This book is based on the papers presented at the "Fourth International Congress on Oxygen Radicals (4-ICOR)," held June 27 - July 3, 1987, at the University of California, La Jolla. The chapters deal with the phenomena associated with highly reactive oxygen species (hydroxy, peroxy, alkoxy, aroxy, and superoxide radicals, as well as singlet oxygen) and their peroxidation products (hydrogen peroxide, hydroperoxides, peroxides, and epoxides) as they relate to the fields of chemistry, food technology, nutrition, biology, pharmacology, and medicine. The kinetics, energetics, and mechanistic aspects of the reactions of these species and the interrelationship of oxygen radicals (or any other free radicals) and peroxidized products have been emphasized. Special attention is focused on the mechanisms of the generation of free radicals and peroxy products in biosystems and on the adverse effects of these radicals and products in humans. The topics span the continuum from the simple chemistry of model systems to the complex considerations of clinical medicine. The book also explores the mechanisms of agents that protect against free radicals and peroxy products in vitro and in vivo. These agents include antioxidants used in materials, food antioxidants, physiological antioxidants, and antioxienzymes (SOD, glutathione peroxidase, and catalases). The use of these inhibitors to prevent damage to organs being prepared for transplantation, thereby maintaining the quality of transplanted organs and/or extending their "shelf-life," also is examined.

Inhalt

to Peroxidation and Antioxidation Mechanisms.- Kinetics and Mechanisms.- The Redox Thermodynamics for Dioxygen Species (O2, O2-·, HOO·, HOOH, and HOO-) and Monooxygen Species (O, O-·, ·OH, and -OH) in Water and Aprotic Solvents.- Electron Spin Resonance Investigations of Oxygen-Centered Free Radicals in Biological Systems.- Superoxide Chemistry in Non-Aqueous Media.- Peroxy Radicals and Singlet Oxygen (1O2) from the Addition of Superoxide Ion (O2-) to CCl4, CF3CCl3, PhCCl3, N-BuBr and N-BuCl in Acetonitrile.- The Uniqueness Both of Superoxide Toxicity and of the Protective Role of Superoxide Dismutase.- Peroxyl Radicals in Aqueous Media.- Aspects of the HO2· Elimination Reaction from Organic Peroxyl Radicals: Some Recent Examples.- Kinetic Studies of Alkoxyl Radicals.- Radical-Induced Degradation of Organic Halogen and Sulfur Compounds in Oxygenated Aqueous Solutions.- Thiyl Free Radical Metabolites of Thiol Drugs and Glutathione.- Oxidation of Quinones by H2O2: Formation of Epoxy- and Hydroxyquinone Adducts and Electronically Excited States.- From Nitric Oxide to Desferal: Nitrogen Free Radicals and Iron in Oxidative Injury.- Singlet Oxygen: Current Mechanistic Aspects of Photo-Oxidation.- Homolysis of Substituted Anisoles: Substituent Effects on Phenoxyl Radical Stabilities.- Redox Properties of Oxy and Antioxidant Radicals.- Generation of Oxy Radicals.- The Role of Metals in Aqueous Superoxide Chemistry.- Fenton Chemistry Revisited: Amino Acid Oxidation.- Iron Redox Reactions and Lipid Peroxidation.- The Generation of Ferryl or Hydroxyl Radicals during Interaction of Hemeproteins with Hydrogen Peroxide.- The Production of Hydroxyl and Semiquinone Free Radicals during the Autoxidation of Redox Active Flavonoids.- Fenton Reactions in Lipid Phases: Iron Solubility, ·OH Production, and Initiation of Lipid Oxidation.- The Role of Hemoglobin in Generating Oxyradicals.- Detection and Measurements.- Specific Detection of Lipid Hydroperoxides Using HPLC-EC Method.- Quantitative Determination of Fatty Acid Hydroperoxides in vivo.- Detection of Lipid Peroxidation Products in Lipids and Tissues by Gas Chromatography-Mass Spectrometry.- Direct Chemical Ionization Mass Spectrometry of Underivatized Arachidonic Acid Metabolites: Application to Leukotriene Biosynthesis.- Chemiluminescence - High Performance Liquid Chromatography of Phosphatidylcholine Hydroperoxide in Human Blood Plasma.- Method for Tracing Oxygen-18 in vivo: Application to Ozone Dosimetry in Animals.- Malondialdehyde Derivatives in Urine.- Electron Spin Resonance of the Semiquinone of the Antitumor Antibiotic Streptonigrin and Its Metal Complexes.- Chemiluminescence.- The Detection of Singlet Oxygen in Biochemical Systems Using 1268 nm Chemiluminescence.- Phagocyte Dioxygenation Reactions Yielding Chemiluminescence: The Maximum Multiplicity and Spin Conservation Rules Relative to Oxygen Reactivity.- Bryostatin Stimulation of Human Neutrophil Luminol and DBA (Lucigenin) Chemiluminescence.- Luciferase Reverse Micellar Bioluminescence: Kinetics and Emission Spectra.- Platelet Chemiluminiscence Induced by Linoleic and Arachidonic Acids.- Low Level Chemiluminescence from Isolated Rat Hepatocytes, Intact Lung and Intestine in situ.- Prevention by Propionylcarnitine of NADPH and tert-Butyl Hydroperoxide-Dependent Chemiluminescence in Heart Microsomes.- Chemiluminescence from Vitamin E-Deficient Erythrocyte Membranes Induced by Xanthine Oxidase Reaction.- Monitoring the Interactions of Environmental Agents by Cell-Dependent Chemiluminescence: Studies with Polycyclic Aromatic Hydrocarbons.- Gel State Chemiluminescence: An Artificial Electron Transport System.- Free Radicals and Oxygen Species in Lipids.- Hydroperoxidation of Unsaturated Fatty Esters.- Lipid Peroxidation and Retinal Phototoxic Degeneration.- Production and Metabolism of Cytotoxic Phospholipids Generated during Incubation of Liposomes with Oxyhemoglobin.- Lipid Peroxidation Dependent on Oxygen and Catalytic Free Iron Ions in situ Storage Muscle Foods.- A Unique Role of Histidine in Fe-Catalyzed Lipid Oxidation by Fish Sarcoplasmic Reticulum.- Cholesterol Epoxidations by Defined Oxygen Species.- Thermal Decomposition of Methyl Linoleate and Methyl Linolenate Hydroperoxides Analyzed by Capillary Gas Chromatography.- Effect of Dietary Lipid Peroxides on Lymphoid Tissues.- Free Radicals and Oxygen Species in Proteins.- Implication of Protein Oxidation in Protein Turnover, Aging, and Oxygen Toxicity.- Role of Oxidative Modification in the Lability of Ceruloplasmin.- The Oxidative Modification of Lens Proteins.- Degradation of the Proteoglycans of Human Articular Cartilage by Reactive Oxygen Metabolites.- Free Radical Denaturation of Immunoglobulin G Is due to Amino Acid Oxidation: Implications for Rheumatoid Arthritis.- A Study of ROS Induced Denaturation of IgG3 Using Monoclonal Antibodies; Implications for Inflammatory Joint Disease.- Oxy Radical-Initiated Protein S-Thiolation and Enzymic Dethiolation.- Free Radicals and Oxygen Species in Lipoproteins.- Modification of Human Low Density Lipoprotein by Lipid Peroxidation.- Is Oxidized Low Density Lipoprotein Involved in the Recruitment and Retention of Monocyte/Macrophages in the Artery Wall during the Initiation of Atherosclerosis?.- Copper and Copper-Nicotinic Acid Complexes Mediated Oxidation of High Density Lipoprotein.- Oxidation of Human Low Density Lipoprotein Initiated by Copper(II)Chloride.- Isolation and Partial Characterization of an Oxidized LDL in Humans.- Coronary Disease: Spectroscopic Correlation of Structure and Size of Plasma Lipoproteins with Patient Clinical History.- Free Radicals and Oxygen Species in DNA.- The Effect of Oxygen on the OH Radical-Induced Strand Break Formation of DNA in vitro and in vitro.- Double Strand Breakage in DNA and Cellular Radiation Sensitivity: Linear Energy Transfer and the Oxygen Effect.- Effect of ·OH Scavenging on the Yield of Radiation-Induced DNA Double-Strand Breaks in Isolated Nuclei.- Sonochemistry of Nucleic Acid Constituents in Aqueous Solution. A Spin-Trapping Study.- Gamma Radiolysis of RNA. An ESR and Spin-Trapping Study.- Interactions of Oxygen and Sulfhydryls with Free Radicals in Irradiated Mammalian Cells.- Oxygen Radicals, Lipid Peroxidation and DNA Damage in Mitochondria.- Involvement of Reactive Oxygen Intermediates in the Mutagenicity of Tumor Promoters.- Oxidative Dama…