4. Purple Mixed-Valent Copper A
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Marcos N. Morgada
Abstract
CuA is a binuclear copper center acting as an electron transfer hub in terminal oxidases such as cytochrome c oxidase and nitrous oxide reductase. Its unique electronic structure is intimately linked to its function and has puzzled the community of biological inorganic chemistry for decades. Here we review the insights provided by different spectroscopic techniques of CuA centers, and the different experimental approaches to tackle its study, that encompass the synthesis of model compounds as well as protein engineering efforts. The contribution of the electronic structure to the thermodynamic and kinetic of electron transfer is extensively discussed. We also describe the proposed mechanism of CuAassembly in different organisms. The recent discovery of a novel CuA site opens new perspectives to this field.
Abstract
CuA is a binuclear copper center acting as an electron transfer hub in terminal oxidases such as cytochrome c oxidase and nitrous oxide reductase. Its unique electronic structure is intimately linked to its function and has puzzled the community of biological inorganic chemistry for decades. Here we review the insights provided by different spectroscopic techniques of CuA centers, and the different experimental approaches to tackle its study, that encompass the synthesis of model compounds as well as protein engineering efforts. The contribution of the electronic structure to the thermodynamic and kinetic of electron transfer is extensively discussed. We also describe the proposed mechanism of CuAassembly in different organisms. The recent discovery of a novel CuA site opens new perspectives to this field.
Chapters in this book
- Frontmatter i
- About the Editors v
- Historical Development and Perspectives of the Series. Metal Ions in Life Sciences* vii
- Preface to Volume 20. Transition Metals and Sulfur: A Strong Relationship for Life ix
- Contents xiii
- Contributors to Volume 20 xix
- Titles of Volumes 1–44 in the Metal Ions in Biological Systems Series xxiii
- Contents of Volumes in the Metal Ions in Life Sciences Series xxv
- 1. Introduction: Transition Metals and Sulfur 1
- 2. Sulfur, the Versatile Non-metal 19
- 3. The Type 1 Blue Copper Site: From Electron Transfer to Biological Function 51
- 4. Purple Mixed-Valent Copper A 91
- 5. The Tetranuclear Copper-Sulfide Center of Nitrous Oxide Reductase 139
- 6. Cytochrome P450. The Dioxygen-Activating Heme Thiolate 165
- 7. Basic Iron-Sulfur Centers 199
- 8. The Cofactors of Nitrogenases 257
- 9. Molybdenum and Tungsten Cofactors and the Reactions They Catalyze 313
- 10. The Siroheme-[4Fe-4S] Coupled Center 343
- 11. Nickel, Iron, Sulfur Sites 381
- 12. Zinc Fingers 415
- SUBJECT INDEX 437
Chapters in this book
- Frontmatter i
- About the Editors v
- Historical Development and Perspectives of the Series. Metal Ions in Life Sciences* vii
- Preface to Volume 20. Transition Metals and Sulfur: A Strong Relationship for Life ix
- Contents xiii
- Contributors to Volume 20 xix
- Titles of Volumes 1–44 in the Metal Ions in Biological Systems Series xxiii
- Contents of Volumes in the Metal Ions in Life Sciences Series xxv
- 1. Introduction: Transition Metals and Sulfur 1
- 2. Sulfur, the Versatile Non-metal 19
- 3. The Type 1 Blue Copper Site: From Electron Transfer to Biological Function 51
- 4. Purple Mixed-Valent Copper A 91
- 5. The Tetranuclear Copper-Sulfide Center of Nitrous Oxide Reductase 139
- 6. Cytochrome P450. The Dioxygen-Activating Heme Thiolate 165
- 7. Basic Iron-Sulfur Centers 199
- 8. The Cofactors of Nitrogenases 257
- 9. Molybdenum and Tungsten Cofactors and the Reactions They Catalyze 313
- 10. The Siroheme-[4Fe-4S] Coupled Center 343
- 11. Nickel, Iron, Sulfur Sites 381
- 12. Zinc Fingers 415
- SUBJECT INDEX 437
