Denisov E.T., Afanas’ev I.B. Oxidation and Antioxidants in Organic Chemistry and Biology

CRC Press, 2005. — 1024 p. — ISBN10: 0824753569; ISBN13: 978-0824753566.Providing a comprehensive review of reactions of oxidation for different classes of organic compounds and polymers, and biological processes mediated by free radicals, Oxidation and Antioxidants in Organic Chemistry and Biology puts the data and bibliographical information you need into one easy-to-use resource. You will find up-to-date information about mechanisms of action of antioxidants, their reactivity, reactions of intermediates, synergism, and antioxidants with cyclic mechanism action. Supplying useful, quantitative data in tables that make the information easy to find, the authors highlight the peculiarities of mechanisms involved in the oxidation of hydrocarbons, polymers, and different organic compounds.
The book provides tabulated values of strengths of C-H bonds of oxygen-containing compounds; of O-H bonds of hydroperoxides, alcohols, and acids; and of attacked antioxidant bonds. The authors collect and discuss over 3000 rate constants of different reactions of peroxyl radicals in oxidation and co-oxidation. They describe a new semiempiric theory of reactivity of reactants in elementary oxidative steps and the algorithm of calculation of activation energies, rate constants, and geometrical parameters of the transition states of free radical reactions. After elucidating the chemistry and kinetics of antioxidant action, the book covers oxidative processes that occur in biological systems.Authors
List of Chemical Symbols and Abbreviations
List of Physicochemical Symbols
List of Biochemical Abbreviations
Part I. Chemistry and Kinetics of Organic Compounds Oxidation by Dioxygen
Molecular Products and Thermochemistry of Hydrocarbon Oxidation
Earlier Concepts of Oxidation
Development of the Chain Theory of Oxidation of Organic Compounds
Hydroperoxides as Primary Molecular Products of Hydrocarbon Oxidation
Products of Hydroperoxide Decomposition
Chain Mechanismof Liquid-Phase Oxidation of Hydrocarbons
The Peculiarities of Chain Reactions
Chain Mechanismof Hydrocarbon Oxidation
Reaction of Alkyl Radicals with Dioxygen
Reactions of Peroxyl Radicals
Chain Termination in Oxidized Hydrocarbons
Reactions of Alkoxyl Radicals
Different Mechanisms of the Aliphatic Hydrocarbon Oxidation in Gas and Liquid Phases
Initiation of Liquid-Phase Oxidation
Initiators
Cage Effect
nitiation of Oxidation by Chemically Active Gases
Photoinitiation
Generation of Radicals by Ionizing Radiation
Oxidation as an Autoinitiated Chain Reaction
Chain Generation by Reaction of Hydrocarbon with Dioxygen
Hydroperoxides
Reactions of Free Radical Generation by Hydroperoxides
Parabolic Model of Bimolecular Homolytic Reaction
nitiation by Reaction of Hydroperoxides with Ketones
Chain Decomposition of Hydroperoxides
Kinetics of Autoinitiated Hydrocarbon Oxidation
Co-Oxidation of Hydrocarbons
Theory of Hydrocarbon Co-oxidation
Hydrocarbon Oxidation with Hydroperoxide
Co-oxidation of Hydrocarbons and Alcohols with Selective Inhibitor
Cross-disproportionation of Peroxyl Radicals
Cross-propagation Reactions of Peroxyl Radicals
High Reactivity of Haloidalkylperoxyl Radicals
Co-oxidation of Hydrocarbon and its Oxidation Intermediates
Catalysis by Nitroxyl Radicals in Hydrocarbon Oxidation
Reactivity of the Hydrocarbons in Reactions with Peroxyl, Alkoxyl, and Alkyl Radicals
Semiempirical Model of Radical Reaction as an Intersection of Two Parabolic Potential Curves
Factors Influencing the Activation Energ
Geometry of the Transition State of Radical Abstraction Reaction
*Intramolecular Hydrogen Transfer Reactions in Peroxyl, Alkoxyl, and Alkyl Radicals
Free Radical Addition Reactions
Free Radical Substitution and Hydrogen AtomTransfer Reactions
Oxidation of Alcohols and Ethers
Oxidation of Alcohols
Oxidation of Ethers
Oxidation of Carbonyl Compounds and Decarboxylation of Acids
Oxidation of Aldehydes
Chemistry of Peracids
Oxidation of Ketones
Oxidative Decarboxylation of Carboxylic Acids
Oxidation of Amines, Amides, and Esters
Oxidation of Aliphatic Amines
Oxidation of Amides
Oxidation of Esters
Catalysis in Liquid-Phase Hydrocarbon Oxidation
Catalysis by Transition Metal Ions and Complexes in Hydrocarbon Oxidation by Dioxygen
Cobalt Bromide Catalysis
Oscillating Oxidation Reactions
Acid Catalysis in Liquid-Phase Oxidation of Hydrocarbons and Alcohols
Catalytic Epoxidation of Olefins by Hydroperoxides
Catalytic Oxidation of Olefins to Aldehydes
Heterogeneous Catalysis in Liquid-Phase Oxidation
Oxidation in Basic Solutions
Oxidation of Hydrocarbons in Microheterogeneous Systems
Emulsion Oxidation of Hydrocarbons
Hydrocarbon Oxidation in Microheterogeneous Systems
Sulfoxidation of HydrocarbonsChain Mechanismof Sulfoxidation
Elementary Steps of Sulfoxidation
Decomposition of Alkylsulfonyl Peracids
Oxidation by Alkylsulfonic Peracids
Oxidation of Polymers
Initiated Oxidation of Polymers
Autoxidation of Polymers
Oxidative Degradation of Macromolecules
Heterogeneous Character of Polymer Oxidation
Part II. Chemistry of Antioxidants
Theory of Inhibition of Chain Oxidation of Organic Compounds
Historical Introduction
Kinetic Classification of Antioxidants
Mechanisms of Inhibition of Initiated Chain Oxidation
Kinetics of Autoxidation of Organic Compounds Inhibited by Acceptors of Peroxyl Radicals
Topological Kinetics of Inhibited Oxidation of Hydrocarbons
Antioxidants Reacting with Peroxyl Radicals
Reaction of Phenols with Peroxyl Radicals
Reaction of Aromatic Amines with Peroxyl Radicals
Reactions of Phenoxyl and Aminyl Radicals with RO2
Recombination and Disproportionation of Phenoxyl and Aminyl Radical
Reactions of Phenoxyl and Aminyl Radicals with Hydrocarbons, Hydroperoxides, and Dioxygen
Direct Oxidation of Phenols and Amines by Dioxygen and Hydroperoxides
Cyclic Chain Termination in Oxidation of Organic Compounds
Cyclic Chain Termination by Aromatic Amines and Aminyl Radicals
Cyclic Chain Termination by Quinones
Cyclic Chain Termination by Nitroxyl Radicals
Acid Catalysis in Cyclic Chain Termination
Transition Metal Ions as Catalysts for Cyclic Chain Termination
Hydroperoxide Decomposing Antioxidants
ntroduction
Organophosphorus Antioxidants
Sulfur-Containing Antioxidants
Metal Thiophosphates and Thiocarbamates
Metal Complexes with Phosphites
Synergismof Antioxidant ActionSynergismof Chain Termination and Hydroperoxide Decomposing
the Antioxidants
Synergismof Two Antioxidants Terminating Chains
Peculiarities of Antioxidant Action in Polymers
Rigid Cage of Polymer Matrix
Antioxidants Reacting with Peroxyl Radicals
Antioxidants Reacting with Alkyl Radicals
Cyclic Chain Termination in Oxidized Polymers
Inhibition of Synthetic Rubber Degradation
Heterogeneous Inhibition of Oxidation
Retarding Action of Solids
Inhibitor Action in Catalyzed Hydrocarbon Oxidation
Dioxygen Acceptors as Stabilizers of Polymers
Part III. Biological Oxidation and Antioxidants
nitiators of Free Radical-Mediated Processes
Superoxide
Hydroxyl Radical
Perhydroxyl Radical
Nitric Oxide
Other Reactive Nitrogen Oxide Species
Peroxynitrite
Iron
Possible Effects of Magnetic Field on Free Radical Formation
Generation of Free Radicals by Prooxidant Enzymes
anthine Oxidase
NADPH Oxidases
Nitric Oxide Synthases
Peroxidases
Production of Free Radicals by Mitochondria
Detection of Active Oxygen Species in Mitochondria
Rates and Mechanismof Superoxide Production in Mitochondria
Free Radical-Mediated Damage to Mitochondria
Mechanisms of Mitochondria Protection fromFree Radical-Mediated Damage
Preconditioning as a Protection of Mitochondria from Oxygen Radical-Mediated Damage
Mitochondrial Oxygen Radical Production and Apoptosis
Mitochondrial Nitrogen Oxide Production and Apoptosis
Production of Free Radicals by Microsomes
Microsomal NADPH-Cytochrome P-450 Reductase and NADH cytochrome b5 Reductase
Production of Free Radicals by Microsomes
Microsomal Free Radical-Mediated Oxidative Processes
Formation and Reactions of Nitrogen Oxygen Species in Microsomes
Nonenzymatic Lipid Peroxidation
Initiation of Nonenzymatic Lipid Peroxidation
Lipid Peroxidation of Unsaturated Fatty Acids
Cholesterol Oxidation
The Formation of Prostanoids
Oxidation of Low-Density Lipoproteins
Enzymatic Lipid Peroxidation
Lipid Peroxidation and Free Radical Production Catalyzed by LOXs
Lipid Peroxidation and Free Radical Production Catalyzed by Prostaglandin H Synthases
Oxidation by Linoleate Diol Synthase
Oxidation of Proteins
Free Radical Mechanisms of Protein Oxidation
Some Examples of Oxidative Processes with the Participation of Proteins
Competition Between Protein and Lipid Oxidatio
Inhibition of Protein Oxidation by Antioxidants and Free Radical Scavengers
Repairing and Proteolysis of Oxidized Proteins
DNA Oxidative Damage
Hydroxyl Radical-Mediated DNA Damage
Superoxide-Dependent DNA Damage
DNA Damage by Enzymatic Superoxide Production
Reactive Oxygen Species as Mediators of Drug- and Xenobiotic-Induced DNA Damage
DNA Damage by Reactive Nitrogen Species
Repair of Free Radical-Mediated DNA Damage
Antioxidants
Vitamin E
Vitamin C
Flavonoids
Phenolic Compounds other than Flavonoids
Thiols
Ubiquinones
Quinones
Uric Acid
Steroids
CalciumAntagonists and b-Blockers
Pyrrolopyrimidines
NADPH
b-Carotene
Melatonin
Ebselen
Metallothioneins and Zinc
Metalloporphyrins
Lactate
Aspirin
Amino Acids
Vitamin B6
Targeted Antioxidants
Natural Antioxidant Mixtures
Chelators
Synergistic Interaction of Antioxidants, Free Radical Scavengers, and Chelators
Antioxidant Enzymes
Superoxide Dismutase: The Latest Developments
Superoxide Reductases
Catalase
Glutathione Redox Cycle
Thioredoxin Reductase
Phase 2 Antioxidant Enzymes and Alkenal/One Oxidoreductase
Free Radicals and Oxidative Stress in Pathophysiological Processes
Cardiovascular Diseases
Cancer, Carcinogenesis, Free Radicals, and Antioxidants
Inflammation
Iron-Catalyzed Pathophysiological Disorders
Bloom’s Syndrome and Down Syndrome
Other Examples of Free Radical Formation in Pathophysiological Disorders
Free Radicals in Aging
Comments on Contemporary Methods of Oxygen and Nitrogen Free Radical Detection
Detection of Superoxide in Biological Systems
Detection of Hydroxyl Radicals
Detection of Nitric Oxide
Detection of Peroxynitrite