Beschreibung
Assembling a program in bioinorganic chemistry that is scientifi cally relevant, well defined, and self-consistent is not an easy task. In this attempt we decided to consider zinc enzymes, copper oxidases, cytochromes and cytochrome oxidase. The choice is in part due to the great attention that the current specialized literature devotes to these topics, which are now debated among chemists, biochemists, biophysicists, etc. We believe that hydration reactions, hydrolytic and oxidative processes have much in common from the point of view of the reaction mechanisms, the comprehension of which represents a frontier of science. For these reasons these topics have been the subject of the NATO-ASI held at San Miniato, Pisa, Italy, from May 28 to June 8, 1982. We hope we can transfer here the main conclusions of what (we believe) was a very stimulating scientific meeting. We would like to thank the local saving bank, Cassa di Risparmio di San Miniato, for helping in many ways. The financial contribution from the European Research Office of the US Army, and from the Bruker Spectrospin s.r.l., Italy, is also acknowledged. The National Science Foundation of the United States has provided a travel grant to one of the participants from the U.S.A. We are grateful to the NATO Scientific Affairs Division which provided a grant to finance this Institute.
Autorenporträt
InhaltsangabeI: The Coordination Properties of the Active Site of Zinc Enzymes.- 1. Introduction.- 2. The Residues Coordinated at the Zinc Ion.- 3. The Acid-Base Properties of Coordinated Water.- 4. The Electronic Spectra of Cobalt (II) Derivatives.- 5. The Water 1H NMR Studies.- 6. The Implications on the Catalytic Mechanism.- II: Coordinated Solvent Molecules in Metalloenzymes and Proteins Studied Using NMRD.- 1. Introduction.- 2. The "Fluoromet" Mechanism.- 3. Fe3+ - Transferrin.- 4. Cu2+ - and V02+ - Transferrin.- 5. Co2+ - Carbonic Anhydrase.- 6. Alcohol Dehydrogenase.- 7. Mn2+ - Carboxypeptidase A.- 8. Conclusions.- III: 113Cd Nuclear Magnetic Resonance Studies of Zinc Metalloproteins.- 1. Introduction.- 2. Chemical Shifts.- 3. Sensitivity.- 4. Information Content.- 5. Concluding Remarks.- IV: Carbonic Anhydrase: Structure, Kinetics, and Mechanism.- 1. Introduction.- 2. Structure.- 3. Kinetics.- 4. Mechanism.- V: Metal Ion Promoted Hydrolysis of Nucleoside 5'-Triphosphates.- 1. Introduction.- 2. Results and Discussion.- VI: Models of Metalloenzymes: Carboxypeptidase A.- 1. Introduction.- 2. Metal Ion Catalyzed Hydrolysis of Amides and Esters.- 3. Results and Discussion.- 4. Cu2+ Mediated Amide Hydrolysis.- 5. Conclusions.- VII: Spectroscopic Studies on Cobalt(II) Carboxypeptidase A.- VIII: Coordination Properties and Mechanistic Aspects of Liver Alcohol Dehydrogenase.- 1. Introduction.- 2. Coordination Chemistry of Metallo Alcohol Dehydrogenases.- 3. Mechanistic Aspects.- IX: Metal-Directed Affinity Labelling and Promoted Alkylation of a Thiol Liganded to the Catalytic Metal Ion in Liver Alcohol Dehydrogenase.- 1. Introduction.- 2. Experimental.- 3. Results and Discussion.- X: Ligand Sphere Transitions: A New Concept in Zinc-Enzyme Catalysis.- 1. Introduction.- 2. Experimental Background.- 3. The Proposed Model Concept.- XI: Molecular Mechamisms of the Superoxide Dismutase Activity of the Cuprozinc Protein of Eucaryotic Cells (CuZn Superoxide Dismutase).- 1. Molecular Properties of the Protein.- 2. General Mechanism of the Superoxide Dismutation by the Copper of the Protein.- 3. Inactivation of the Enzyme.- 4. Inhibition of the Enzyme.- 5. Role of the Zinc.- XII: A Comment on Anion Binding to Superoxide Dismutase.- XIII: Kinetic and Magnetic Resonance Studies on Amine Oxidases.- 1. Introduction.- 2. Studies on the Copper Cofactor.- 3. Mechanistic Studies.- XIV: Metal Coordination and Mechanism of Blue Copper Containing Oxidases.- 1. Introduction.- 2. Chemical Composition and Reactions Catalyzed.- 3. Spectroscopic Data.- 4. Oxidation-Reduction Properties.- 5. The Catalytic Mechanism.- XV: Metal Replacement Studies of Chinese Laccase.- 1. Introduction.- 2. Metal-Replacement Studies of Small Blue Proteins.- 3. The Removal and Replacement of Copper from Chinese Laccase.- 4. The Preparation of a Mixed-Metal Hybrid of Laccase.- XVI: Reactions of Rhus Vernicifera Laccase with Azide and Fluoride, Formation of a "Half-Met-N3 -Type" Binding.- 1. Reactions with N3- as Studied by EPR.- 2. Reactions with N3- in the Presence of Redox Reagents.- 3. Half-Met-N3-Type Binding in Laccase.- 4. Reactions with Fluoride.- 5. Temperature Effects.- XVII: Structural Magnetic Correlations in Exchange Coupled Systems.- 1. Spin Hamiltonian Approach to Exchange Coupling.- 2. Molecular Orbital Approach to Exchange Coupling.- XVIII: Structural and Magnetic Investigations on Model CU4O4 Cubane-Like Clusters.- 1. Introduction.- 2. Structural Description.- 3. Magnetic Properties and Structural Data.- 4. Extension of the Correlations Between Magnetism and Structures.- 5. Example.- XIX: Neurospora Tyrosinase: Intrinsic and Extrinsic Fluorescence.- 1. Introduction.- 2. Intrinsic Fluorescence.- 3. Extrinsic Fluorescence.- XX: Comparison of Two Fungal Tyrosinases.- 1. Introduction.- 2. Molecular Properties.- 3. Properties of the Copper Site.- 4. Identification of Endogenous Ligands.- 5. Inhibition by Anions.- XXI: Activation of Molecular Oxygen.- 1. Introduction.- 2. Autox
