Advances in Inorganic Chemistry (eBook)

Front Cover 1
Advances in Inorganic Chemistry, Volume 38 4
Copyright Page 5
Contents 6
Helmut Beinert 10
Chapter 1. Trinuclear Cuboidal and Heterometallic Cubane-Type Iron–Sulfur Clusters: New Structural and Reactivity Themes in Chemistry and Biology 14
I. Introduction 14
II. Homometallic Cubane-Type Clusters 15
III. Trinuclear Cuboidal Clusters 29
IV. Heterometallic MFe3S4 Cubane-Type Clusters 42
References 75
Chapter 2. Replacement of Sulfur by Selenium in Iron–Sulfur Proteins 86
I. Introduction 87
II. Selenium in Biology 87
III. Preparation of Selenium-Substituted Iron–Sulfur Proteins 93
IV. Mechanisms of Iron–Sulfur Cluster Assembly in Vitro and in Vivo 97
V. Biochemical Properties of Iron–Selenium Proteins 99
VI. Magnetic Properties of Iron–Selenium Clusters 102
VII. Ground Spin State Variability in [4Fe-4S(e)]+ Clusters 104
VIII. Vibrational Spectroscopy of Iron–Selenium Clusters 117
IX. Prospects 121
References 122
Chapter 3. Dynamic Electrochemistry of Iron–Sulfur Proteins 130
I. Introduction 130
II. Background 132
III. Applications 141
IV. Conclusions 172
References 173
Chapter 4. EPR Spectroscopy of Iron–Sulfur Proteins 178
I. Introduction 178
II. Fundamentals of Iron–Sulfur EPR 184
III. g Strain in Doublet Systems 199
IV. High-Spin Kramer’s Systems 207
V. Non-Kramer’s Systems 221
VI. Epilogue 228
References 229
Chapter 5. Structural and Functional Diversity of Ferredoxins and Related Proteins 236
I. Introduction 236
II. [2Fe–2S] Ferredoxins and Related Proteins 237
III. [4Fe–4S] and [3Fe–4S] Ferredoxins and Related Proteins 254
IV. 2[4Fe–4S] or [4Fe–4S][3Fe–4S] Ferredoxins and Related Proteins 267
V. Polyferredoxins 277
VI. Conclusions 278
References 280
Chapter 6. Iron–Sulfur Clusters in Enzymes: Themes and Variations 294
I. Introduction 294
II. Methods of Identifying Iron-Sulfur Clusters in Proteins 295
III. Classification of Iron–Sulfur Proteins. 311
IV. Membrane-Bound Iron–Sulfur Enzymes of Bioenergetic Systems 315
V. Soluble Proteins with Iron–Sulfur Clusters 317
VI. Concluding Remarks 325
References 326
Chapter 7. Aconitase: An Iron–Sulfur Enzyme 336
I. Introduction 336
II. Properties of the Fe–S Cluster 337
III. Interaction of Cluster and Substrate in the Enzymatic Reaction 339
IV. Crystallographic Structure 341
V. Studies on Mutants 347
VI. Relationship of Cytoplasmic Aconitase to Iron-Responsive Element Binding Protein 350
References 351
Chapter 8. Novel Iron–Sulfur Centers in Metalloenzymes and Redox Proteins from Extremely Thermophilic Bacteria 354
I. Introduction 354
II. Extremely Thermophilic Bacteria 355
III. Pyrococcus furiosus 357
IV. Thermotoga maritima 397
V. Summary 402
References 403
Chapter 9. Evolution of Hydrogenase Genes 410
I. Introduction 410
II. Hydrogenase Operons 413
III. Evolution of Hydrogenase Genes: ''Redon Shuffling" and Hydrogenase Export 423
IV. Functions of Hydrogenases 427
V. Perspectives 431
References 433
Chapter 10. Density-Functional Theory of Spin Polarization and Spin Coupling in Iron-Sulfur Clusters 436
I. Introduction 437
II. Perturbation Formalism for Spin Coupling in Transition Metal Clusters 438
III. The Density-Functional and Broken Symmetry Methods 449
IV. Monomeric Iron-Sulfur Complexes 453
V. Iron–Sulfur Dimers 454
VI. Three-Iron Clusters 465
VII. Four-Iron Clusters 468
VIII. Conclusions and Prospects for Future Work 479
References 482
Index 486
Contents of Recent Volumes 499