化（Gas－atomization）技术制备的AB5型球形合金粉，作为镍氢电池负极材料具有很多优点：粉粒呈球状便于在多孔基片内装填；耐压耐磨性好；抗碱能力强且不易解胶．但它的电化学初活性差，难于活化．有碍电池中的应用．采用适宜的氧化剂（铜盐水溶液）处理，使球粒表面形成一个富铜、富镍亚层，显著地改善了合金粉的电化学活性．经处理的MlNi3.8CO0.5Mn0.3Al0.4球形合金粉，仅3次充放电循环其放电量便可达到240mA·h·g-1；而未经处理的同一合金粉即便经6次充放电循环其放电量也只有103mA·h·g-1．     

Alternative reference system in the thermodynamics of solid elastic electrodes

Basic quantities in the thermodynamics of the solid elastic electrode are the surface tension tensor g _mn and the work needed for the formation of the surface (interface) γ. It is scarcely mentioned explicitly anywhere that these intensive (specific) quantities are related to the surface of the elastically deformed electrode. On the other hand, in the thermodynamics of the volume elasticity, the free energy density of the deformed solid is related to the volume of the undeformed solid. In this paper, we introduce equivalently the undeformed surface of the solid elastic electrode as reference for both the surface tension tensor and the work of formation of the surface. Generalizing the analysis of two model systems, we deduce the corresponding alternative form of the Shuttleworth equation, where the two quantities appear as generalized force and generalized potential, and discuss consequences for the formulation of the differential of the surface excess of the internal energy.Dedicated to the memory of W. Schwabe     

Electrode reactions of palladium(II) in chloride solution at carbon paste electrodes modified with derivatives of N-benzoylthiourea

The study of the electrode reactions of palladium(II) at non-modified carbon paste electrodes (CPEs) in chloride solution has revealed the existence of a chloropalladate(II) complex at the electrode surface. The complex is formed during the application of anodic potentials after preceding palladium deposition. In the present paper the electrode reactions of Pd^II at CPEs modified with some N′,N′-disubstituted derivatives of N-benzoylthiourea [as selective ligands for palladium(II)] are studied in chloride solution by cyclic voltammetry. Two reduction peaks are observed in the cathodic scans recorded after deposition of palladium and anodization of the electrode. From the results it is concluded that [in addition to the chloropalladate(II) complex, observed at the non-modified electrode] a second palladium complex is formed at positive potentials. The formation of the palladium(II) complex of the N-benzoylthiourea derivatives by ligand exchange at the electrode surface is assumed. The ligand exchange itself occurs without charge transfer across the electrode|solution interface; therefore, it cannot be detected electrochemically. After palladium deposition and anodic treatment a pronounced "inverse" peak (i.e., an anodic peak in the cathodic scan) with peak currents up to 100 μA is observed at about +0.8 V. Its peak current increases with the amount of deposited palladium and the number of cycles. The reactions at the electrode surface are discussed. The results of the study reveal the existence of two different surface complexes of palladium(II) at ligand-modified CPEs, but the surface reactions could not be elucidated in detail. Electronic Publication     

面向脑机接口的犹他神经电极技术

A human brain is composed of a large number of interconnected neurons forming a neural network. To study the functional mechanism of the neural network, it is necessary to record the activity of individual neurons over a large area simultaneously. Brain-computer interface (BCI) refers to the connection established between the human/animal brain and computers/other electronic devices, which enables direct interaction between the brain and external devices. It plays an important role in understanding, protecting, and simulating the brain, especially in helping patients with neurological disorders to restore their impaired motor and sensory functions. Neural electrodes are electrophysiological devices that form the core of BCI, which convert neuronal electrical signals (carried by ions) into general electrical signals (carried by electrons). They can record or interfere with the state of neural activity. The Utah Electrode Array (UEA) designed by the University of Utah is a mainstream neural electrode fabricated by bulk micromachining. Its unique three-dimensional needle-like structure enables each electrode to obtain high spatiotemporal resolution and good insulation between each other. After implantation, the tip of each electrode affects only a small group of neurons around it even allowing to record the action potential of a single neuron. The availability of a large number of electrodes, high quality of signals, and long service life has made UEA the first choice for collecting neuronal signals. Moreover, UEA is the only implantable neural electrode that can record signals in the human cerebral cortex. This article mainly serves as an introduction to the construction, manufacturing process, and functioning of UEA, with a focus on the research progress in fabricating high-density electrode arrays, wireless neural interfaces, and optrode arrays using silicon, glass, and metal as that material of construction. We also discuss the surface modification techniques that can be used to reduce the electrode impedance, minimize the rejection by brain tissue, and improve the corrosion resistance of the electrode. In addition, we summarize the clinical applications where patients can control external devices and get sensory feedback by implanting UEA. Furthermore, we discuss the challenges faced by existing electrodes such as the difficulty in increasing electrode density, poor response of integrated wireless neural interface, and the problems of biocompatibility. To achieve stability and durability of the electrode, advancements in both material science and manufacturing technology are required. We hope that this review can broaden the scope of ideas for the development of UEA. The realization of a fully implantable neural microsystem can contribute to an improved understanding of the functional mechanisms of the neural network and treatment of neurological diseases.     

贮氢合金电极的活化方法和作用机理研究

比较研究了采用电化学方法、ＫＢＨ４还原，ＫＯＨ刻蚀及ＫＯＨ＋ＫＢＨ４联合作用对Ｍｍ（ＮｉＣｏＭｎＡｌ）５型贮氢电极的活化作用，发现采用浓热ＫＯＨ处理的电极可以实现快速充分的活化，且具有放电电压低、稳定容量高及操作简便的特点．对活化过程的作用机理研究表明，ＫＯＨ活化主要是通过溶解反应使稀土和镍元素富集生成有利于吸氢反应的表面组成．ＫＢＨ４及电化学活化方法则是利用反应产生的活性氢裂解合金颗粒，生成高活性的新鲜表面和晶体缺陷     

硫酸溶液中Pt电极表面过程的EQCM研究

应用电化学循环伏安和石英晶体微天平(EQCM)方法研究了0.1mol·L-1硫酸溶液中Pt电极表面的吸附和氧化过程.从电极表面质量变化的结果分析,可认为正向电位扫描时氢区表面质量的增加是由于水分子取代Had引起的,而双电层区的质量增加则是由于水的吸附模式逐渐由氢端吸附转向氧端吸附所致.根据频率变化和电量数据,进一步推算出水在双电层区是以低放电吸附形式出现的,1molPt原子和水分子只发生0.054mol的电荷转移.本文结果可为认识Pt电极表面过程提供定量的新数据.     

Electropolymerization of polypyrrole, modified with germanium, on a passivated titanium electrode in aqueous nitrate solution: new results on catalytic reduction of protons and dissolved oxygen

Conductive polypyrrole (PPy) films and PPy films containing Ge microparticles were synthesized by anodic oxidation of pyrrole in acidic nitrate solutions using a bare passivated titanium electrode. Well-adhering black PPy films were obtained both under galvanostatic and potentiodynamic polarization. After the formation of the PPy film, during the first anodic cycle, an increase of the anodic deposition current with the number of cycles was observed, revealing the increase of conductivity of the growing film. The variations of the electrode surface area were estimated by impedance spectroscopy measurements. The kinetics of the PPy film formation is controlled by diffusion of the Py monomer in the solution. The diffusion coefficient, estimated by two different methods, was ca. 2×10^–6 cm² s^–1. The reduction rate of oxygen and protons at the Ti/PPy/Ge electrodes depends on how the Ge microparticles are incorporated in the PPy film. Optimum conditions for this incorporation are realized with thin PPy films and high Ge loading. Thermogravimetric analysis shows that the PPy film containing Ge microparticles is more thermally stable than the blank PPy film. Electronic Publication     

Synthesis and characterization of high-integrity solid-contact polymeric ion sensors

High-integrity solid-contact (SC) polymeric ion sensors have been produced by using spin casting and electropolymerization techniques in the preparation of the SC employing the conductive polymer, poly(3-octylthiophene) (POT). The physical and chemical integrity of the POT SCs have been evaluated using scanning electron microscopy (SEM), atomic force microscopy (AFM), secondary ion mass spectrometry (SIMS), and X-ray photoelectron spectroscopy (XPS). Furthermore, the electrochemical stability of SC polymeric ion sensors has been investigated using electrochemical impedance spectroscopy (EIS). The results of this study demonstrate that electropolymerization and spin casting methods also comprising annealing of the synthesized SC film are capable of producing SCs that are relatively free of imperfections such as pores and pinholes. This leads to electrochemically stable and robust polymeric ion sensors where the SC/sensor interface is resistant to the formation of a detrimental water layer that normally gives rise to spurious ion fluxes and a degradation in the sensitivity and selectivity of the SC polymeric ion sensor.     

Electrochemical properties and structures of surface-fluorinated graphite for the lithium ion secondary battery

Surface modification of graphite powder has been performed by elemental fluorine and radiofrequency (rf) plasma fluorination. Both methods give rise to an enlargement of the surface areas of graphite samples and a change of the pore volume distribution. The capacities of surface-fluorinated graphite samples are higher than those of original samples and even more than the theoretical capacity of graphite, 372 mAh g⁻¹, without any reduction of the first colombic efficiencies. The increments of the capacities are ∼5, 10, and 15% for graphite samples with average particle diameters of 7, 25 and 40 μm, respectively.