Sulfur-Centered Reactive Intermediates in Chemistry and Biology

ISBN-13: 9781468458763 / Angielski / Miękka / 2012 / 462 str.

C. Chatgilialoglu; Klaus-Dieter Asmus

Opis

A wonderfully successful NATO Advanced Study Institute on "Sulfur-Centered Reactive Intermediates in Chemistry and Biology" was held 18-30 June, 1989, at the Hotel Villa del Mare in Maratea, Italy. Despite the beautiful setting with mountains behind us and over looking the clear blue Mediterranean Sea under a cloudless sky (and with a private beach available), the lectures were extremely well attended. While some credit can go to the seriousness of the students, more must go to the calibre of speakers and the high quality of C. Chatgilialoglu, and Co-Director, Professor K. -D. their presentations. The Director, Dr. Asmus, are to be congratulated for putting together such an outstanding scientific program. Dr. Chatgilialoglu is also to be commended for arranging an equally stimulating social pro gram which included bus, train and boat trips to many local sites of interest. It was particularly fitting that a meeting on the chemistry and biochemistry of sulfur should be held in Italy since Italian chemists have made major contributions to our under standing of the organic chemistry of sulfur, including the chemistry of its reactive inter mediates. The early Italian interest in sulfur chemistry arose from the fact that Italy, or more specifically, Sicily, was a major world producer of sulfur prior to the development and exploitation of the Frasch process in Texas and Louisiana."

Spis treści

Force-Field and Molecular Orbital Calculations in Organosulfur Chemistry.- Electronic Transitions in Sulfur-Centered Radicals by Means of MSX? Calculations.- The Electronic Properties of Sulfur-Containing Substituents and Molecules: An Ab Initio Study.- Reactivity of Sulfur-Centered Nucleophiles Towards Dia- and Paramagnetic Reagents The Frontier Orbitals Approach.- Alkanethiylperoxyl Radicals.- Thermochemistry of Sulfur-Centered Intermediates.- Experimental Procedures in Electrolysis.- Single Electron Transfer in Aliphatic Nucleophilic Substitution.- Electrochemistry as a Tool for the Study of Reactive Intermediates.- Electrochemical Reduction of Some Sulfur Compounds.- Photocatalytic Formation of Sulfur-Centered Radicals by One-Electron Redox Processes on Semiconductor Surfaces.- Applications of Pulse Radiolysis for the Study of Short-Lived Sulphur Species.- Structure and Reaction Mechanisms in Sulphur-Radical Chemistry Revealed by E.S.R. Spectroscopy.- Sulfur-Centered Three-Electron Bonded Radical Species.- Radical Cations of Conjugated Cyclic Disulfides.- Beam Experiments as a Means for the Generation of Elusive Sulfur-Containing Molecules.- Dications from Cyclic Polythioethers.- Sulfenylium Cation Carriers in Chemistry and Biochemistry.- Neighboring Group Participation: General Principles and Application to Sulfur-Centered Reactive Species.- Design, Synthesis, and Conformational Analysis of Compounds Tailored for the Study of Sulfur-Centered Reactive Intermediates.- The Stereochemical Course of Sulphate Activation and Transfer.- Anionic Organosulfur Compounds in Synthesis: New Applications of the Ramberg-Bäcklund Reaction.- The Synthesis and Metal Complexes of Sulfur-Containing Models for Nitrogenase Enzymes.- Biologically Active Organosulfur Compounds from Garlic and Onions: The Search for New Drugs.- Free Radical Processes in the Reactions of Organometallics with Organic Sulfur Compounds.- The Invention of Radical Chain Reactions of Value in Organic Synthesis.- Recent Advances in the Chemistry of Compounds Containing S-Si Moieties.- Reaction Kinetics of Sulfur-Centered Radicals.- Redox Systems with Sulphur-Centered Species.- Electrochemistry of Thioethers as Models for Biological Electron Transfer.- Free-Radical Reactions Involving Thiols and Disulphides.- Hydrogen Abstraction by Thiyl Radicals from Activated C-H Bonds of Alcohols, Ethers and Polyunsaturated Fatty Acids.- Thiyl Free Radicals: Electron Transfer, Addition or Hydrogen Abstraction Reactions in Chemistry and Biology, and the Catalytic Role of Sulphur Compounds.- Free Radical Transfer Involving Sulphur Peptide Functions.- Electron Spin Resonance Investigation of the Thiyl Free Radical Metabolites of Cysteine, Glutathione, and Drugs.- Sulphur Compounds and “Chemical Repair” in Radiation Biology.- Thiol Reactivity Towards Drugs and Radicals: Some Implications in the Radiotherapy and Chemotherapy of Cancer.- In Vivo Hemoglobin Thiyl Radical Formation as a Consequence of Hydrazine-Based Drug Metabolism.- The Biological Actions of the Glutathione/Disulfide System: An Overview.