Sunday, July 14, 2019

Oxidation and Antioxidants in Organic Chemistry and Biology

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Oxidation of organic compounds by dioxygen is a phenomenon of exceptional importance in nature, technology, and life. The liquid-phase oxidation of hydrocarbons forms the basis of several efficient technological synthetic processes such as the production of phenol via cumene oxidation, cyclohexanone from cyclohexane, styrene oxide from ethylbenzene, etc. The intensive development of oxidative petrochemical processes was observed in 1950–1970. Free radicals participate in the oxidation of organic compounds. Oxidation occurs very often as a chain reaction. Hydroperoxides are formed as intermediates and accelerate oxidation. The chemistry of the liquid-phase oxidation of organic compounds is closely interwoven with free radical chemistry, chemistry of peroxides, kinetics of chain reactions, and polymer chemistry.

The science of oxidation processes developed intensively during the 20th century. In the very beginning of this century, A.N. Bach and C. Engler formulated the peroxide conception of oxidation by dioxygen. H. Backstrom proved the chain mechanism of slow liquid-phase oxidation (1927). N.N. Semenov formulated the theory of chain oxidation with degenerate branching of chains applied to hydrocarbon oxidation (1934). A line of brilliant kinetic experiments were performed in the period 1960–1980 concerning elementary steps of liquidphase oxidation of hydrocarbons. The results of these studies were collected in two volumes edited by W.O. Lundberg, Autoxidation and Antioxidants (1961) and monograph Liquid- Phase Oxidation of Hydrocarbons written by N.M. Emanuel, E.T. Denisov, and Z.K. Maizus (1967). The results of the study of oxidation of oxygen-containing compounds were systematized in the monograph Liquid-Phase Oxidation of Oxygen-Containing Compounds (E.T. Denisov, N.I. Mitskevich, V.E. Agabekov, 1977). Several new excellent experimental methods were developed in the second half of the 20th century for the study of free radical reactions. A great body of kinetic data on reactions of alkyl, peroxyl, alkoxyl, and others radicals was obtained in many publications from 1960 to 1990 (see Database applied to the book).

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
Chapter 1: Molecular Products and Thermochemistry of Hydrocarbon Oxidation
Chapter 2: Chain Mechanism of Liquid-Phase Oxidation of Hydrocarbons.
Chapter 3: Initiation of Liquid-Phase Oxidation
Chapter 4: Oxidation as an Autoinitiated Chain Reaction
Chapter 5: Co-Oxidation of Hydrocarbons
Chapter 6: Reactivity of the Hydrocarbons in Reactions with Peroxyl, Alkoxyl, and Alkyl Radicals
Chapter 7: Oxidation of Alcohols and Ethers
Chapter 8: Oxidation of Carbonyl Compounds and Decarboxylation of Acids
Chapter 9: Oxidation of Amines, Amides, and Esters
Chapter 10: Catalysis in Liquid-Phase Hydrocarbon Oxidation
Chapter 11: Oxidation of Hydrocarbons in Microheterogeneous Systems
Chapter 12: Sulfoxidation of Hydrocarbons
Chapter 13: Oxidation of Polymers
Part II: Chemistry of Antioxidants
Chapter 14: Theory of Inhibition of Chain Oxidation of Organic Compounds
Chapter 15: Antioxidants Reacting with Peroxyl Radicals
Chapter 17: Hydroperoxide Decomposing Antioxidants
Chapter 18: Synergism of Antioxidant Action
Chapter 19: Peculiarities of Antioxidant Action in Polymers
Chapter 20: Heterogeneous Inhibition of Oxidation
Part III: Biological Oxidation and Antioxidants
Chapter 21: Initiators of Free Radical-Mediated Processes
Chapter 22: Generation of Free Radicals by Prooxidant Enzymes
Chapter 23: Production of Free Radicals by Mitochondria
Chapter 24: Production of Free Radicals by Microsomes
Chapter 25: Nonenzymatic Lipid Peroxidation
Chapter 26: Enzymatic Lipid Peroxidation
Chapter 27: Oxidation of Proteins
Chapter 28: DNA Oxidative Damage
Chapter 29: Antioxidants
Chapter 30: Antioxidant Enzymes
Chapter 32: Comments on Contemporary Methods of Oxygen and Nitrogen Free Radical Detection

Author Details
"Evgeny T. Denisov"

"Igor B. Afanas’ev"

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