Biological Inorganic Chemistry (eBook)

Cover 1
Preface 6
Contents 8
Chapter 1. An Overview of Metals in Biology 14
Introduction 14
Why do we Need Anything Other Than C, H, N and O (Together with Some P And S)? 15
What are the Essential Metal Ions? 16
References 25
Chapter 2. Basic Coordination Chemistry for Biologists 26
Introduction 26
Hard and Soft Ligands 28
Coordination Geometry 31
Crystal Field Theory and Ligand Field Theory 32
References 39
Chapter 3. Biological Ligands for Metal Ions 40
Introduction 40
Protein Amino Acid Residues (and Derivatives) as Ligands 40
An Example of a Non-Protein Ligand: Carbonate and Phosphate 42
Engineering Metal Insertion Into Organic Cofactors 43
Chelatase: Terminal Step in Tetrapyrrole Metallation 43
Iron–Sulfur Cluster Containing Proteins 45
Iron–Sulfur Cluster Formation 46
Copper Insertion into Superoxide Dismutase 48
More Complex Cofactors: MoCo, FeMoCo, P-Clusters, H-Clusters and CuZ 49
Siderophores 52
References 55
Chapter 4. Structural and Molecular Biology for Chemists 56
Introduction 56
The Structural Building Blocks of Proteins 56
Primary, Secondary, Tertiary and Quaternary Structures of Proteins 60
Secondary and Tertiary Structures of Nucleic Acids 69
References 89
Chapter 5. An Overview of Intermediary Metabolism and Bioenergetics 90
Introduction 90
Redox Reactions in Metabolism 91
The Central Role of ATP in Metabolism 92
The Types of Reaction Catalysed by Enzymes of Intermediary Metabolism 95
An Overview of Intermediary Metabolism: Catabolism 99
Selected Case Studies: Glycolysis and the Tricarboxylic Acid Cycle 101
An Overview of Intermediary Metabolism: Anabolism 105
Bioenergetics: Generation of Phosphoryl Transfer Potential at the Expense of Proton Gradients 110
References 117
Chapter 6. Methods to Study Metals in Biological Systems 118
Introduction 118
Magnetic Properties 120
Electron Paramagnetic Resonance (EPR) Spectroscopy 121
Mössbauer Spectroscopy 122
NMR Spectroscopy 123
Electronic and Vibrational Spectroscopies 125
Circular Dichroism and Magnetic Circular Dichroism 126
Resonance Raman Spectroscopy 127
Extended X-Ray Absorption Fine Structure 128
X-Ray Diffraction 128
References 129
Chapter 7. Metal Assimilation Pathways 130
Introduction 130
Metal Assimilation in Bacteria 130
Metal Assimilation in Plants and Fungi 134
Metal Assimilation in Mammals 139
References 142
Chapter 8. Transport, Storage and Homeostasis of Metal Ions 144
Introduction 144
Metal Storage and Homeostasis in Bacteria 144
Metal Transport, Storage and Homeostasis in Plants and Fungi 149
Metal Transport, Storage and Homeostasis in Mammals 157
References 163
Chapter 9. Sodium and Potassium„Channels and Pumps 164
Introduction: „Transport Across Membranes 164
Sodium Versuspotassium 165
Sodium Channels 168
References 176
Chapter 10. Magnesium–Phosphate Metabolism and Photoreceptors 178
Introduction 178
Magnesium-Dependent Enzymes 179
Phosphoryl Group Transfer: Kinases 180
Phosphoryl Group Transfer: Phosphatases 183
Stabilization of Enolate Anions: The Enolase Super Family 186
Enzymes of Nucleic Acid Metabolism 188
Magnesium and Photoreception 191
References 194
Chapter 11. Calcium: Cellular Signalling 196
Introduction: „Comparison of Ca2+ and Mg2+ 196
The Discovery of a Role for Ca2+ Other Than as a Structural Component. 196
Plasma Membrane Uptake Pathways 198
Calcium Export from Cells 198
CA2+ Transport Across Intracellular Membranes 201
Ca2+ and Cell Signalling 204
References 208
Chapter 12. Zinc: Lewis Acid and Gene Regulator 210
Introduction 210
Mononuclear Zinc Enzymes 211
Carbonic Anhydrase 212
Carboxypeptidases and Thermolysins 213
Alcohol Dehydrogenases 215
Other Mononuclear Zinc Enzymes 216
Multinuclear and Cocatalytic Zinc Enzymes 218
Zinc Fingers – DNA- and RNA-Binding Motifs 221
References 223
Chapter 13. Iron: Essential for Almost All Life 224
Introduction 224
Iron and Oxygen 225
The Biological Importance of Iron 227
Biological Functions of Iron-Containing Proteins 229
Haemoproteins 230
Iron–Sulfur Proteins 239
Other Iron-Containing Proteins 244
References 252
Chapter 14. Copper: Coping with Dioxygen 254
Introduction 254
Blue Copper Proteins Involved in Electron Transport 255
Copper-Containing Enzymes in Oxygen Activation and Reduction 257
Copper Enzymes Involved with Other Low-Molecular Weight Substrates 264
Mars and Venus: The Role of Copper in Iron Metabolism 266
References 267
Chapter 15. Nickel and Cobalt: Evolutionary Relics 270
Introduction: Comparison of Nickel and Cobalt 270
Nickel Enzymes 271
Methyl-Coenzyme M Reductase 276
Cobalamine and Cobalt Proteins 276
B12-Dependent Isomerases 277
B12-Dependent Methyltransferases 279
Non-Corrin Co-Containing Enzymes 281
References 282
Chapter 16. Manganese: Water Splitting, Oxygen Atom Donor 284
Introduction: Manganese Chemistry 284
Mn2+ and Detoxification of Oxygen Free Radicals 285
Non-Redox Di-Mn Enzymes: Arginase 287
Photosynthetic Oxidation of Water: Oxygen Evolution 289
References 291
Chapter 17. Molybdenum, Tungsten, Vanadium and Chromium 292
Introduction 292
Molybdenum and Tungsten 292
Molybdenum Enzyme Families 295
Tungsten Enzymes 298
Nitrogenases 299
Vanadium Biochemistry 304
Vanadium Biology 305
Chromium in Biology 307
References 308
Chapter 18. Metals in Brain and Their Role in Various Neurodegenerative Diseases 310
Introduction: Metals in Brain 310
Calcium 310
Zinc 313
Copper 314
Disorders of Copper Metabolism: Wilson’s and Menkes Diseases 314
Aceruloplasminaemia 316
Creutzfeldt–Jakob and Other Prion Diseases 316
Iron 319
Redox Metal Ions, Oxidative Stress and Neurodegenerative Diseases 321
References 333
Chapter 19. Biomineralization 334
Introduction 334
Iron Deposition in Ferritin 335
Calcium-Based Biominerals: Calcium Carbonates in Ascidians and Molluscs 343
Biomineralization in Bone and Enamel Formation 346
The Organic Matrix, Mineral Phase and Bone Mineralization 347
References 349
Chapter 20. Metals in Medicine and the Environment 352
Introduction 352
Metallotherapeutics with Lithium 353
Cisplatin: An Anti-Cancer Drug 354
Contrast Agents for Magnetic Resonance Imaging 357
Metals in the Environment 359
References 365
Index 366