The field of Bioinorganic Chemistry has grown significantly in recent years; now one of the major sub-disciplines of Inorganic Chemistry, it has also pervaded other areas of the life sciences due to its highly interdisciplinary nature. Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life, Second Edition provides a detailed introduction to the role of inorganic elements in biology, taking a systematic element-by-element approach to the topic. The second edition of this classic text has been fully revised and updated to include new structure information, emerging developments in the field, and an increased focus on medical applications of inorganic compounds. New topics have been added including materials aspects of bioinorganic chemistry, elemental cycles, bioorganometallic chemistry, medical imaging and therapeutic advances. Topics covered include: * Metals at the center of photosynthesis * Uptake, transport, and storage of essential elements * Catalysis through hemoproteins * Biological functions of molybdenum, tungsten, vanadium and chromium * Function and transport of alkaline and alkaline earth metal cations * Biomineralization * Biological functions of the non-metallic inorganic elements * Bioinorganic chemistry of toxic metals * Biochemical behavior of radionuclides and medical imaging using inorganic compounds * Chemotherapy involving non-essential elements This full color text provides a concise and comprehensive review of bioinorganic chemistry for advanced students of chemistry, biochemistry, biology, medicine and environmental science.

InhaltsangabePreface to the Second Edition xi Preface to the First Edition xiii 1 Historical Background, Current Relevance and Perspectives 1 References 6 2 Some General Principles 7 2.1 Occurrence and Availability of Inorganic Elements in Organisms 7 Insertion: The Chelate Effect 14 Insertion: "Hard" and "Soft" Coordination Centers 14 2.2 Biological Functions of Inorganic Elements 14 2.3 Biological Ligands for Metal Ions 16 2.3.1 Coordination by Proteins: Comments on Enzymatic Catalysis 17 Insertion: The "Entatic State" in Enzymatic Catalysis 20 2.3.2 Tetrapyrrole Ligands and Other Macrocycles 22 Insertion: Electron Spin States in Transition Metal Ions 28 2.3.3 Nucleobases, Nucleotides and Nucleic Acids (RNA, DNA) as Ligands 31 Insertion: Secondary Bonding 32 2.4 Relevance of Model Compounds 34 References 34 3 Cobalamins, Including Vitamin and Coenzyme B12 37 3.1 History and Structural Characterization 37 Insertion: Bioorganometallics I [1] 38 3.2 General Reactions of Alkylcobalamins 41 3.2.1 Oneelectron Reduction and Oxidation 41 3.2.2 CoC Bond Cleavage 42 Insertion: Electron Paramagnetic Resonance I 43 3.3 Enzyme Functions of Cobalamins 45 3.3.1 Adenosylcobalamin (AdoCbl)-dependent Isomerases 45 Insertion: Organic Redox Coenzymes 48 3.3.2 Alkylation Reactions of Methylcobalamin (MeCbl)-dependent Alkyl Transferases 51 3.4 Model Systems and the Enzymatic Activation of the Co-C Bond 52 References 53 4 Metals at the Center of Photosynthesis: Magnesium and Manganese 57 4.1 Volume and Efficiency of Photosynthesis 57 4.2 Primary Processes in Photosynthesis 59 4.2.1 Light Absorption (Energy Acquisition) 59 4.2.2 Exciton Transport (Directed Energy Transfer) 59 4.2.3 Charge Separation and Electron Transport 62 Insertion: Structure Determination by X-ray Diffraction 62 4.3 Manganese-catalyzed Oxidation of Water to O2 68 Insertion: Spin-Spin Coupling 73 References 75 5 The Dioxygen Molecule, O2: Uptake, Transport and Storage of an Inorganic Natural Product 77 5.1 Molecular and Chemical Properties of Dioxygen, O2 77 5.2 Oxygen Transport and Storage through Hemoglobin and Myoglobin 82 5.3 Alternative Oxygen Transport in Some Lower Animals: Hemerythrin and Hemocyanin 92 5.3.1 Magnetism 92 5.3.2 Light Absorption 93 5.3.3 Vibrational Spectroscopy 93 Insertion: Resonance Raman Spectroscopy 93 5.3.4 M¨ossbauer Spectroscopy 94 Insertion: M¨ossbauer Spectroscopy 94 5.3.5 Structure 95 5.4 Conclusion 96 References 96 6 Catalysis through Hemoproteins: Electron Transfer, Oxygen Activation and Metabolism of Inorganic Intermediates 99 6.1 Cytochromes 101 6.2 Cytochrome P-450: Oxygen Transfer from O2 to Nonactivated Substrates 103 6.3 Peroxidases: Detoxification and Utilization of Doubly Reduced Dioxygen 108 6.4 Controlling the Reaction Mechanism of the Oxyheme Group: Generation and Function of Organic Free Radicals 110 6.5 Hemoproteins in the Catalytic Transformation of Partially Reduced Nitrogen and Sulfur Compounds 112 Insertion: Gasotransmitters 113 References 114 7 IronSulfur and Other Nonheme Iron Proteins 117 7.1 Biological Relevance of the Element Combination Iron-Sulfur 117 Insertion: Extremophiles and Bioinorganic Chemistry 118 7.2 Rubredoxins 122 7.3 [2Fe2S] Centers 122 7.4 Polynuclear Fe/S Clusters: Relevance of the Protein Environment and Catalytic Activity 123 7.5 Model Systems for Fe/S Proteins 128 7.6 Ironcontaining Enzymes without Porphyrin or Sulfide Ligands 130 7.6.1 Ironcontaining Ribonucleotide Reductase 130 7.6.2 Soluble Methane Monooxygenase 132 7.6.3 Purple Acid Phosphatases (Fe/Fe and Fe/Zn) 133 7.6.4 Mononuclear Non-heme Iron Enzymes 133 References 135 8 Uptake, Transport and Storage of an Essential Element, as Exemplified by Iron 139 Insertion: Metallome 139 8.1 The Problem of Iron Mobilization: Oxidatio

Leseprobe