Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life

Transcription

1 Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life An Introduction and Guide Wolfgang Kaim Universität Stuttgart, Stuttgart, Germany and Brigitte Schwederski Universität Stuttgart, Stuttgart, Germany John Wiley & Sons Chichester New York Brisbane Toronto Singapore

2 Contents Preface xi 1 Historical Background, Current Relevance and Perspectives 1 References 5 2 Some General Principles Occurrence and Availability of Inorganic Elements in Organisms Biological Functions of Inorganic Elements Biological Ligands for Metal Ions Coordination by Proteins Comments on Enzymatic Catalysis Tetrapyrrole Ligands and Other Macrocycles Nucleobases, Nucleotides and Nucleic Acids (RNA, DNA) as Ligands Relevance of Model Compounds 35 References 36 3 Cobalamins Including Vitamin and Coenzyme B, History and Structural Characterization Reactions of the Alkylcobalamins One-Electron Reduction and Oxidation Co C Bond Cleavage Mutase Activity of Coenzyme B Alkylation Reactions of Methylcobalamin Model Systems and the Role of the Apoenzyme 53 References 54 4 Metals at the Center of Photosynthesis: Magnesium and Manganese Volume and Total Efficiency of Photosynthesis Primary Processes in Photosynthesis Light Absorption (Energy Acquisition) Exciton Transport (Directed Energy Transfer) Charge Separation and Electron Transport Manganese-Catalyzed Oxidation of Water to : 68 References 79 5 The Dioxygen Molecule, 0 2 : Uptake, Transport, and Storage of an Inorganic Natural Product Molecular and Chemical Properties of Dioxygen, O z Oxygen Transport and Storage through Hemoglobin and Myoglobin 88

3 VI CONTENTS 5.3 Alternative Oxygen Transport in Some Lower Animals: Hemerythrin and Hemocyanin Magnetism Light Absorption Vibrational Spectroscopy Mössbauer Spectroscopy Structure 103 References Catalysis Through Hemoproteins: Electron Transfer, Oxygen Activation and Metabolism of Inorganic Intermediates Cytochromes Cytochrome P-450: Oxygen Transfer from O z to Nonactivated Substrates Peroxidases: Detoxification and Utilization of Doubly Reduced Dioxygen Controlling the Reaction Mechanism of the Oxyheme Group Generation and Function of Organic Free Radicals Hemoproteins in the Catalytic Transformation of Partially Reduced Nitrogen and Sulfur Compounds 122 References Iron-Sulfur and Other Nonheme Iron Proteins Biological Relevance of the Element Combination Iron/Sulfur Rubredoxins [2Fe-2S] Centers Polynuclear Fe/S Clusters: Relevance of the Protein Environment and Catalytic Activity Model Systems for Iron-Sulfur Proteins Iron-Containing Enzymes without Porphyrin or Sulfide Ligands Iron-Containing Ribonucleotide Reductase (RR) Soluble Methane Monooxygenase (MMO) Purple Acid Phosphatases (Fe/Fe and Fe/Zn) Mononuclear Nonheme Iron Enzymes 144 References Uptake, Transport and Storage of an Essential Element as Exemplified by Iron The Problem of Iron Mobilization Oxidation States, Solubility and Medical Relevance Siderophores: Iron Uptake by Microorganisms Phytosiderophores: Iron Uptake by Plants Transport and Storage of Iron Transferrin Ferritin Hemosiderin 169 References Nickel-Containing Enzymes: The Remarkable Career of a Long Overlooked Biometal Overview Urease 173

4 CONTENTS Vll 9.3 Hydrogenases CO Dehydrogenase = CO Oxidoreductase == Acetyl-CoA Synthase Methyl-Coenzyme M Reductase Model Compounds 183 References Copper-Containing Proteins: An Alternative to Biological Iron Type 1: 'Blue' Copper Centers Type 2 and Type 3 Copper Centers in 0 2 -Activating Proteins: Oxygen Transport and Oxygenation Copper Proteins as Oxidases/Reductases Cytochrome c Oxidase Cu,Zn and Other Superoxide Dismutases: Substrate-Specific Antioxidants 209 References Biological Functions of the 'Early' Transition Metals: Molybdenum, Tungsten, Vanadium and Chromium Oxygen Transfer through Tungsten- and Molybdenum-Containing Enzymes Overview Enzymes Containing the Molybdopterin Cofactor Metalloenzymes in the Biological Nitrogen Cycle: Molybdenum-Dependent Nitrogen Fixation Alternative Nitrogenases Biological Vanadium Outside Nitrogenases Chromium(III) in the Metabolism? 238 References Zinc: Structural and Gene-Regulatory Functions and the Enzymatic Catalysis of Hydrolysis or Condensation Reactions Overview Carboanhydrase (CA) Carboxypeptidase A (CPA) and Other Hydrolases Catalysis of Condensation Reactions by Zinc-Containing Enzymes Alcohol Dehydrogenase (ADH) and Related Enzymes The 'Zinc Finger' and Other Gene Regulatory Zinc Proteins Insulin, hgh, Metallothionein and DNA Repair Systems as Zinc-Containing Proteins 262 References Unequally Distributed Electrolytes: Function and Transport of Alkali and Alkaline Earth Metal Cations Characterization of K +, Na +, Ca 2+ and Mg Complexes of Alkali and Alkaline Earth Metal Ions with Macrocycles Ion Channels Ion Pumps 281 References 284

5 Vlll CONTENTS 14 Catalysis and Regulation of Bioenergetic Processes by the Alkaline Earth Metal Ions Mg 2+ and Ca Magnesium: Catalysis of Phosphate Transfer by Divalent Ions The Ubiquitous Regulatory Role of Ca References « Biomineralization: The Controlled Assembly of 'Advanced Materials' in Biology Overview Nucleation and Crystal Growth Examples of Biominerals Calcium Phosphate in the Bones of Vertebrates Calcium Carbonate Amorphous Silica Iron Biominerals Strontium and Barium Sulfates 315 References Biological Functions of the Nonmetallic Inorganic Elements Overview Boron Silicon Arsenic and PH Bromine Fluorine Iodine Selenium 323 References The Bioinorganic Chemistry of the Qu int essen tially Toxic Metals Overview Lead Cadmium Thallium Mercury Aluminum Beryllium Chromium as Chromate(VI) 346 References Biochemical Behavior of Inorganic Radionuclides: Radiation Risks and Medical Benefits Overview Natural and Man-Made Radioisotopes Outside Medical Applications Bioinorganic Chemistry of Radiopharmaceuticals Overview Technetium a 'Man-Made Bioinorganic Element' 358 References 362

6 CONTENTS IX 19 Chemotherapy with Compounds of Some Nonessential Elements Overview Platinum Complexes in Cancer Therapy Discovery, Application and Structure-Effect Relationships Cisplatin: Mode of Action Cytotoxic Compounds of Other Metals Gold-Containing Drugs Used in the Therapy of Rheumatoid Arthritis Historical Development Gold Compounds as Anti-Rheumatic Agents Hypotheses on the Mode of Action of Gold-Containing Anti-Rheumatic Drugs Lithium in Psychopharmacological Drugs 376 References 376 Bibliography 379 Glossary 381 List of Inserts 384 Index 387