超重力场中水溶液的电化学反应特性

以Fe3+/Fe2+电对体系和铁氰酸根离子为研究对象, 分别采用循环伏安法、线性扫描伏安法和计时电流法等考察了在超重力条件下Fe3+/Fe2+电对体系和铁氰化钾离子的电化学行为, 为认识和发展超重力场中电化学反应过程的研究提供了一定的理论及实验依据.     

Electrochemical Fluoro-Chalcogenation

Electrochemical fluoro-chalcogenation (S, Se) of alkenes and alkynes, and recycle use of in situ generated PhSeF for allylic fluorination are discussed.     

Electrochemical immunoassays

Immunoassays (IA) use the specific antigen antibody complexation for analytical purposes. Radioimmunoassays (RIA), fluorescence immunoassays (FIA) and enzyme immunoassays (EIA) are well established in clinical diagnostics. For the development of hand-held devices which can be used for point of care measurements, electrochemical immunoassays are promising alternatives to existing immunochemical tests. Moreover, for opaque or optically dense matrices electrochemical methods are superior. Potentiometric, capacitive and amperometric transducers have been applied for direct and indirect electrochemical immunoassays. However, due to their fast detection, broad linear range and low detection limit, amperometric transducers are preferred. Competitive and non-competitive amperometric immunoassays have been developed with redox compounds or enzymes as labels. This review will give an overview of the most frequently applied principles in electrochemical immunoassays. The potential of an indirect competitive amperometric immunoassay for the determination of creatinine within nanomolar range and the circumvention of the most serious problem in electrochemical immunoassays, namely regeneration, will be discussed.     

Electrochemical metamaterials

Journal of Solid State Electrochemistry -     

Electrochemical Capacitors

The current literature sources on the electrochemical capacitors, which are divided into the film (dielectric), electrolytic, and supercapacitors, are reviewed. The supercapacitors are in turn subdivided into the double-layer capacitors, which use the EDL recharge on a highly-developed interfacial surface of electrodes; pseudocapacitors, where the charge is stored in a faradaic pseudocapacitance of sufficiently reversible redox reactions and the EDL capacitance; and hybrid capacitors, which employ a variety of electrodes. A macrokinetic theory of operation of double-layer capacitors is considered. Effect of various factors on the properties of electrodes utilized in supercapacitors is analyzed. A novel type of hybrid capacitor, which has a negative electrode of activated carbon cloth and a PbSO₄/PbO₂ positive electrode, is proposed. A theory of capillary equilibrium in hermetically sealed electrochemical capacitors is considered. Specific features of the application of voltammetric and impedance methods to studying electrochemical processes in supercapacitors are revealed. Characteristics of electrochemical capacitors and batteries are compared.     

Electrochemical nanomachining

Free of tool wear, residual stress, and surface damage, electrochemical nanomachining (ECNM) plays an irreplaceable role in advanced manufacturing, via the production of ultra-large scale integrated circuits, microelectromechanical systems, and various nanodevices. The principles of ECNM are classified as electroforming, electrolysis, electrochemical corrosion, and etching. The working modes of ECNM include direct writing and template forming. ECNM applies to not only the fabrication of three-dimensional nanostructures but also the production of super-smooth surfaces with roughness no higher than 1 nm. Both of these are crucial in modern advanced manufacturing. The key point of ECNM is the spatial confinement of electrochemical reactions. This review will focus on this point and briefly introduce the principles, methodologies, applications, and prospects of ECNM.     

Electrochemical immunoassays

Immunoassays (IA) use the specific antigen antibody complexation for analytical purposes. Radioimmunoassays (RIA), fluorescence immunoassays (FIA) and enzyme immunoassays (EIA) are well established in clinical diagnostics. For the development of hand-held devices which can be used for point of care measurements, electrochemical immunoassays are promising alternatives to existing immunochemical tests. Moreover, for opaque or optically dense matrices electrochemical methods are superior. Potentiometric, capacitive and amperometric transducers have been applied for direct and indirect electrochemical immunoassays. However, due to their fast detection, broad linear range and low detection limit, amperometric transducers are preferred. Competitive and noncompetitive amperometric immunoassays have been developed with redox compounds or enzymes as labels. This review will give an overview of the most frequently applied principles in electrochemical immunoassays. The potential of an indirect competitive amperometric immunoassay for the determination of creatinine within nanomolar range and the circumvention of the most serious problem in electrochemical immunoassays, namely regeneration, will be discussed.     

电化学分析

本文是《分析试验室》定期评述中“电化学分析”第五篇评述文章，它评述了从１９９５年１月至１９９６年１２月期间我国电化学分析的进展，内容分基础与理论和方法与应用研究两部分，后者包括极谱与伏安法，络合吸附与催化波，单扫示波极谱与示差脉冲极谱法，溶出分析法，示波分析法，微电极，超微电极与化学修饰电极，离子选择电极与各类传感器，光谱电化学，扫描隧道显微法和液－液界面电化学分析，色谱电化学及电泳，免疫法，电位     

电化学分析

本文是《分析试验室》定期评述中电化学分析第六篇评述文章。它评述了从１９９７年１月至１９９８年１０月期间我国电化学分析的进展。内容分基础理论与应用研究两大部分。前者包括电化学分析理论研究、电分析化学中的化学计量学方法,后者包括极谱与伏安法,络合吸附波与催化波,线性扫描伏安法,示差脉冲伏安法,吸附溶出分析法,示波分析法,微电极、超微电极与化学修饰电极,离子选择电极与各类传感器,光谱电化学,扫描隧道显微法和液／液界面电化学分析,电化学检测／电泳、色谱技术,电化学免疫法,电位分析法及其它等。共引用文献４８３篇。     

暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程

对硝基苯硫酚是表面增强拉曼光谱研究中最常用的探针分子之一,对硝基苯硫酚在电极表面电化学还原反应的研究有助于对芳香族硝基化合物还原机理的认识. 本文应用暂态电化学-表面增强拉曼光谱技术,研究了对硝基苯硫酚在循环伏安和计时电流法过程中的表面增强拉曼光谱. 结果表明,实验实现了完全与电化学检测时间分辨率同步的表面增强拉曼光谱检测,以最快5毫秒的时间分辨率研究了对硝基苯硫酚分子在金电极表面的还原过程. 结果分析推测其此反应过程极快,在5毫秒的时间分辨率下仍难以捕获其中间物种. 本研究为人们更深层次研究和认识硝基苯类化合物电化学还原过程提供了参考和方向.     

Electrochemical synthesis of perfluoroalkylacetones

The interaction of electrochemically generated radicals in the electrolysis of the perfluorocarboxylic acids R_FCF₂COOH (I), where R_F=F (a), CF₃ (b), C₂F₅ (c), C₃F₇ (d), C₅F₁₁ (e), and C₇H₁₅ (f), with isopropenyl acetate (II) was studied. The dependence of the results of the electrolysis on the adsorption capacity of the anode permits the proposition that the interaction of (II) with the ECG-radicals occurs close to the surface of the electrode. The yield of the perfluoroalkylacetones comprised 30–37%.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1578–1584, July, 1991.     

Electrochemical oxidation of nitroylides

Conclusions The mechanisms of the electrochemical oxidation of mono- and dinitroylides of S and Se on a Pt electrode in CH₃CN have been studied for the first time. It was shown that the cation radical formed as intermediate was able to react with the medium with removal of an H atom and with the formation of an onium cation or to undergo decomposition. Competition of these processes determines the special features of the electrooxidation of mononitroylides, while on oxidation of dinitroylides the intermediate cation radical decomposed to oxides of nitrogen.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1332–1338, June, 1981.     

Electrochemical hydrogenation of citral

The effect of a water-organic mixed solvent of varying composition (H₂O-DMF, H₂0-EtOH) on the selectivity of electrocatalytic hydrogenation of citral at a copper cathode was studied. The experimental results were discussed from the standpoint of the effect of the solvent structure on the heterogeneous electrochemical process involving a bulky organic molecule.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 82–86, January, 1996.     

Electrochemical ultramicromethods of analysis

Summary Electroanalytical methods have been used under the conditions of chemical experimentation on the ultramicroscale. Capillary cells for coulometric titration with detection of equivalence points by various methods are described. A design is suggested for a reference palladium-hydrogen microelectrode with its own gas supply and a technique is described for measuring p_H by the quinhydrone method with the use of an insignificant fraction of the small test volume of solution. Coulometric ultramicrodeterminations based on oxidation-reduction, precipitation and complex formation have been carried out. By the suggested experimental technique, Zn, In and Ni have been determined in small samples of semiconductor alloys and cosmic particles.

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Zusammenfassung Elektrochemische Analysenmothoden wurden, im Ultramikromaßstab angewendet. Kapillarzellen für coulometrische Titrationen mit verschiedenen Methoden der Endpunktanzeige wurden beschrieben. Eine Palladium-Wasserstoff-Bezugselektrode mit eigener Gasversorgung wurde angegeben und ein Verfahren beschrieben, um p_H-Bestimmungen nach der Chinhydronmethode in einem ganz kleinen Teil einer Probelösung auszuführen. Coulometrische Ultramikrobestimmungen auf der Grundlage von Redoxvorgängen, von Fällungsreaktionen und von Komplexbildungen wurden ausgearbeitet. Mit Hilfe der empfohlenen Arbeitsweise wurden Zn, In und Ni in kleinen Proben von Halbleiterlegierungen und kosmischen Partikeln bestimmt.

     

Electrochemical treatment of tumours

The electrochemical treatment (EChT) of tumours implies that tumour tissue is treated with a continuous direct current through two or more electrodes placed in or near the tumour. The treatment offers considerable promise of a safe, simple and relatively noninvasive anti-tumour therapy for treatment of localised malignant as well as benign tumours. Although more than 10,000 patients have been treated in China during the past 10 years, EChT has not yet been universally accepted. The reason for this is the lack of essential preclinical studies and controlled clinical trials. Uncertainties regarding the destruction mechanism of EChT also hinder the development of an optimised and reliable dose-planning methodology. This article reviews the collected Chinese and occidental experiences of the electrochemical treatment of tumours, alone and in combination with other therapies. The current knowledge of the destruction mechanism underlying EChT is presented along with different approaches towards a dose planning methodology. In addition, we discuss our view of different important parameters that have to be accounted for, if clinical trials are to be initiated outside of China.     

Electrochemical behavior of zopiclone

The electrochemical properties of zopiclone, an anxiolytic and hypnotic drug, have been investigated by different techniques. The compound is reduced in two 2-electron steps in the pH range 0-12. The first step, which corresponds to the reduction of the pyrazine ring, is reversible in acidic and neutral solutions. Strong adsorption phenomena accompany the reduction process in acidic and neutral media. Zopiclone can be quantitatively measured over the entire pH range using DC polarography. However, the use of differential pulse and square-wave modes for quantitative measurements is more limited due to a slope modification in the current-concentration relationship. Adsorptive stripping voltammetry can be applied to the determination of low levels of the drug at pH 9, but only short deposition times may be used because large amounts of material accumulated under stirring conditions due to fast adsorption kinetics are rapidly released from the electrode surface. Detection limits are 1 x 10(-7)M and 2 x 10(-10)M for polarography and adsorptive stripping voltammetry, respectively. Only the first wave is of analytical interest for both techniques.     

Electrochemical methoxylation of alkenyldichloroanisoles

Electrochemical oxidation of chlorinated alkenylanisoles in anhydrous methanol was studied.     

头孢拉定的电化学行为

头孢拉定在ＮｏＯＨ溶液中降解后，于０．３ｍｏｌ／Ｌ ＮａＯＨ底液中有一灵敏的导数还原峰。电峰位为－０．８４Ｖ左右，峰电流ｉｐ与头孢拉定浓度在２．０＊１０＾－８－５．０＊１０＾Ｔ－６ｍｏｌ／Ｌ范围内呈线性关系，检测限为５．０＊１０＾－９ｍｏｌ／Ｌ。