Table Of ContentREDOX CHEMISTRY
AND INTERFACIAL
BEHAVIOR OF
BIOLOGICAL MOLECULES
REDOX CHEMISTRY
AND INTERFACIAL
BEHAVIOR OF
BIOLOGICAL MOLECULES
Edited by
Glenn Dryhurst
The University oj Oklahoma
Norman, Oklahoma
and
Katsumi Niki
Yokohama National University
Yokohama, Japan
PLENUM PRESS • NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
International Symposium on Redox Mechanisms and Interfacial Properties of
Molecules of Biological Importance (3rd: 1987: Honolulu, Hawaii)
Redox chemistry and interfacial behavior of biological molecules / edited by
Glenn Dryhurst and Katsumi Niki.
p. cm.
"Proceedings of the Third International Symposium on Redox Mechanisms and
Interfacial Properties of Molecules of Biological Importance, held October 19-23,
1987, in Honolulu, Hawaii" - T.p. verso.
Includes index.
ISBN·13: 978·1·4615·9536·6 e·ISBN·13: 978-1·4615·9534-2
DOl: 10.1007/978-1·4615-9534-2
1. Bioelectrochemistry - Congresses. 2. Oxidation-reduction reaction - Con
gresses. 3. Biomolecules - Surfaces - Electric properties - Congresses. 1. Dryhurst,
Glenn, 1939- . II. Niki, Katsumi. III. Title.
QP517.B53I58 1987 88-29382
574.19'283-dc19 CIP
Proceedings of the Third International Symposium on
Redox Mechanisms and Interfacial Properties of Molecules
of Biological Importance, held October 19-23, 1987,
in Honolulu, Hawaii
© 1988 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1988
A Division of Plenum Publishing Corporation
233 Spring Street, New York, N.Y. 10013
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
PREFACE
The papers in this book were presented at the Third
International Symposium on Redox Mechanisms and Interfacial
Properties of Molecules of Biological Importance held in
Honolulu, Hawaii between October 19-23, 1987. This Symposium
was held as part of the 172nd Meeting of The Electrochemical
Society which was cosponsored by The Electrochemical Society
of Japan with the cooperation of The Japan Society of Applied
Physics.
The aim of the Symposium was to bring together a group of
electrochemists and bio-medical scientists with interests in
electrochemistry from around the world to present their most
current research results and/or to present up-to-date reviews
of current areas of research activity.
It is quite clear from the diversity of topics covered
in the various papers that electrochemistry and electrochemical
techniques and principles have much to contribute to our under
standing of many important biochemical phenomena. For example,
electrochemical studies are providing important insights into
the redox properties of biomolecules ranging from relatively
small organic molecules such as indoleamine neurotransmitters
to very large organic/organometallic molecules which include
various redox enzymes or model enzyme systems. Many of the
most powerful analytical techniques are now being coupled to
electrodes to monitor potential-controlled behaviors of bio
logical molecules at charged interfaces. Electrochemical
techniques are now being developed which permit extraordinarily
small electrodes to be inserted into single cells to monitor
electroactive biomolecules. Other microelectrodes are being
employed to control cell growth and to manipulate single cells.
Electrochemical techniques utilizing modified electrodes are
now being employed for very sensitive and selective analytical
measurements. All of these topics and many more are covered in
the forty six papers presented in this book. We hope that there
is much here to interest not only electrochemists and electro
analytical chemists but also the biomedical research community
in general.
It is always of very great importance to the success of
any major symposium to have the participation of established
scientists from throughout the world and, equally importantly,
v
young investigators at the beginning of their independent
scientific careers. We are thus very pleased to acknowledge
the financial support provided by the following organizations
which permitted many such people to attend the Symposium:
Office of Naval Research
EE&G Princeton Applied Research Corporation
Eli Lilly Corporation
The Organic and Biological Electrochemistry
Division of The Electrochemical Society
We would also like to express our thanks to Melanie
Yelity and Lisa Honski of Plenum Publishing Corporation for
help and advice concerning the preparation of the manuscript.
Finally, we would like to thank Susan Kyncl who typed the
entire manuscript and provided help in numerous other ways.
Glenn Dryhurst
Konstanz
Katsumi Niki
Yokohama
May 1988
CON'l'EN'rS
Supramolecular Effects in the Redox and Coordination 1
Chemistry of Superstructured Porphyrins
D. Lexa and J.M. Saveant
Electrochemistry of Metalloporphyrins Containing a 27
Metal-Metal or Metal-Carbon Bond
K.M. Kadish
A study of the Effects of Ionic Strength and Anion 47
Binding on the Reduction Potential of Cytochrome c
Using Microelectrodes
S. Sun, D.E. Reed and F.M. Hawkr~dge
Electrochemical Reactivity of Strongly Adsorbed 63
Cytochrome c
J.L. Willit and E.F. Bowden
Redox Reactivity of Manganese "Capped" Metalloporphyrins 77
L.A. Bottomley, J.F. Luck, F.L. Neely and J.S. Quick
Metalloporphyrin Films on Solid Electrodes: Reflectance 87
Spectroscopy and AC Impedance Studies in Aqueous and
Nonaqueous Media
T. Malinski and J.E. Bennett
Bacterial Cytochrome P-450 Enzymes and Reactions on 105
Immobilized Electrodes. I. Preliminary Studies
V.L. Vilker, F. Khan, D. Shen, M.M. Baizer and
K. Nobe
Interfacial Electrochemistry of Promoter-Modified 113
Electrodes for the Rapid Electron-Transfer of
Cytochrome c
I. Taniguchi
SERS Studies on the Electrode Reaction of 125
Cytochrome c at Silver Electrodes in the Presence
of Pyridine Derivatives
F. Ke-jun, I. Satake, K. Ueda, H. Akutsu and
K. Niki
vii
The Electrochemical Characterization of Oxene Adducts 139
of PFe (Cl04 ), PFeI I, and PFeI I (SR) [P = Tetrakis
(2,6-Dichlorophenyl)porphinato Dianion] in Acetonitrile:
Models for Compounds I and II of Horseradish Peroxidase
and for Activated Cytochrome P-450
D.T. Sawyer, H. Sugimoto, H.-C. Tung and
P.K.S. Tsang
Direct Electrical Communication Between Chemically 151
Modified Enzymes and Metal Electrodes:
III. Electron-Transfer Relay Modified Glucose
Oxidase and D-Amino Acid Oxidase
A. Heller and Y. Degani
Potential-Controlled Enzymatic Activity of Conducting 173
Enzyme Membrane
M. Aizawa, So-ichi Yabuki and H. Shinohara
Electro-Enzymatic Studies of the Interfacial Behavior 181
of Proteins
F.W. Scheller, R. Hintsche, V. Bogdanovskaja
and P. Ohlsson
Catalytic Oxidation of D-Glucose at an Enzyme- 193
Modified Electrode with Entrapped Mediator
I. Ikeda, H. Hiasa and M. Senda
Electrochemistry of the Iron-Molybdenum Cofactor 203
of Nitrogenase: Evidence for Multiple Speciation
and ElectrocatalyticBehavior
F.A. Schultz, S.F. Gheller and W.E. Newton
SERRS as a Probe of Electrode Processes: 217
Interaction of Glucose Oxidase and FAD at Silver
Electrodes
R.E. Holt and T.M. Cotton
Surface Electrochemistry of Amino Acids: 229
Voltammetry Assisted by EELS, Auger Spectroscopy
and LEED
A.T. Hubbard, D.G. Frank,
M.J. Tarlov, N. Batina, N. Walton,
E. Wellner and J.W. McCarger
Electrochemistry and Spectroelectrochemistry 247
of Adenine and Adenosine Complexes with
3d Transition Metals
T. Malinski, J.R. Fish, C.N. Mikulski
and N.M. Karayannis
viii
Electrochemical Study of the Mechanism and 267
Kinetics of Oxygen Reduction Mediated by
Anthracycline Antibiotics Adsorbed on Electrode
Surface
K. Kano, T. Konse, B. Uno and T. Kubota
Studies on Redox Phototransformations of Reduced 281
Forms of Coenzyme RADP+ and Related Compounds
B. Czochralska, E. Bojarska and K. Pawlicki
Anticancer Quinones and Quinolines: Mode of Action 295
via Electron Transfer and Oxidative Stress
P. Kovacic, J.R. Ames, J.W. Grogan,
B. Hazra and M.D. Ryan
Oxidation Pathways of Purine Drugs: 309
Electrochemical, Liquid Chromatographic and Mass
Spectrometric Insights
K.J. Volk, T. Peterson, K. McKenna,
P.J. Kraske and A. Brajter-Toth
Electron Transfer Mechanism for Cocaine Action 323
P. Kovacic, J.R. Ames, M. Jawdosiuk
and M.D. Ryan
Studies of Acid-Base, Hydration-Dehydration and 333
Keto-Enol Equilibria in Aqueous Solutions of
a-Ketoacids by Polarography, Linear Sweep
Voltammetry and Spectroscopy
J. Kozlowski and P. Zuman
Electron Transfer Oxy-Radical Mechanism for 345
Anticancer Agents: Etoposide, Cu DIPS, and
Bis(9-aminoacridines)
P. Kovacic, J.R Adams and M.D Ryan
Surface Enhanced Raman Scattering (SERS) 359
Spectroscopy of Guanine Derivatives
E. Koglin and J.-M. Sequaris
Electrochemistry in Cancer: Applications to 369
Pharmacological Studies and Quinone-Containing
Antitumor Agents
P.L. Gutierrez and B. Nguyen
On the Electrocatalytic Oxidation of D-Glucose 383
and Related Polyols on Large Pt and Au Electrodes
o. Enea
Electrochemistry of Some Synthetic Oxygen Carrier 397
Molecules in Water
J.P. Ciccone, L.A. Deardurff, E.S. DeCastro,
J.B. Kerr and B.D Zenner
Electrochemical Studies on the Generation of 407
Active Oxygen Species in Biological Systems with
the Use of Mediators
S. Kwee
Intracellular Voltammetry with Ultrasmall Carbon 417
Ring Electrodes
J.B. Chien, R.A. Saraceno and A.G. Ewing
Oxidation Chemistry of CNS Indoles 425
M.Z. Wrona, K. Humphries and G. Dryhurst
Organic Electrochemistry IV: Electrochemical 447
Desulfurization Reactions of Thiolumazines
W. Pfleiderer and B.S. Schulz
Determination of Cationic Drugs on a Nafion 457
Coated Electrode
T. Matsue, A. Aoki and I. Uchida
Adsorptive Stripping Voltammetric Studies of 469
Biologically-Significant Compounds
J. Wang
Modified Electrodes Used to Elucidate Electro 479
chemical Behaviors of Biologically Significant
Molecules
G.J. Patriarche, J.-M. Kauffmann and J.-C. Vire
Studies of the Kinetics of Mediated Electrochemical 499
Oxidation at Polymer-Coated Electrodes
M. Sharp
Electrochemical Preparation of Metallophthalocyanine 515
Films
S.-i. Iijima, F. Mizutani, Y. Tanaka and
K. Ichimura
Selective Determination of Phosphate with PhoE 521
Porin-Lecithin Membrane Electrode
T. Matsunaga, A. Shigematsu, Y. Asakura,
H. Abe and S. Takezawa
x
Membrane Bioenergetics as Viewed from Reconstitution 529
Experiments
H. Ti Tien
Surface Charge Determines the Aggregation of Hemoglobin 557
Subunits as Predicted by the Surface Free Energy
M. Blank
Electrocatalysis in Membrane Mimetic Media 565
J.F. Rusling, C.-N. Shi and E.C. Couture
Some Techniques for Investigation of Electrochemical 583
and Ion Transport Properties of Biological Cell
Membranes: The Case of Chara Corallina
F. Homble, A. Jenard and H.D. Hurwitz
Vectorial Control of Cell Growth with Microelectrodes 613
H. Matsuoka, S. Matsumoto and M. Kinoshita
Electrochemical Manipulation of Single Cell with a 623
Microelectrode
M. Yaoita, J. Kojima, H. Shinohara and M. Aizawa
Y. Ikariyama
Introduction of New Alcohol Binding Sites at the 631
Lipid/Water Interface by the Incorporation of
Monosialogangliosides into DPPC Liposomes
G.P. Kreischman, C. Grahame-Brittain,
H.E. Schueler and R.J. Hitzemann
Index 641
