SUBCELLULAR BIOCHEMISTRY Volume 35 Enzyme-Catalyzed Electron and Radical Transfer Edited by Andreas Holzenburg and Nigel S. Scrutton Enzyme-Catalyzed Electron and Radical Transfer Subcellular Biochemistry Volume 35 SUBCELLULAR BIOCHEMISTRY SERIES EDITOR J. ROBIN HARRIS, Institute of Zoology, University of Mainz, Mainz, Germany ASSISTANT EDITORS H. J. HILDERSON, University of Antwerp, Antwerp, Belgium B. B. BISWAS, University of Calcutta, Calcutta, India Recent Volumes in This Series Volume 26 myo - Inosital Phosphates, Phosphoinositides, and Signal Transduction Edited by B. B. Biswas and Susweta Biswas Biology of the Lysosome Edited by John B. Lloyd and Robert W. Mason Cholesterol: Its Functions and Metabolism in Biology and Medicine Edited by Robert Bittman PlantñMicrobe Interactions Edited by B. B. Biswas and H. K. Das Fat-Soluble Vitamins Edited by Peter J. Quinn and Valerian E. Kagan Intermediate Filaments Edited by Harald Herrmann and J. Robin Harris α -Gal and Anti-Gal: α 1,3 -Galactosyltransferase, α -Gal Epitopes, and the Natural Anti-Gal Antibody Edited by Uri Galili and JosÈ Luis Avila Bacterial Invasion into Eukaryotic Cells Edited by Tobias A. Oelschlaeger and Jˆrg Hacker Fusion of Biological Membranes and Related Problems Edited by Herwig Hilderson and Stephen Fuller Enzyme-Catalyzed Electron and Radical Transfer Edited by Andreas Holzenburg and Nigel S. Scrutton Volume 27 Volume 28 Volume 29 Volume 30 Volume 31 Volume 32 Volume 33 Volume 34 Volume 35 A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher. Enzyme-Catalyzed Electron and Radical Transfer Subcellular Biochemistry Volume 35 Edited by Andreas Holzenburg Texas A&M University College Station, Texas (formerly of University of Leeds Leeds, United Kingdom) and Nigel S. Scrutton University of Leicester Leicester, United Kingdom Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: http://www.kluweronline.com and Kluwer's eBookstore at: http://www.ebooks.kluweronline.com Print ISBN 0-306-46399-7 eBook ISBN 0-306-46828-X ©2002 Kluwer Academic / Plenum Publishers, New York 233 Spring Street, New York, N. Y. 10013 Prin 2000 KluwerAcademic / Plenum Publishers, New Yorkt © INTERNATIONAL ADVISORY EDITORIAL BOARD R. BITTMAN, City University of New York, New York, USA N. BORGESE, CNR Center for Cytopharmacology, University of Milan, Milan, Italy D. DASGUPTA, Saha Institute of Nuclear Physics, Calcutta, India H. ENGELHARDT, Max-Planck-Institute for Biochemistry, Martinsried, Germany A H. ETEMADI, University of Paris VI, Paris France S. FULLER, University of Oxford, Oxford, UK J. HACKER, University of W¸rzburg, W¸rzburg, Germany H. HERRMANN, German Cancer Research Center, Heidelberg, Germany A. HOLZENBURG, Texas A&M University, College Station, Texas, USA J. B. LLOYD, University of Sunderland, Sunderland, England, UK P. QUINN, Kingís College London, London, England, UK S. ROTTEM, The Hebrew University, Jerusalem, Israel This page intentionally left blank. To Our Parents This page intentionally left blank. Contributors Christopher Anthony Division of Biochemistry and Molecular Biology, School of Biological Sciences, University of Southampton, Southamp- ton, SO16 7PX, United Kingdom Edward A. Berry E.O. Lawrence Berkeley National Laboratory, Uni- versity of California, Berkeley, California 94720 Brian J. Brazeau Department of Biochemistry, Molecular Biology, and Biophysics, University of Minnesota, Minneapolis, Minnesota 55455 Marion E. van Brederode Faculty of Sciences, Division of Physics and Astronomy, Department of Biophysics and Physics of Complex Systems, Free University of Amsterdam, 1081 HV Amsterdam, The Netherlands Stephen K. Chapman Department of Chemistry, University of Edin- burgh, Edinburgh EH9 3JJ, Scotland, United Kingdom Xiaoxi Chen Johnson Research Foundation, Department of Biochem- istry and Biophysics, University of Pennsylvania, Philadelphia, Penn- sylvania 19104 Louise Cunane Department of Biochemistry and Molecular Bio- physics, Washington University School of Medicine, St. Louis, Missouri 63110 Victor L. Davidson Department of Biochemistry, University of Missis- sippi Medical Center, Jackson, Mississippi 39214-4505 Rosemary C. E. Durley Department of Biochemistry and Molecular Biophysics, Washington University School of Medicine, St. Louis, Missouri 63110 ix [...]... Complexity of Protein Electron Transfer Reactions 4.2.1 True Electron Transfer 4.2.2 Coupled Electron Transfer 4.2.3 Gated Electron Transfer 4.3 Electron Transfer from TTQ to Copper 4.3.1 Non-Adiabatic Electron Transfer Reactions 4.3.2 Mutation of Amicyanin Alters the HAB f o r Electron Transfer from MADH... 4.3 Theoretical Considerations on Radical Transfer and Protein Dynamics 5 Generation of the Stable Tyrosyl Radical in Protein R2 5.1 Radical Generation Involves the Radical Transfer Pathway 5.2 Interactions between Metal Sites 5.3 Non-Native Radicals and Secondary Radical Transfer Pathways Observed in Mutant R2... 3.2 Ubiquinol Formation and Re-Reduction of P + 3.3 Light-Driven Cyclic Electron Transfer Coupled to Proton Translocation Biological Electron Transfer 4.1 Non-Adiabatic Electron Transfer 4.2 Adiabatic Electron Transfer Studies of Ultrafast Electron Transfer in a Light-Activated Protein... Selectivity and Electron Transfer in a Model Cytochrome P450 Andrew W Munro, Michael A Noble, Tobias W B Ost, Amanda J Green, Kirsty J MacLean, Laura Robledo, Carolyn S Miles, Jane Murdoch, and Stephen K Chapman 1 2 3 4 5 6 7 Introduction Bacterial Model P450 Systems P450 BM3 Structure and Mechanism Electron Transfer and. .. for exponential decay of electron transfer in vacuum to be about 2.8≈ ñ1 Much less of a barrier is presented by a surrounding organic Electron Transfer in Natural Proteins 3 medium, where the positively charged nuclei can interact favorably with the electron Studies of the distance dependence of electron transfer between donors and acceptors bridged by rigid covalent linkers and dissolved in an organic... Detailed understanding of these reactions requires knowledge of the role of protein dynamics, chemistries of the redox-active prosthetic groups, the mechanisms governing the diffusional encounter and assembly of electron transfer complexes and the role of protein structure in controlling the physical parameters (reorganisational energy and electronic coupling matrix element) that govern the transfer rate... 5.1 The Role of the BA Monomeric BChl 5.2 The Asymmetry of Primary Electron Transfer 5.2.1 Evidence for the Asymmetry of Primary Electron Transfer 5.2.2 Origins of the Asymmetry of Primary Electron Transfer 5.2.3 Re-Routing Primary Electron Transfer 5.3 Temperature DependenceóActivationless Reactions 5.4 Dispersive... Chapter 1 Electron Transfer in Natural Proteins Theory and Design Christopher C Moser, Christopher C Page, Xiaoxi Chen, and P Leslie Dutton 1 INTRODUCTION Biochemical catalysis and redox energy conversion requires the engineering of electron transfer from site to site within proteins Yet, the protein interior is a good electrical insulator More than 30 years ago, Devault & Chance (Devault and Chance,... (Devault and Chance, 1966) made it clear that Nature relies on electron tunneling to move electrons over tens of ≈ngstroms In flash activated photosynthetic membranes, visible spectroscopy can monitor heme and chlorophyll oxidation and reduction electron transfer kinetics down to liquid helium temperatures At temperatures below 100K, electron transfer kinetics became temperature independent, the hallmark... the electron over the insulating barrier, quantum tunneling through the energy barrier is still possible Electron tunneling, undeniable in CHRISTOPHER C MOSER, CHRISTOPHER C PAGE, XIAOXI CHEN and P LESLIE DUTTON Johnson Research Foundation, Department of Biochemistry and Biophysics, University of Pennsylvania, Philadelphia, PA 19104 Subcellular Biochemistry, Volume 35: Enzyme-Catalyzed Electron and Radical . SUBCELLULAR BIOCHEMISTRY Volume 35 Enzyme-Catalyzed Electron and Radical Transfer Edited by Andreas Holzenburg and Nigel S. Scrutton Enzyme-Catalyzed Electron and Radical Transfer Subcellular Biochemistry Volume. . 94 94 95 97 97 100 102 105 105 105 107 109 110 112 119 120 121 121 124 125 125 126 128 128 128 129 131 xviii Contents 4.1. Electron Transfer Theory 4.2. Kinetic Complexity of Protein Electron Transfer Reactions 4.2.1. True Electron Transfer . 4.2.2. Coupled Electron Transfer . 4.2.3. Gated Electron Transfer . of Biological Membranes and Related Problems Edited by Herwig Hilderson and Stephen Fuller Enzyme-Catalyzed Electron and Radical Transfer Edited by Andreas Holzenburg and Nigel S. Scrutton Volume