Copper-Oxygen Chemistry E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: Wiley Series of Reactive Intermediates
• Sprache: Englisch

Seitenzahl: 847

Veröffentlichungsjahr: 2011

Beschreibung

Covers the vastly expanding subject of oxidative processes mediated by copper ions within biological systems

Copper-mediated biological oxidations offer a broad range of fundamentally important and potentially practical chemical processes that cross many chemical and pharmaceutical disciplines. This newest volume in the Wiley Series on Reactive Intermediates in Chemistry and Biology is divided into three logical areas within the topic of copper/oxygen chemistry— biological systems, theory, and bioinorganic models and applications—to explore the biosphere for its highly evolved and thus efficient oxidative transformations in the discovery of new types of interactions between molecular oxygen and copper ion. Featuring a diverse collection of subject matter unified in one complete and comprehensive resource, Copper-Oxygen Chemistry probes the fundamental aspects of copper coordination chemistry, synthetic organic chemistry, and biological chemistry to reveal both the biological and chemical aspects driving the current exciting research efforts behind copper-oxygen chemistry. In addition, Copper-Oxygen Chemistry:

• Addresses the significantly increasing literature on oxygen-atom insertion and carbon-carbon bond-forming reactions as well as enantioselective oxidation chemistries

• Progresses from biological systems to spectroscopy and theory, and onward to bioinorganic models and applications

• Covers a wide array of reaction types such as insertion and dehydrogenation reactions that utilize the cheap, abundant, and energy-containing O2 molecule

With thorough coverage by prominent authors and researchers shaping innovations in this growing field, this valuable reference is essential reading for bioinorganic chemists, as well as organic, synthetic, and pharmaceutical chemists in academia and industry.

Leseprobe

Contents

Cover

Wiley Series of Reactive Intermediates in Chemistry and Biology

Title Page

Copyright

Preface to Series

Introduction

Contributors

Chapter 1: Insights into the Proposed Copper–Oxygen Intermediates that Regulate the Mechanism of Reactions Catalyzed by Dopamine β-Monooxygenase, Peptidylglycine α-Hydroxylating Monooxygenase, and Tyramine β-Monooxygenase

1.1. General Introduction

1.2. Comparative Properties of Dopamine β-Monooxygenase (DβM), Peptidylglycine α-Hydroxylating Monooxygenase (PHM), and Tyramine β-Monooxygenase (TβM)

1.3. Sequence, Structure, and Spectroscopy

1.4. Enzyme Mechanisms Derived from Kinetic Characterization and Kinetic Isotope Effects

1.5. A Network of Communication Between CuM and CuH

1.6. Concluding Remarks and Future Prospects

Abbreviations

References

Chapter 2: Copper Dioxygenases

2.1. Introduction

2.2. Fungal Flavonol 2,4-Dioxygenase Enzymes

2.3. Model Systems

2.4. Concluding Remarks

Acknowledgments

References

Chapter 3: Amine Oxidase and Galactose Oxidase

3.1. Introduction

3.2. Basic Structures

3.3. Post-Translational Modification

3.4. Catalytic Mechanism

3.5. Conclusions and Future Prospects

Abbreviations

References

Chapter 4: Energy Conversion and Conservation by Cytochrome Oxidases

4.1. Introduction

4.2. Structural Features of Heme–Copper Oxidases

4.3. Electron Transfer

4.4. proton-conducting Pathways

4.5. Functional Aspects of Cytochrome c Oxidase

4.6. Catalytic Cycle

4.7. Conclusion and Future Prospects

Abbreviations

References

Chapter 5: Multicopper Proteins

5.1. Introduction

5.2. Molecular Architecture of Multicopper Oxidases

5.3. Structure of the Copper-Binding Centers

5.4. Spectral Properties

5.5. Substrate Binding and Specificity

5.6. Four-Electron Reduction of Dioxygen by Multicopper Oxidases

5.7. Modification of Multicopper Oxidases

5.8. Conclusions and Future Prospects

Acknowledgments

Abbreviations

References

Chapter 6: Structure and Reactivity of Copper–Oxygen Species Revealed by Competitive Oxygen-18 Isotope Effects

6.1. Introduction

6.2. Instrumentation

6.3. Methodology

6.4. Oxygen Equilibrium Isotope Effects

6.5. Oxygen Kinetic Isotope Effects

6.6. Mechanisms of Copper Enzymes

6.7. Conclusions

Acknowledgments

References

Chapter 7: Theoretical Aspects of Dioxygen Activation in Dicopper Enzymes

7.1. Introduction

7.2. Dicopper Models of Dioxygen Activation

7.3. Reaction Pathway for Dioxygen Cleavage

7.4. Structure of Tyrosinase

7.5. Mechanisms of Tyrosinase by DFT Calculations

7.6. Dicopper Site of Particulate Methane Monooxygenase

7.7. A Methane Hydroxylation Mechanism of pMMO

7.8. Concluding Remarks

Acknowledgments

References

Chapter 8: Chemical Reactivity of Copper Active-Oxygen Complexes

8.1. Introduction

8.2. Reactivity of Mononuclear Copper Active-Oxygen System

8.3. Reactivity of Dinuclear Copper Active-Oxygen System

8.4. Summary

References

Chapter 9: Cytochrome c Oxidase and Models

9.1. Introduction

9.2. Cytochrome c Oxidase synthetic Model Derivatives of Picket Fence Porphyrins and the Electrochemical Approach

9.3. Synthetic Models of Cytochrome c Oxidase Based on Heme/O2/Cu Assemblies and the Intermediates Detection Approach

9.4. His-Tyr Cross-Link At the Cytochrome c Oxidase Active Site Heme a3/CuB Center

9.5. Summary

References

Chapter 10: Supramolecular Copper Dioxygen Chemistry

10.1. Introduction

10.2. Control of the Active Site Nuclearity

10.3. Interlocking Metal Binding and Cavity Effect

10.4. Supramolecular Control of the Redox Process

10.5. Dioxygen Activation and Reactivity

10.6. Conclusion and Future Prospects

Abbreviations

References

Chapter 11: Organic Synthetic Methods Using Copper Oxygen Chemistry

11.1. Introduction and Organization

11.2. Oxidase-Type Reactions

11.3. Oxygenase-Type Reactions

11.4. Conclusion and Future Prospects

Acknowledgments

References

Color plate

Index

Wiley Series of Reactive Intermediates in Chemistry and Biology

Steven E. Rokita, Series Editor

Quinone Methides

Edited by Steven E. Rokita

Radical and Radical Ion Reactivity in Nucleic Acid Chemistry

Edited by Marc Greenberg

Carbon-Centered Free Radicals and Radical Cations

Edited by Malcolm D. E. Forbes

Copper-Oxygen Chemistry

Edited by Kenneth D. Karlin and Shinobu Itoh

Copyright š 2011 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Copper-oxygen chemistry / edited by Kenneth D. Karlin, Shinobu Itoh.

p. cm. – (Wiley series of reactive intermediates in chemistry and biology ; v. 8)

Includes index.

ISBN 978-0-470-52835-8 (hardback)

1. Copper proteins. 2. Copper–Peroxidation. 3. Bioinorganic chemistry. I.

Karlin, Kenneth D., 1948- II. Itoh, Shinobu.

QP535.C9C67 2011

612.3'924–dc22

2011010606

oBook ISBN: 978-1-118-09436-5

ePDF ISBN: 978-1-118-09434-1

ePub ISBN: 978-1-118-09435-8

Preface to Series

Most stable compounds and functional groups have benefitted from numerous monographs and series devoted to their unique chemistry, and most biological materials and processes have received similar attention. Chemical and biological mechanisms have also been the subject of individual reviews and compilations. When reactive intermediates are given center stage, presentations often focus on the details and approaches of one discipline despite their common prominence in the primary literature of physical, theoretical, organic, inorganic and biological disciplines. The Wiley Series on Reactive Intermediates in Chemistry and Biology is designed to supply a complementary perspective from current publications by focusing each volume on a specific reactive intermediate and endowing it with the broadest possible context and outlook. Individual volumes may serve to supplement an advanced course, sustain a special topics course, and provide a ready resource for the research community. Readers should feel equally reassured by reviews in their speciality, inspired by helpful updates in allied areas and intrigued by topics not yet familiar.

This series revels in the diversity of its perspectives and expertise. Where some books draw strength from their focused details, this series draws strength from the breadth of its presentations. The goal is to illustrate the widest possible range of literature that covers the subject of each volume. When appropriate, topics may span theoretical approaches for predicting reactivity, physical methods of analysis, strategies for generating intermediates, utility for chemical synthesis, applications in biochemistry and medicine, impact on the environmental, occurrence in biology and more. Experimental systems used to explore these topics may be equally broad and range from simple models to complex arrays and mixtures such as those found in the final frontiers of cells, organisms, earth and space.

Advances in chemistry and biology gain from a mutual synergy. As new methods are developed for one field, they are often rapidly adapted for application in the other. Biological transformations and pathways often inspire analogous development of new procedures in chemical synthesis, and likewise, chemical characterization and identification of transient intermediates often provide the foundation for understanding the biosynthesis and reactivity of many new biological materials. While individual chapters may draw from a single expertise, the range of contributions contained within each volume should collectively offer readers with a multi-disciplinary analysis and exposure to the full range of activities in the field. As this series grows, individualized compilations may also be created through electronic access to highlight a particular approach or application across many volumes that together cover a variety of different reactive intermediates.

Interest in starting this series came easily, but the creation of each volume of this series required vision, hard work, enthusiasm and persistence. I thank all of the contributors and editors who graciously accepted the challenge.

Steven E. Rokita

University of Maryland

Introduction

There is a great deal of current interest in the subject of oxidative processes mediated by copper ion. Not only have there been considerable recent advances in chemical applications, those useful to synthetic organic and pharmaceutical researchers, but there have been major advances in the clarification of biochemical oxidations that occur widely and critically in biological systems. In fact, the two areas have a synergistic relationship.

Copper-mediated biological oxidations include a diverse array of reaction types. The insertion of one or both oxygen atoms from molecular oxygen (O2) into an organic substrate underscores mild and highly selective transformations. Such transformations have been and are highly worthy of careful attention by synthetic and catalytic chemists. Many other oxidation (i.e., dehydrogenation) reactions utilize the cheap, abundant, and energy containing O2 molecule. Copper metalloproteins thus also mediate energetic processes.

In synthetic chemistry, many recent successes have in actual fact been bioinspired. The subfield of catalytic alcohol oxidation chemistry, using O2, has seen explosive growth and following insights obtained from complementary copper protein studies. Also, there now exists a significantly increasing literature on oxygen-atom insertion, CH bond activation, and CC bond formation reactions, as well as very important enantioselective oxidative chemistries. Specific applications to the synthesis of sophisticated molecules important in natural product or pharmaceutical chemistries derive from information on copper enzymes or their synthetic models. Long known industrial examples include the oxidative coupling of phenols, requiring molecular oxygen and copper catalysis.

In addition, as mentioned, there has been an explosion of recent activity and significant insights obtained from biochemical and model compound chemistries. These studies have highlighted the application of advanced physical–spectroscopic techniques, theory, and synthesis and study of copper coordination complex biomimics. The result has been the discovery of new types of interactions of molecular oxygen with copper ion, and most importantly the elucidation of reactivity patterns or oxidative capabilities, many previously unknown.

Thus, the current Volume (Vol. 4) on Copper–Oxygen Chemistry, within the Wiley Series on Reactive Intermediates in Chemistry and Biology (S. R. Rokita, Ed.), will be an important addition. The authors have been selected for their international reputations and expertise. We choose to divide the topics and volume into logical areas, (A) Biological Systems, (B) Theory, and (C) Bioinorganic Models and Applications. The overlap seen between these areas will be very apparent in the final published volume, because of the synergism that exists. There will be considerable reference to other chapters and subjects covered in this volume.

The treatment here will be broad, including all the major and important areas and aspects of the field of Copper–Oxygen Chemistry. This volume will unquestionably appeal to a very broad audience. Biochemists, biophysicists, medical–pharmaceutical chemists, organic synthetic and (bio)inorganic chemists in academia and industry should find the volume to be highly interesting and useful, covering front-line areas and thorough in its coverage by prominent authors in the field.

Kenneth D. Karlin

John's Hopkins University

Shinobu Itoh

Osaka University

Contributors

Doreen E. Brown, Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, USA

Simon de Vries, Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC, Delft, The Netherlands

David M. Dooley, Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, and University of Rhode Island, Green Hall, 35 Campus Avenue, Kingston, RI, USA

Zakaria Halime, Department of Chemistry, Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD 21218, USA

Shinobu Itoh, Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, 2–1 Yamada–oka, Suita, Osaka 565–0871, Japan

József Kaizer, Department of Chemistry, University of Pannonia, 8201 Veszprém, Hungary

Kenneth D. Karlin, Department of Chemistry, Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD 21218, USA

Kunishige Kataoka, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920–1192, Japan

Judith P. Klinman, Department of Chemistry, Department of Molecular and Cellular Biology, and California Institute for Quantitative Biosciences, University of California – Berkeley, Berkeley, CA 94720, USA

Marisa C. Kozlowski, Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania, 19104, USA

Robert L. Osborne, Department of Chemistry and California Institute for Quantitative Biosciences, University of California – Berkeley, Berkeley, CA 94720, USA

József Sándor Pap, Department of Chemistry, University of Pannonia, 8201 Veszprém, Hungary

Angela Paulus, Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC, Delft, The Netherlands

Jean–Noël Rebilly, Université Paris Descartes, UMR 8601, Laboratoire de Chimie et Biochimie, Pharmacologiques et Toxicologiques, 45 rue des Saints–Pères, 75006 Paris, France

Olivia Reinaud, Université Paris Descartes, UMR 8601 Laboratoire de Chimie et Biochimie, Pharmacologiques et Toxicologiques, 45 rue des Saints–Pères, 75006 Paris, France

Dalia Rokhsana, Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, USA

Justine P. Roth, Department of Chemistry, Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD 21218, USA

Takeshi Sakurai, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920–1192, Japan

Eric M. Shepard, Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, USA

Gábor Speier, Department of Chemistry, University of Pannonia, 8201 Veszprém, Hungary

Kazunari Yoshizawa, Institute for Materials Chemistry and Engineering and International Research, Center for Molecular Systems, Kyushu University, Fukuoka 819–0395, Japan