Table Of ContentChemistry
and
Biochemistry
of
Flavoenzymes
Volume III
Editor
Franz Muller, Ph.D,
Head
Central Development
Toxicology
Sandoz Agro, Ltd.
Basle, Switzerland
and
Adjunct Professor
Department of Biochemistry
University of Georgia
Athens, Georgia
Boca Raton London New York
CRC Press
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BToacylao r R& aFrtaoncnis GAronunp, Aanr inbfoorrm aL bousnindesosn
First published 1992 by CRC Press
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Library of Congress Cataloging-in-Publication Data
(Revised for volume 3)
Chemistry and biochemistry of flavoenzymes.
Includes bibliographical references and index.
1. Flavoproteins. 2. Flavins. I. Müller, Franz,
1934–
QP552.F54C44 1990 574.19’258 90-40024
ISBN 0-8493-4393-3 (v. 1)
ISBN 0-8493-4394-1 (v. 2)
ISBN 0-8493-4395-x (v. 3)
A Library of Congress record exists under LC control number: 90040024
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PREFACE
Flavin was discovered about a century ago. Since its discovery, the field of flavin and
flavoproteins has developed into a mature science. Although a few flavoproteins had already
been discovered during the first three decades of the 20th century, a profound understanding
of the enzymic reaction mechanisms of flavoproteins became possible only after full de-
velopment of the chemical and physical properties of free flavin. This development was
initiated about 60 years ago and was mainly concerned with the chemical synthesis of the
flavin molecule. Research in the field of flavins and flavoproteins was discontinued during
the Second World War, but revived in the 1950s. The postwar period brought increased
progress in the chemistry of free flavin, which knowledge was instrumental in understanding
the biochemical properties of flavoproteins.
Flavoproteins are involved in a variety of biological reactions including electron transfer,
oxidation, dehydrogenation, and monooxygenation reactions. Many flavoproteins contain
flavin as the sole prosthetic group, but the reaction mechanisms can still be complex. Other
flavoproteins are composed of flavin and heme and non-heme iron, molybdenum and other
metal ions, or pteridin. Although they represent a minority, flavoproteins resulting from
covalent bondings of the prosthetic group to amino acid residues of proteins have enhanced
the variety of flavoproteins.
Present knowledge in the field discussed in this work would not be possible without
advancements in biophysical equipment. New techniques have contributed a great deal to
the elucidation of primary, secondary, tertiary, and quaternary structures of flavoproteins.
In recent years the three-dimensional structures of a few flavoproteins have become available,
and it can be expected that this research will continue to advance. These data will provide
the basis for new research on flavoproteins — namely, cloning of genes, encoding for
flavoproteins, followed by site-directed mutagenesis of flavoproteins. This research is pres-
ently in its infancy, but is expected to develop and provide even deeper insight into the
enzymic mechanisms of flavoproteins and the biochemical principles governing the catalytic
action of particular flavoenzymes.
Given the wealth of data available on flavins and flavoproteins, it seems appropriate to
report on the progress of a century of research in the field. In the present work an attempt
has been made to summarize this knowledge as comprehensively as possible. Despite lim-
itations of space and unavailability of some material, this and succeeding volumes of the
Chemistry and Biochemistry of Flavoenzymes should be a valuable reference for researchers
in the field and those entering it, as well as a source for lecturers in biochemistry, biophysics,
chemistry, pharmacology, toxicology, and medicine.
In conclusion I wish to thank all contributors for their cooperation and their efforts to
meet our deadlines, and I would also like to express personal appreciation to my wife, Rita,
and our daughters, Sandra and Kirsten, for their patience over many weekends in the
development of this series.
Franz Miiller
THE EDITOR
Franz Muller, Ph.D., is Head, Central Development of Toxicology, Sandoz Agro Ltd.,
Basle, Switzerland and Adjunct Professor of Biochemistry, University of Georgia, Athens,
Georgia.
Dr. Muller obtained his training at the University of Basle, and received his M.S. degree
in 1961 and Ph.D. degree in 1964 from the Departments of Organic and Inorganic Chemistry.
After doing postdoctoral work at the Medical Nobel Institute, Department of Biochemistry,
Stockholm, Sweden, he was first a Research Associate in the Department of Biological
Chemistry at the University of Michigan in Ann Arbor, and later Instructor, and a recipient
of a Career Research Development Award from the National Institutes of Health. In 1971
he was appointed an Associate Professor of Biochemistry at the Agricultural University,
Wageningen, The Netherlands, and Research Professor in 1977, where he served as Chairman
of the Department of Biochemistry and chaired the university's Science Committee and the
Committee for Biotechnology. In 1987 he assumed his present position.
Dr. Muller is a member of the Swiss Chemical Society, the Swiss Association of
Chemists, the Federation of European Biochemical Societies and the New York Academy
of Sciences.
He received the Venia Legendi (Habilitation) from the University of Constance, Federal
Republic of Germany, in 1970.
Dr. Muller has been the recipient of research grants from The Netherlands Science
Foundation. He was also a member of the Committee for Natural Sciences of the grant
agency and chaired the Section for Protein Chemistry. He has published more than 200
papers. His current research interests are in biochemical transformation of pesticides.
CONTRIBUTORS
Brian A. C. Ackrell, Ph.D. Bruno Curti, Ph.D.
Molecular Biology Division Department of General Physiology
Veterans Administration Medical Center and Biochemistry
San Francisco, California University of Milano
Milano, Italy
Thomas O. Baldwin, Ph.D.
Department of Biochemistry and Biophysics Paul C. Engel, D. Phil.
Texas A&M University Department of Molecular Biology
College Station, Texas and Biotechnology
Krebs Institute University of Sheffield
David P. Ballou, Ph.D. Sheffield, England
Department of Biological Chemistry
University of Michigan Robert P. Gunsalus, Ph.D.
Ann Arbor, Michigan Department of Microbiology and Molecular
Genetics and Molecular Biology Institute
Michael J. Barber, D. Phil. University of California
Department of Biochemistry and Molecular Los Angeles, California
Biology
College of Medicine Russ Hille, Ph.D.
University of South Florida Department of Medical Biochemistry
Tampa, Florida Ohio State University
Columbus, Ohio
P. I. H. Bastiaens, M.Sc.
Department of Biochemistry T. R. Hopkins, Ph.D.
Agricultural University Biospec Products, Inc.
Wageningen, The Netherlands Bartlesville, Oklahoma
Christopher J. Bade, Ph.D. Michael K. Johnson, Ph.D.
Department of Biochemistry and Department of Chemistry
Molecular Biology University of Georgia
University of Louisiana Medical School Athens, Georgia
New Orleans, Louisiana
Andrew Karplus, Ph.D.
Gary Cecchini, Ph.D. Biochemistry, Molecular and Cell Biology
Molecular Biology Division Section
Veterans Administration Medical Center Cornell University
San Francisco, California Ithaca, New York
Jorge E. Churchich, Ph.D. Jung-Ja P. Kim, Ph.D.
Department of Biochemistry Department of Biochemistry
University of Tennessee Medical College of Wisconsin
Knoxville, Tennessee Milwaukee, Wisconsin
Carl C. Correll, M.Sc. Francis Kwok, Ph.D.
Department of Biological Chemistry Department of Applied Biology
and Biophysics Research Division and Chemical Technology
University of Michigan Hong Kong Polytechnic
Ann Arbor, Michigan Hong Kong
Jorge Lampreia, Ph. D, Emil F, Pai, Dr. rer. nat.
Center of Chemical and Biological Department of Biophysics
Technology (CTQB) Max-Planck-Institute for Medical Research
Oeiras, Portugal Heidelberg, Germany
John Lee, Ph.D. Harry D. Peck, Jr., Ph.D.
Department of Biochemistry Department of Biochemistry
University of Georgia University of Georgia
Athens, Georgia Athens, Georgia
Jean LeGall, Ph.D.
Severino Ronchi, Ph.D.
Department of Biochemistry
Institute of Veterinary Physiology
University of Georgia
and Biochemistry
Athens, Georgia
University of Milano
Milano, Italy
Ylva Lindquist, Ph.D.
Department of Molecular Biology
John V. Schloss, Ph.D.
Swedish University of Agricultural Science
Department of Medicinal Chemistry
Uppsala, Sweden
University of Kansas
Lawrence, Kansas
Martha L. Ludwig, Ph.D.
Biophysics Research Division
and Department of Biological Chemistry G. E. Schulz, Dr. Rer. Nat.
University of Michigan Institute of Organic and Biochemistry
Ann Arbor, Michigan Albert-Ludwigs University
Freiburg, Germany
Catherine L. Luschinsky, M. S.
Department of Biological Chemistry Mirella Pilone Simonetta, D. Biol. S.,
University of Michigan Department of General Physiology
Ann Arbor, Michigan and Biochemistry
University of Milano
Stephen G. Mayhew, Ph.D. Milano, Italy
Department of Biochemistry
University College
Larry P. Solomonson, Ph.D.
Belfield
Department of Biochemistry and
Dublin, Ireland
Molecular Biology
College of Medicine
Isabel Moura, Ph. D.
University of South Florida
Center of Chemical and Biological
Tampa, Florida
Technology (CTQB)
Oeiras, Portugal
Gordon Tollin, Ph.D.
Department of Biochemistry
Jose J. G. Moura, Ph.D.
University of Arizona
Center of Chemical and Biological
Tucson, Arizona
Technology (CTQB)
Oeiras, Portugal
Maria A. Vanoni, Ph.D.
Franz Muller, Ph.D. Department of General Physiology
Department of Toxicology and Biochemistry
Sandoz, Ltd. University of Milano
Basle. SwitvfM-i^rn-i \s:\~~~. T+~U.
Charles H. Williams, Jr., Ph.D. Antonio V. Xavier, Ph.D.
Research Service Center of Chemical and Biological
Department of Veterans Affairs Technology (CTQB)
Medical Center Oeiras, Portugal
Ann Arbor, Michigan
G. Zanetti, Ph.D.
Jin Wu, B.S. Department of General Physiology
Department of Chemistry and Biochemistry
Syracuse University University of Milano
Syracuse, New York Milano, Italy
Miriam M. Ziegler, Ph.D.
Department of Biochemistry and Biophysics
Texas A&M University
College Station, Texas
TABLE OF CONTENTS
Chapter 1
Pyridoxine-5-P Oxidase 1
F, Kwok and J. E. Churchich
Chapter 2
Xanthine Oxidase, Xanthine Dehydrogenase, and Aldehyde Oxidase 21
R. Hille
Chapter 3
D- and L-Amino Acid Oxidases 69
B. Curti, S. Ronchi, and M. P. Simonetta
Chapter 4
Methanol Oxidase 95
F. Miiller, T. R. Hopkins, J. Lee, and P. I. H. Bastiaens
Chapter 5
Lipoamide Dehydrogenase, Glutathione Reductase, Thioredoxin Reductase,
and Mercuric Ion Reductase — A Family of Flavoenzyme Transhydrogenases 121
C. H. Williams, Jr.
Chapter 6
Refined Three-Dimensional Structure of Glutathione Reductase 213
P. A. Karplus and G. E. Schulz
Chapter 7
Structure and Function of Succinate Dehydrogenase and Fumarate Reductase 229
B. A. C. Ackrell, M. K. Johnson, R. P. Gunsalus, and G. Cecchini
Chapter 8
Three-Dimensional Structure of Medium-Chain Acyl-CoA Dehydrogenase 299
J.-J. P. Kim and J. Wu
Chapter 9
Glutamate Synthase 309
M. A. Vanoni, B. Curti, and G. Zanetti
Chapter 10
Assimilatory Nitrate Reductase 319
M. J. Barber and L. P. Solomonson
Chapter 11
Biological Reduction and Formation of Sulfate; the Role of APS Reductase,
and FAD(Iron-Sulfur)-Containing Protein 333
J. Lampreia, L Moura, A, V. Xavier, J. Le Gall, H. D. Peck, Jr.,
and J. J. G. Moura
Chapter 12
The Stereochemistry of the Prosthetic Groups of Flavoproteins 357
E. F. Pai
Chapter 13
Structure and Mechanism of Spinach Glycolate Oxidase 367
Y. Lindqvist
Chapter 14
General Properties of Flavodoxins 389
S. G. Mayhew and G. Tollin
Chapter 15
Structure and Redox Properties of Clostridial Flavodoxin 427
M. L. Ludwig and C. L. Luschinsky
Chapter 16
Biochemistry and Molecular Biology of Bacterial Bioluminescence 467
T. O. Baldwin and M. M. Ziegler
Chapter 17
Acetolactate Synthase 531
J. V. Schloss
Chapter 18
Phthalate Dioxygenase Reductase and Related Flavin-Iron-Sulfur-Containing
Electron Transferases 543
C. J. Bade, D. P. Ballou, and C. C. Correll
Chapter 19
Nuclear Magnetic Resonance Studies on Flavoproteins 557
F. Miiller
Chapter 20
Acyl-Coenzyme A Dehydrogenases 597
P. C. Engel
Index 657
