Electrochemistry II PDF
Preview Electrochemistry II
43 Topics ni Current Chemistry Electrochemistry II Editor: E. Steckhan htiW snoitubirtnoC yb .G .S Calabrese, .W .R Heineman, A. Henglein, .C .E Lunte, R. Memming, .K M. O'Connell With 97 Figures and 9 Tables Springer-Verlag Berlin Heidelberg NewYork London Paris Tokyo This series presents critical reviews of the present position and future trends in modern chemical research. It is addressed to all research and industrial chemists who wish to keep abreast of advances in their subject. As a rule, contributions are specially commissioned. The editors and publishers will, however, always be pleased to receive suggestions and supplementary information. Papers are accepted for "Topics in Current Chemistry" in English. ISBN 8-62281-045-3 Heidelberg Springer-Verlag Berlin New York ISBN 8-62281-783-0 Springer-Verlag New York Heidelberg Berlin Library of Congress Cataloging-in-Publication Data (Revised for Vol. 2) Electrochemistry. (Topics in current chemistry; 142- ) .1 Electrochemistry -- Collected works. I. Steckhan, E. (Eberhard), 1943 . II. Fox, Marye Anne, 1947 . III. Series: Topics in current chemistry; 142, etc. QDI.F58 vol. 142 [QD 552] 540 s 541.3'7 87-9780 ISBN 0-387-17871-6 (New York: v. )1 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, re-use of illustra- tions, recitation, broadcasting, reproduction on microfilms or in other ways, and storage in data banks. Duplication of this publication or parts thereof is only permitted under the provisions of the German Copyright Law of September 9, 1965, in its version of June 24, 1985, and a copyright fee must always be paid. Violations fall under the prose- cution act of the German Copyright Law. © Springer-Ver[ag Berlin Heidelberg 1988 Printed in GDR The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulationsa nd therefore free for general use. Bookbinding: Lfideritz & Bauer, Berlin 2152/3020-543210 Editorial Board Prof. Dr. Michael J. S. Dewar Department of Chemistry, The University of Texas Austin, TX ,21787 USA Prof. Dr. Jack D. Dunitz Laboratorium fur Organische Chemie der Hochschule Eidgen6ssischen eBartssti~tisrevinU 6/8, CH-8006 hciri~Z Prof. Dr. Klaus Hafner Institut fiir der Organische Chemie TH PetersenstraBe .51 Darmstadt D-6100 Prof. Dr. Edgar Heilbronner Institut der Physikalisch-Chemisches ti~tisrevinU eBartsgreblegnilK ,08 CH-4000 lesaB Prof. Dr. Sh6 It6 Department of Chemistry, Tohoku University, Sendai, Japan 089 Prof. Dr. Jean-Marie Lehn Institut de Chimie, @tisrevinU de Strasbourg, i, rue esialB Pascal, .B .P Z 296/R8, 80076-F Strasbourg-Cedex Prof. Dr. Kurt Niedenzu University of Kentucky, College of Arts and secneicS Department of Chemistry, Lexington, KY ,60504 USA Prof. Dr. N. Kenneth Raymond Department of Chemistry, University of California, ,yelekreB California ,02749 USA Prof. Dr. Charles W. Rees Hofmann Professor of Organic Chemistry, Department of Imperial Chemistry, egelloC of ecneicS Technology, and South Kensington, London 7WS 2AY, England Prof. Dr. Fritz V6gtle Institut fiir und Organische Chemie Biochemie der Universitat, Gerhard-Domagk-Str. ,1 0035-D Bonn 1 Prof. Dr. Georg Wittig Institut fiir Organische der Chemie ti~tisrevinU Im Neuenheimer Heidelberg Feld D-6900 270, 1 Preface to the Series on Electrochemistry The scope of electrochemistry having broadened tremendously within the last ten years has become a remarkably diverse science. In the field of electroorganic synthesis, for example, selectivity has been improved by use of electrogenerated reagents, energy uptake lowered and space-time yields have been improved by using mediated reactions. In addition, electroorganic chemistry has applied been efficiently to the synthesis of key building blocks for complex molecules and has established its role as a new tool in organic synthesis. However electrochemistry has also found new and interesting applications in quite different fields of chem- istry. Photoelectrochemistry, as one example, si not only valuable for transformations of organic molecules but also for the very important goal of energy conversion. More insight has been gained in the processes occurring on illuminated semiconductor electrodes and micro particles. Designing the composition of electrode surfaces can lead to the selective activation of electrodes. Electrochemical sensors and techniques present new opportunities fotrh e analysis of biological compounds in medicine and biology. Research in the field of conducting polymers si very intensive because of interesting potential applications. Therefore I am very happy that Springer-Verlag has decided to account for these important developments by introducing a series of volumes on new trends in electrochemistry within its series Topics in Current Chemistry. The volumes will cover the important trends in electrochemistry as outlined above in the following manner: cinagroortcelE Synthesis by Indirect lacimehcortcelE Methods; New snoitacilppA of lacimehcortcelE ;seuqinhceT Recent tnempoleveD ni cinagroortcelE .sisehtnyS The guest editor is very happy and thankful that well-known experts who are actively engaged in research in these fields have agreed to contribute to the volumes. It is hoped that this collection of reviews is not only valuable to investigators in the respective fields but also to many chemists who are not so familiar with electrochemistry. Bonn, Mai 7891 Eberhard Steckhan Preface to Volume II Two volumes of the electrochemistry series in Topics in Current Chemistry are dedicated to new applications of electrochemical techniques. The contributions in Volume II cover two fields: -- Application of electrochemical methods as analytical tools for the detection as well as the concentration and activity determi- nation of biologically active compounds in bioanalysis and medicine; -- Electrochemical processes for photoelectrochemical energy conversion using semiconductor electrodes or microparticles. In the first two contributions electroanalytical techniques are described for application in bioanalysis and medicine. The increasing interest in this field is mainly due to the excellent selectivities and detection limits. In addition, the possibilities of miniaturization allow the development of in vivo analysis. The following two papers deal mainly with problems in energy conversion, in particular, the transformation of irradiation energy into electrical or chemical energy. The present status and future possible developments of photoelectrochemical energy conversion is presented. In a second paper electrochemical developments are connected to colloidal chemistry and the application of colloidal particles as catalysts for electron transfer reactions and as photo- catalysts are discussed. These articles may show that electrochemical developments and studies not only influence a restricted area but are also important for a number of other fields. Bonn, June 1987 Eberhard Steckhan Table of Contents Electrochemical Techniques in Bioanalysis C. E. Lunte, W. R. Heineman . . . . . . . . . . . . . Medical Applications of Electrochemical Sensors and Techniques G. S. Calabrese, K. M. O'Connell . . . . . . . . . . . . 49 Photoelectrochemical Solar Energy Conversion R. Memming . . . . . . . . . . . . . . . . . . . . . 79 Mechanism of Reactions on Colloidal Microelectrodes and Size Quantization Effects A. Henglein . . . . . . . . . . . . . . . . . . . . 113 AuthoIrn dex Volumes 101-143 . . . . . . . . . . . . . 181 Table of Contents of Volume 142 Electrochemistry I Organic Syntheses Electrochemically with Regenerable Redox Systems E. Steckhan Selective Formation of Organic sdnuopmoC Photoelectrosynthesis by at Particles Semiconductor M. A. Fox Oxidation of Organic Compounds at the Nickel Hydroxide Electrode H.-J. Sch/ifer Electrogenerated Bases J. Utley The Chemistry of Electrogenerated Acids (EGA) K. Uneyama Electrochemical Techniques ni Bioanalysis Craig E. Lunte* and William R. Heineman Department of Chemistry, University of Cincinnati, Cincinnati, Ohio ,2710-12254 U.S.A. Table of Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2 Potentiometry . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2.1 Ion-Selective Electrodes . . . . . . . . . . . . . . . . . . . . . 4 2.2 Gas-Sensing Electrodes . . . . . . . . . . . . . . . . . . . . . 6 2.3 Biocatalytic Membrane Electrodes : Biosensors . . . . . . . . . . . 7 2.4 Ion Sensitive Field Effect Transistor (ISFET) . . . . . . . . . . . . 11 2.5 Miniature Electrodes and in vivo Measurements . . . . . . . . . . . 21 2.6 Potentiometric Immunoassay . . . . . . . . . . . . . . . . . . . 14 3 Dynamic Techniques . . . . . . . . . . . . . . . . . . . . . . . . . 16 3.1 Liquid Chromatography/Electrochemistry . . . . . . . . . . . . . 19 3.1.1 Hydrodynamic Voltammetry . . . . . . . . . . . . . . . . 91 3.1.2 Mobile Phase Considerations . . . . . . . . . . . . . . . . 20 3.1.3 Electrode Materials . . . . . . . . . . . . . . . . . . . . 20 3.1.4 Cell Design . . . . . . . . . . . . . . . . . . . . . . . . 12 3.1.5 Conversion Efficiency . . . . . . . . . . . . . . . . . . . 24 3.1.6 Performance Evaluation . . . . . . . . . . . . . . . . . . 24 3.1.7 Applications . . . . . . . . . . . . . . . . . . . . . . . 25 3.1.7.1 Oxidative Applications . . . . . . . . . . . . . . . . 25 3.1.7.2 Reductive Applications . . . . . . . . . . . . . . . . 27 3.1.8 Voltammetric Detection . . . . . . . . . . . . . . . . . . . 28 3.2 Enzyme Linked Electrochemical Techniques . . . . . . . . . . . . 28 3.2.1 Off-Line Techniques . . . . . . ~ . . . . . . . . . . . . . 29 3.2.2 Enzyme Reactors . . . . . . . . . . . . . . . . . . . . . 30 3.2.3 Enzyme Electrodes . . . . . . . . . . . . . . . . . . . . . 13 * Current Address: Department of Chemistry, The University of Kansas, Lawrence, KS ,6400-54066 U.S.A. Topics in Current Chemistry, Vol, 341 © Springer-Verlag, Berlin Heidelberg fg~S Craig E. Lunte and William R. Heineman 3.2.4 Electrochemical Enzyme Immunoassay . . . . . . . . . . . . 31 3.2.4.1 Heterogeneous Immunoassays . . . . . . . . . . . . . 33 3.2.4.2 Homogeneous Immunoassays . . . . . . . . . . . . . 34 3.3 In vivo Electrochemical Techniques . . . . . . . . . . . . . . . . 35 3.3.1 Measurement Techniques . . . . . . . . . . . . . . . . . . 35 3.3.1.1 Chronoamperometry . . . . . . . . . . . . . . . . . 35 3.3.1.2 Linear Sweep Voltammetry . . . . . . . . . . . . . . 37 3.3.1.3 Differential Pulse Voltammetry . . . . . . . . . . . . 37 3.3.2 Electrodes for in vivo Analysis . . . . . . . . . . . . . . . . 37 3.3.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . 38 3.4 Anodic Stripping Voltammetry . . . . . . . . . . . . . . . . . . 39 4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 Electroanalytical techniques are currently gaining popularity in the area of biochemical analysis. There are several reasons for this growth. Electrochemical techniques provide both excellent detection limits with wide dynamic range. These methods are typically readily amenable to miniaturization. This leads to being able to use very small sample volumes. In vivo analysis is also possible. Finally, electrochemical techniques are generally very selective and when not selective enough can easily be coupled to even more selective techniques such as liquid chromatography or immunoassay. In this chapter, the basic concepts underlying electroanalytical methods of bioanalysis will be described. How these techniques can be used in bioanalytical chemistry will be illustrated. In ~ddition, the inter- relationship of the various electroanalytical techniques will be discussed.
The list of books you might like
