Table Of Content43
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
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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.
