Oxidation and Antioxidants in Organic Chemistry and Biology

by Denisov; Evgeny T.

• ISBN13: 9780824753566
• ISBN10: 0824753569
• Edition: CD
• Format: Hardcover
• Copyright: 2005-03-29
• Publisher: CRC Press

Summary

Covering the chemistry of liquid-phase oxidation of organic compounds, this book includes the results of analysis with the parabolic model as applied to reactions of peroxyl radicals with C-H bond of different organic compounds. It supplies chemical mechanistic information about antioxidants and their action on the autoxidation of hydrocarbons, alcohols, and other organic compounds and polymers. The authors explore the development of the theory of antioxidant reactivity using the conception of intersection of parabolic potential curves and discuss the physiological and pathophysiological oxidative processes mediated by free radical activity.

Table of Contents

Preface	xxiii
Authors	xxvii
List of Chemical Symbols and Abbreviations	xxix
List of Physicochemical Symbols	xxxi
List of Biochemical Abbreviations	xxxv
Part I Chemistry and Kinetics of Organic Compounds Oxidation by Dioxygen	1	(462)
Molecular Products and Thermochemistry of Hydrocarbon Oxidation	3	(20)
Earlier Concepts of Oxidation	3	(3)
Development of the Chain Theory of Oxidation of Organic Compounds	6	(3)
Hydroperoxides as Primary Molecular Products of Hydrocarbon Oxidation	9	(4)
Hydroperoxides	9	(2)
Dihydroperoxides	11	(1)
Cyclic and Polymeric Peroxides	12	(1)
Epoxides	13	(1)
Products of Hydroperoxide Decomposition	13	(10)
Hydroperoxides as the Intermediates of Hydrocarbon Oxidation	13	(1)
Alcohols	14	(2)
Ketones	16	(1)
Acids	16	(2)
References	18	(5)
Chain Mechanism of Liquid-Phase Oxidation of Hydrocarbons	23	(62)
The Peculiarities of Chain Reactions	23	(4)
Free-Valence Persistence in Reactions of Free Radicals with Molecules	23	(1)
Condition of Cyclicity of Radical Conversions	23	(1)
Priority of Chain Propagation Reaction	24	(1)
Generation of Free Radicals	24	(1)
Competition of Chain and Molecular Reactions	25	(1)
High Chemical Reactivity of Free Radicals and Atoms	25	(1)
Conservation of Orbital Symmetry in Chemical Reaction	26	(1)
Configuration of Transition State	26	(1)
Chain Mechanism of Hydrocarbon Oxidation	27	(7)
Reaction of Alkyl Radicals with Dioxygen	34	(5)
Reactions of Peroxyl Radicals	39	(16)
Structure and Thermochemistry of Peroxyl Radicals	39	(4)
Reaction RO2 + RH → ROOH + R	43	(2)
Intramolecular Hydrogen Atom Transfer in Peroxyl Radical	45	(4)
Addition of Peroxyl Radical to the Double Bond	49	(6)
Chain Termination in Oxidized Hydrocarbons	55	(14)
Tetroxides	55	(2)
Disproportionation of Tertiary Peroxyl Radicals	57	(1)
Disproportionation of Primary and Secondary Peroxyl Radicals	58	(4)
Chemiluminescence	62	(5)
Chain Termination via Alkyl Radicals	67	(2)
Reactions of Alkoxyl Radicals	69	(3)
Different Mechanisms of the Aliphatic Hydrocarbon Oxidation in Gas and Liquid Phases	72	(13)
References	76	(9)
Initiation of Liquid-Phase Oxidation	85	(52)
Initiators	85	(9)
Mechanisms of Decomposition of Initiators	85	(1)
Unimolecular Decomposition of Initiator with One Bond Splitting	85	(1)
Concerted Fragmentation of Initiators	86	(1)
Anchimerically Assisted Decomposition of Peroxides	87	(1)
Decay of Initiators to Molecular Products	88	(1)
Chain Decomposition of Initiators	89	(1)
Peroxides	90	(1)
Azo-Compounds	90	(4)
Cage Effect	94	(7)
Experimental Evidences for Cage Effect	94	(1)
Quantum Yield	94	(1)
Products of Radical Pair Combination	95	(1)
Oxygen-18 Scrambling and Racemization	95	(1)
Crossover Experiments	96	(1)
Racemization	97	(1)
Influence of Viscosity	98	(1)
Influence of Pressure	99	(1)
Spin Multiplicity Effects	99	(1)
Mechanistic Schemes of the Cage Effect	99	(2)
Initiation of Oxidation by Chemically Active Gases	101	(17)
Ozone	101	(9)
Nitrogen Dioxide	110	(3)
Halogens	113	(5)
Photoinitiation	118	(10)
Intramolecular and Intermolecular Photophysical Processes	120	(3)
Photosensitizers	123	(1)
Photoinitiators	124	(1)
Azo-compounds	124	(2)
Peroxides	126	(1)
Carbonyl Compounds	127	(1)
Nonchain Photooxidation	127	(1)
Generation of Radicals by Ionizing Radiation	128	(9)
Primary Radiation-Chemical Processes	128	(1)
Radiolytic Initiation of Hydrocarbon Oxidation	129	(3)
References	132	(5)
Oxidation as an Autoinitiated Chain Reaction	137	(48)
Chain Generation by Reaction of Hydrocarbon with Dioxygen	137	(7)
Bimolecular Reaction of Dioxygen with the C---H Bond of the Hydrocarbon	137	(4)
Trimolecular Reaction of Hydrocarbon with Dioxygen	141	(1)
Bimolecular and Trimolecular Reactions of Dioxygen with the Double Bond of Olefin	141	(3)
Hydroperoxides	144	(5)
Analysis	145	(1)
Structure of Hydroperoxides	146	(1)
Thermochemistry of Hydroperoxides	147	(1)
Hydrogen Bonding between Hydroperoxides	147	(2)
Reactions of Free Radical Generation by Hydroperoxides	149	(9)
Unimolecular Decomposition of Hydroperoxides	149	(5)
Bimolecular Decomposition of Hydroperoxides	154	(1)
Bimolecular Reactions of Hydroperoxides with π-Bonds of Olefins	154	(3)
Bimolecular Reactions of Hydroperoxides with C---H, N---H, and O---H Bonds of Organic Compounds	157	(1)
Parabolic Model of Bimolecular Homolytic Reaction	158	(9)
Main Equations of IPM	158	(2)
Calculation of E and k of a Bimolecular Reaction	160	(3)
Bimolecular Reactions of Radical Generation	163	(1)
Bimolecular Splitting of Hydroperoxides	163	(1)
Reaction of Hydroperoxides with Olefins	163	(1)
Reaction of Hydroperoxides with Hydrocarbons	164	(1)
Reaction of Hydroperoxides with Alcohols and Acids	164	(3)
Initiation by Reaction of Hydroperoxides with Ketones	167	(1)
Chain Decomposition of Hydroperoxides	168	(5)
Kinetics of Autoinitiated Hydrocarbon Oxidation	173	(12)
Initial Stage of Autoxidation	173	(3)
Autoxidation with Bimolecular Hydroperoxide Decay	176	(1)
Initiation by Reactions of Hydroperoxide with Products of Oxidation	177	(1)
Hydroperoxide as the Intermediate Product of Autoxidation	178	(1)
Self-Inhibition of Hydrocarbon Oxidation	179	(2)
References	181	(4)
Co-Oxidation of Hydrocarbons	185	(28)
Theory of Hydrocarbon Co-oxidation	185	(2)
Hydrocarbon Oxidation with Hydroperoxide	187	(4)
Co-oxidation of Hydrocarbons and Alcohols with Selective Inhibitor	191	(5)
Cross-disproportionation of Peroxyl Radicals	196	(3)
Cross-propagation Reactions of Peroxyl Radicals	199	(4)
High Reactivity of Haloidalkylperoxyl Radicals	203	(1)
Co-oxidation of Hydrocarbon and its Oxidation Intermediates	204	(3)
Catalysis by Nitroxyl Radicals in Hydrocarbon Oxidation	207	(6)
References	209	(4)
Reactivity of the Hydrocarbons in Reactions with Peroxyl, Alkoxyl, and Alkyl Radicals	213	(48)
Semiempirical Model of Radical Reaction as an Intersection of Two Parabolic Potential Curves	213	(6)
Introduction	213	(1)
Intersecting Parabolas Model (IPM)	214	(2)
Calculation of the Activation Energy	216	(3)
Factors Influencing the Activation Energy	219	(14)
Reaction Enthalpy	219	(5)
Force Constants of the Reacting Bonds	224	(1)
Triplet Repulsion in the Transition State	225	(1)
Electron Affinity of Atoms of Reaction Center	226	(2)
Radii of Atoms of Reaction Center	228	(2)
Influence of Adjacent π-Bonds	230	(1)
Polar Effect	231	(1)
Influence of Solvation	232	(1)
Geometry of the Transition State of Radical Abstraction Reaction	233	(3)
Intramolecular Hydrogen Transfer Reactions in Peroxyl, Alkoxyl, and Alkyl Radicals	236	(5)
Peroxyl Radicals	236	(1)
Alkoxyl Radicals	236	(2)
Alkyl Radicals	238	(3)
Free Radical Addition Reactions	241	(10)
Enthalpy of Free Radical Addition	241	(1)
Parabolic Model of Radical Addition Reaction	241	(1)
Triplet Repulsion in Radical Addition Reactions	242	(1)
Influence of the Neighboring π-Bonds on the Activation Energy of Radical Addition	243	(3)
Role of the Radius of the Atom Bearing a Free Valence	246	(1)
Interaction of Polar Groups	247	(3)
Steric Hindrance	250	(1)
Free Radical Substitution and Hydrogen Atom Transfer Reactions	251	(10)
Free Radical Substitution Reactions	251	(3)
Reaction of Peroxides with Ketyl Radicals	254	(3)
References	257	(4)
Oxidation of Alcohols and Ethers	261	(38)
Oxidation of Alcohols	261	(20)
Introduction	261	(1)
Chain Mechanism of Alcohol Oxidation	261	(2)
Kinetics of Oxidation	263	(1)
Reactions of Ketyl Radicals with Dioxygen	263	(1)
Reactions of Alkylhydroxyperoxyl and Hydroperoxyl Radicals	263	(6)
Chain Termination in Oxidized Alcohols	269	(1)
Co-Oxidation of Alcohols and Hydrocarbons	270	(3)
Reactivity of Alcohols in Reaction with Peroxyl Radicals	273	(5)
Chain Generation in Autoxidation of Alcohols	278	(1)
Chain Generation by Reaction with Dioxygen	278	(1)
Decomposition of Hydrogen Peroxide into Free Radicals	278	(1)
Chain Generation by Reaction of Hydrogen Peroxide with Carbonyl Compound	279	(2)
Oxidation of Ethers	281	(18)
Introduction	281	(2)
Chain Oxidation of Ethers	283	(4)
Co-Oxidation of Ethers and Hydrocarbons	287	(4)
Reactivity of Ethers in Reactions with Peroxyl Radicals	291	(5)
References	296	(3)
Oxidation of Carbonyl Compounds and Decarboxylation of Acids	299	(30)
Oxidation of Aldehydes	299	(9)
Introduction	299	(1)
Chain Mechanism of Aldehyde Oxidation	300	(3)
Co-Oxidation of Aldehydes with Hydrocarbons, Alcohols, and Aldehydes	303	(3)
Reactivity of Aldehydes in Reactions with Peroxyl Radicals	306	(2)
Chemistry of Peracids	308	(3)
Oxidation of Ketones	311	(9)
Chain Mechanism of Ketone Oxidation	311	(3)
Reactivity of Ketones in Reactions with Peroxyl Radicals	314	(3)
Interaction of Ketones with Hydroperoxides	317	(1)
Chemistry of Ketone Oxidation	318	(2)
Oxidative Decarboxylation of Carboxylic Acids	320	(9)
Attack of Peroxyl Radicals on C---H Bonds	320	(1)
Oxidative Decarboxylation of Acids	321	(3)
References	324	(5)
Oxidation of Amines, Amides, and Esters	329	(30)
Oxidation of Aliphatic Amines	329	(7)
Introduction	329	(2)
Chain Mechanism of Alkylamine Oxidation	331	(2)
Reactivity of Amines in Reaction with Peroxyl Radicals	333	(3)
Oxidation of Amides	336	(5)
Introduction	336	(2)
Chain Mechanism of Amide Oxidation	338	(1)
Decomposition of Hydroperoxides	338	(3)
Oxidation of Esters	341	(18)
Introduction	341	(2)
Chain Mechanism of Ester Oxidation	343	(6)
Reactivity of Esters in Reactions with Peroxyl Radicals	349	(1)
Effect of Multidipole Interaction in Reactions of Polyfunctional Esters	350	(5)
References	355	(4)
Catalysis in Liquid-Phase Hydrocarbon Oxidation	359	(52)
Catalysis by Transition Metal Ions and Complexes in Hydrocarbon Oxidation by Dioxygen	359	(24)
Introduction	359	(1)
Catalytic Decomposition of Hydrogen Peroxide by Ferrous Ions	360	(3)
Catalysis by Transition Metal Ions and Complexes in Liquid-Phase Oxidation of Hydrocarbons and Aldehydes by Dioxygen	363	(5)
Competition between Homolytic and Heterolytic Catalytic Decompositions of Hydroperoxides	368	(2)
Reactions of Transition Metals with Free Radicals	370	(7)
Reactions of Transition Metal Ions with Dioxygen	377	(5)
Catalytic Oxidation of Ketones	382	(1)
Cobalt Bromide Catalysis	383	(3)
Oscillating Oxidation Reactions	386	(3)
Acid Catalysis in Liquid-Phase Oxidation of Hydrocarbons and Alcohols	389	(1)
Catalytic Epoxidation of Olefins by Hydroperoxides	390	(4)
Catalytic Oxidation of Olefins to Aldehydes	394	(2)
Catalysis by Palladium Salts	394	(1)
Kinetics and Mechanism of Reaction	395	(1)
Heterogeneous Catalysis in Liquid-Phase Oxidation	396	(4)
Introduction	396	(1)
Decomposition of Hydroperoxides on Catalyst Surface	397	(1)
Activation of Dioxygen	398	(1)
Critical Phenomena in Heterogeneous Catalysis	399	(1)
Selectivity of Catalytic Oxidation	400	(1)
Oxidation in Basic Solutions	400	(11)
References	403	(8)
Oxidation of Hydrocarbons in Microheterogeneous Systems	411	(6)
Emulsion Oxidation of Hydrocarbons	411	(2)
Hydrocarbon Oxidation in Microheterogeneous Systems	413	(4)
References	415	(2)
Sulfoxidation of Hydrocarbons	417	(14)
Introduction	417	(1)
Chain Mechanism of Sulfoxidation	418	(2)
Elementary Steps of Sulfoxidation	420	(4)
Decomposition of Alkylsulfonyl Peracids	424	(1)
Oxidation by Alkylsulfonic Peracids	425	(6)
Oxidation of Aromatic Hydrocarbons	425	(1)
Oxidation of Olefins	426	(2)
Oxidation of Ketones	428	(1)
References	429	(2)
Oxidation of Polymers	431	(32)
Initiated Oxidation of Polymers	431	(12)
Cage Effect in Solid Polymers	431	(1)
Migration of Free Valence in Solid Polymers	432	(1)
Initiated Polymer Oxidation	433	(3)
Diffusion of Dioxygen in Polymer	436	(3)
Diffusion Regime of Polymer Oxidation	439	(2)
Isomerization of Alkyl and Peroxyl Radicals of Polypropylene	441	(2)
Autoxidation of Polymers	443	(8)
Chain Generation by Dioxygen	443	(1)
Decomposition of Hydroperoxyl Groups	444	(3)
Specificity of Formation of the Hydroperoxyl Group and its Decay in PP	447	(2)
Chain Decay of Hydroperoxyl Groups of PP	449	(2)
Oxidative Degradation of Macromolecules	451	(5)
Heterogeneous Character of Polymer Oxidation	456	(7)
References	458	(5)
Part II Chemistry of Antioxidants	463	(210)
Theory of Inhibition of Chain Oxidation of Organic Compounds	465	(26)
Historical Introduction	465	(1)
Kinetic Classification of Antioxidants	466	(3)
Classification	466	(2)
Capacity, Strength, and Efficiency of Antioxidants	468	(1)
Mechanisms of Inhibition of Initiated Chain Oxidation	469	(8)
Characteristics of Antioxidant Efficiency	475	(2)
Kinetics of Autoxidation of Organic Compounds Inhibited by Acceptors of Peroxyl Radicals	477	(3)
Nonstationary Kinetics of Inhibited Autoxidation	477	(1)
Quasistationary Kinetics of Inhibited Autoxidation	478	(2)
Topological Kinetics of Inhibited Oxidation of Hydrocarbons	480	(11)
Initiated Oxidation	482	(4)
Inhibited Autoxidation	486	(2)
References	488	(3)
Antioxidants Reacting with Peroxyl Radicals	491	(50)
Reaction of Phenols with Peroxyl Radicals	491	(10)
Reaction Enthalpy	491	(3)
Triplet Repulsion in Transition State	494	(2)
Steric Factor	496	(1)
Effect of Hydrogen Bonding on Activity of Inhibitors	497	(4)
Reaction of Aromatic Amines with Peroxyl Radicals	501	(7)
Dissociation Energies of N---H Bonds of Aromatic Amines	501	(1)
Rate Constants of Reaction of RO2 with Aromatic Amines	501	(6)
Electronegativity of Atoms in the Transition State	507	(1)
Reactions of Phenoxyl and Aminyl Radicals with RO2	508	(4)
Recombination of Peroxyl with Phenoxyl Radicals	508	(3)
Reaction of Peroxyl with Aminyl Radicals	511	(1)
Recombination and Disproportionation of Phenoxyl and Aminyl Radicals	512	(7)
Recombination and Disproportionation of Phenoxyl Radicals	512	(3)
Reactions Controlled by Rotational Diffusion	515	(1)
Disproportionation of Semiquinone Radicals	516	(1)
Recombination and Disproportionation of Aminyl Radicals	516	(3)
Reactions of Phenoxyl and Aminyl Radicals with Hydrocarbons, Hydroperoxides, and Dioxygen	519	(9)
Triplet Repulsion	521	(3)
Steric Factor	524	(1)
Electron Affinity of Atoms in the TS	525	(2)
Reactions of Phenoxyl Radicals with Dioxygen	527	(1)
Direct Oxidation of Phenols and Amines by Dioxygen and Hydroperoxides	528	(13)
References	537	(4)
Cyclic Chain Termination in Oxidation of Organic Compounds	541	(32)
Cyclic Chain Termination by Aromatic Amines and Aminyl Radicals	541	(11)
Cyclic Chain Termination by Quinones	552	(3)
Cyclic Chain Termination by Nitroxyl Radicals	555	(6)
Acid Catalysis in Cyclic Chain Termination	561	(3)
Transition Metal Ions as Catalysts for Cyclic Chain Termination	564	(9)
References	569	(4)
Hydroperoxide Decomposing Antioxidants	573	(26)
Introduction	573	(1)
Organophosphorus Antioxidants	573	(7)
Reaction with Hydroperoxides	573	(4)
Reaction with Peroxyl Radicals	577	(3)
Sulfur-Containing Antioxidants	580	(8)
Reaction with Hydroperoxide	580	(3)
Reaction with Peroxyl Radicals	583	(5)
Metal Thiophosphates and Thiocarbamates	588	(3)
Metal Complexes with Phosphites	591	(8)
References	595	(4)
Synergism of Antioxidant Action	599	(28)
Introduction	599	(1)
Synergism of Chain Termination and Hydroperoxide Decomposing the Antioxidants	600	(3)
Synergism of Two Antioxidants Terminating Chains	603	(24)
Combined Action of Phenol and Amine on Hydrocarbon Oxidation	603	(4)
Combined Action of Two Phenols	607	(4)
Synergism of Phenol and Nitroxyl Radical Action on Hydrocarbon Oxidation	611	(5)
Synergistic Action of Quinone in Combination with Phenol or Amine	616	(4)
The Combined Action of Fe and Cu Salts	620	(5)
References	625	(2)
Peculiarities of Antioxidant Action in Polymers	627	(38)
Rigid Cage of Polymer Matrix	627	(17)
Comparison of Bimolecular Reactions in Liquid and Solid Phases	627	(4)
Conception of Rigid Cage of Polymer Matrix	631	(10)
The Phenomena of Reactivity Leveling in Polymeric Matrix	641	(2)
Reactions Limited by Rotational Diffusion in Polymer Matrix	643	(1)
Antioxidants Reacting with Peroxyl Radicals	644	(5)
Antioxidants Reacting with Alkyl Radicals	649	(3)
Cyclic Chain Termination in Oxidized Polymers	652	(7)
Regeneration of Nitroxyl Radicals in Polymer Oxidation	652	(2)
Cyclic Chain Termination in Oxidized Polypropylene	654	(5)
Inhibition of Synthetic Rubber Degradation	659	(6)
References	662	(3)
Heterogeneous Inhibition of Oxidation	665	(8)
Retarding Action of Solids	665	(3)
Inhibitor Action in Catalyzed Hydrocarbon Oxidation	668	(2)
Dioxygen Acceptors as Stabilizers of Polymers	670	(3)
References	671	(2)
Part III Biological Oxidation and Antioxidants	673	(294)
Initiators of Free Radical-Mediated Processes	675	(26)
Superoxide	675	(1)
Hydroxyl Radical	676	(1)
Perhydroxyl Radical	677	(1)
Nitric Oxide	677	(4)
Formation and Lifetime of Nitric Oxide	677	(1)
Reaction with Dioxygen	678	(1)
Reaction with Superoxide and Inorganic Nitrogen Compounds	678	(1)
Reactions with Biomolecules	679	(2)
Interaction with Enzymes	681	(1)
Other Reactive Nitrogen Oxide Species	681	(2)
Peroxynitrite	683	(6)
Formation, Decomposition, and Reactions of Peroxynitrite	683	(4)
Reaction of Peroxynitrite with Carbon Dioxide	687	(1)
Examples of Biological Functions of Nitric Oxide and Peroxynitrite	688	(1)
Iron	689	(4)
Structure and Origins of ``Free'' Iron	689	(1)
Iron-Stimulated Free Radical-Mediated Damaging Processes	690	(2)
Iron-Stimulated Toxic Effects of Pathogenic Fibers and Particles	692	(1)
Possible Effects of Magnetic Field on Free Radical Formation	693	(8)
References	695	(6)
Generation of Free Radicals by Prooxidant Enzymes	701	(30)
Xanthine Oxidase	701	(3)
Mechanisms of Oxygen Radical Production	701	(2)
Reactions of XO with Organic and Inorganic Substrates	703	(1)
Free Radical-Mediated Biological Activity of Xanthine Oxidoreductase	704	(1)
NADPH Oxidases	704	(6)
Leukocyte NADPH Oxidase	705	(2)
NADPH Oxidase of Nonphagocytic Cells	707	(3)
Nitric Oxide Synthases	710	(5)
Types and Structure of Nitric Oxide Synthases	710	(1)
Free Radical Production by Nitric Oxide Synthases	711	(3)
Mitochondrial Nitric Oxide Synthase	714	(1)
Peroxidases	715	(16)
Mechanism of Free Radical Production	715	(1)
Oxidation of Phenolic Compounds	716	(2)
Oxidation of Glutathione and Other Organic Substrates	718	(1)
Reactions with Inorganic Compounds	718	(1)
Mechanism of the Interaction of Peroxidases with Hydroperoxides. Role of Superoxide and Hydroxyl Radicals in Reactions Catalyzed by Peroxidases	719	(2)
Peroxidase-Catalyzed Oxidative Processes	721	(1)
Interaction with Nitrogen Oxides	721	(2)
References	723	(8)
Production of Free Radicals by Mitochondria	731	(16)
Detection of Active Oxygen Species in Mitochondria	731	(1)
Rates and Mechanism of Superoxide Production in Mitochondria	732	(3)
Free Radical-Mediated Damage to Mitochondria	735	(1)
Mechanisms of Mitochondria Protection from Free Radical-Mediated Damage	736	(1)
Preconditioning as a Protection of Mitochondria from Oxygen Radical-Mediated Damage	736	(2)
Mitochondrial Oxygen Radical Production and Apoptosis	738	(3)
Reactive Oxygen Species as Mediators of Apoptosis	738	(1)
Mechanisms of the Activation of Apoptosis by Reactive Oxygen Species	739	(1)
Protection Against Apoptosis Activated by Reactive Oxygen Species	740	(1)
Mitochondrial Nitrogen Oxide Production and Apoptosis	741	(6)
References	743	(4)
Production of Free Radicals by Microsomes	747	(10)
Microsomal NADPH--Cytochrome P-450 Reductase and NADH cytochrome b5 Reductase	747	(2)
Production of Free Radicals by Microsomes	749	(1)
Microsomal Free Radical-Mediated Oxidative Processes	750	(3)
Formation and Reactions of Nitrogen Oxygen Species in Microsomes	753	(4)
References	754	(3)
Nonenzymatic Lipid Peroxidation	757	(32)
Initiation of Nonenzymatic Lipid Peroxidation	757	(8)
HO and O2 as Initiators of Lipid Peroxidation	757	(3)
NO, NO Metabolites, and HOCL	760	(3)
Xenobiotics as Initiators of Lipid Peroxidation	763	(2)
Phagocytes as Initiators of Lipid Peroxidation	765	(1)
Lipid Peroxidation of Unsaturated Fatty Acids	765	(1)
Cholesterol Oxidation	766	(3)
The Formation of Prostanoids	769	(7)
Oxidation of Low-Density Lipoproteins	776	(13)
Mechanism of LDL Oxidation	776	(1)
Initiation of LDL Oxidation	777	(2)
Role of Nitric Oxide and Peroxynitrite in the Initiation of LDL Oxidation	779	(1)
Initiation of LDL Oxidation by MPO	779	(3)
Major Products and Pathophysiological Effects of LDL Oxidation	782	(1)
References	783	(6)
Enzymatic Lipid Peroxidation	789	(20)
Lipid Peroxidation and Free Radical Production Catalyzed by LOXs	789	(9)
Mechanism of LOX Catalysis	789	(2)
LOX-Catalyzed Oxidation of Unsaturated Acids	791	(2)
LOX-Catalyzed Oxidation of Low-Density Lipoproteins	793	(2)
LOX-Catalyzed Cooxidation of Substrates	795	(1)
Oxygen Radical Formation by LOX-Catalyzed Reactions	796	(1)
Effects of Nitrogen Oxides on LOX-Catalyzed Processes	796	(2)
Comments on Pathophysiological Activities of LOXs	798	(1)
Lipid Peroxidation and Free Radical Production Catalyzed by Prostaglandin H Synthases	798	(5)
Mechanism of Reactions Catalyzed by Prostaglandin H Synthases	798	(2)
Production and Interaction with Oxygen Radicals	800	(1)
Cyclooxygenase-Catalyzed Cooxidation of Substrates	801	(1)
Effects of Reactive Nitrogen Species on Prostaglandin H-Catalyzed Processes	801	(2)
Oxidation by Linoleate Diol Synthase	803	(6)
References	805	(4)
Oxidation of Proteins	809	(10)
Free Radical Mechanisms of Protein Oxidation	809	(5)
Free Radical Initiation of Protein Oxidation	809	(2)
Metal Ion-Catalyzed Oxidation of Proteins	811	(1)
Protein Oxidation Initiated by Peroxynitrite, Nitric Oxide, and Hypoclorite	812	(2)
Some Examples of Oxidative Processes with the Participation of Proteins	814	(1)
Competition Between Protein and Lipid Oxidation	814	(1)
Inhibition of Protein Oxidation by Antioxidants and Free Radical Scavengers	815	(1)
Repairing and Proteolysis of Oxidized Proteins	815	(4)
References	816	(3)
DNA Oxidative Damage	819	(16)
Hydroxyl Radical-Mediated DNA Damage	819	(3)
Mechanism of Hydroxyl Radical and DNA Reactions	819	(1)
Reactions of Hydroxyl and Hydroxyl-Like Radicals Produced by the Fenton Reaction with Nucleic Acids	820	(2)
Superoxide-Dependent DNA Damage	822	(1)
DNA Damage by Enzymatic Superoxide Production	823	(2)
Phagocyte-Stimulated DNA Damage	823	(2)
Reactive Oxygen Species as Mediators of Drug- and Xenobiotic-Induced DNA Damage	825	(2)
Effects of Prooxidants	825	(1)
Damaging Effects of Antioxidants	826	(1)
Damaging Effects of Mineral Dusts and Fibers	827	(1)
DNA Damage by Reactive Nitrogen Species	827	(1)
Repair of Free Radical-Mediated DNA Damage	828	(7)
References	830	(5)
Antioxidants	835	(60)
Vitamin E	836	(5)
Antioxidant and Prooxidant Activity of Vitamin E	836	(2)
Biological Activity	838	(2)
Effects of Vitamin E Supplementation in Aging and Heart Diseases	840	(1)
Synthetic Analogs of Vitamin E	841	(1)
Vitamin C	841	(3)
Antioxidant and Prooxidant Activity of Vitamin C	841	(1)
Biological Activity	842	(1)
Interaction Between Vitamins E and C	843	(1)
Flavonoids	844	(13)
Free Radical Scavenging Activity	845	(4)
Protection Against Free Radical-Mediated Damage	849	(1)
Comparison of Free Radical Scavenging and Chelating Activities	850	(2)
Inhibition of Free Radical-Mediated Damage in Cells	852	(1)
Inhibition LDL Oxidation and Enzymatic Lipid Peroxidation	853	(1)
Other Examples of Protective Activity of Flavonoids Against Free Radical-Mediated Damage in Biological Systems	853	(1)
Antioxidant Effect of Metal-Flavonoid Complexes	854	(2)
Comments on Prooxidant Activity of Flavonoids	856	(1)
Phenolic Compounds other than Flavonoids	857	(3)
Thiols	860	(4)
Lipoic Acid	860	(2)
Glutathione	862	(2)
N-Acetylcysteine and Tetradecylthioacetic Acid	864	(1)
Ubiquinones	864	(2)
Quinones	866	(1)
Uric Acid	867	(1)
Steroids	867	(3)
Calcium Antagonists and β-Blockers	870	(3)
Pyrrolopyrimidines	873	(1)
NADPH	874	(1)
β-Carotene	874	(2)
Melatonin	876	(1)
Ebselen	877	(1)
Metallothioneins and Zinc	878	(1)
Metalloporphyrins	878	(1)
Lactate	879	(1)
Aspirin	879	(1)
Amino Acids	880	(1)
Vitamin B6	880	(1)
Targeted Antioxidants	880	(1)
Natural Antioxidant Mixtures	880	(2)
Chelators	882	(1)
Synergistic Interaction of Antioxidants, Free Radical Scavengers, and Chelators	883	(12)
References	884	(11)
Antioxidant Enzymes	895	(10)
Superoxide Dismutase: The Latest Developments	895	(3)
Mechanism of Superoxide-Dismuting Activity of SODs	895	(1)
SOD Mimics and SOD Modification	896	(1)
Biological Effects of SOD	897	(1)
Superoxide Reductases	898	(1)
Catalase	899	(1)
Glutathione Redox Cycle	900	(1)
Thioredoxin Reductase	900	(1)
Phase 2 Antioxidant Enzymes and Alkenal/One Oxidoreductase	901	(4)
References	901	(4)
Free Radicals and Oxidative Stress in Pathophysiological Processes	905	(46)
Cardiovascular Diseases	905	(10)
Ischemia--Reperfusion	905	(2)
Atherosclerosis	907	(1)
Mitochondria and NADPH Oxidase as Initiators of Oxygen Radical Overproduction in Heart Diseases	908	(1)
Antioxidants and Heart Disease	908	(2)
Hypertension	910	(1)
Preeclampsia	911	(1)
Hyperglycemia and Diabetes Mellitus	911	(1)
Hyperglycemia-Induced Oxidative Stress in Diabetes	911	(2)
Free Radical-Mediated Processes in Diabetes Mellitus	913	(1)
Antioxidants and Diabetes Mellitus	914	(1)
Cancer, Carcinogenesis, Free Radicals, and Antioxidants	915	(5)
Mechanisms of Free Radical Reactions in Tumor Cells	915	(2)
The Treatment of Cancer with Prooxidants	917	(1)
The Treatment of Cancer with Antioxidants	918	(2)
Inflammation	920	(8)
Mechanisms of Free Radical-Mediated Inflammatory Processes	920	(1)
Rheumatoid Arthritis	921	(1)
Lung Diseases	922	(2)
Skin Inflammation	924	(1)
Brain Inflammatory Diseases	925	(1)
Multiple Sclerosis	925	(1)
Amyotrophic Lateral Sclerosis	925	(1)
Alzheimer's Disease	925	(1)
Parkinson's Disease	926	(1)
Kidney Diseases	927	(1)
Liver Diseases	927	(1)
Septic Shock, Pancreatitis, and Inflammatory Bowel Disease	928	(1)
Iron-Catalyzed Pathophysiological Disorders	928	(5)
Hemochromatosis and Hemodialysis of Patients	929	(1)
Thalassemia	929	(2)
Sickle Cell Disease	931	(1)
Fanconi Anemia	932	(1)
Bloom's Syndrome and Down Syndrome	933	(1)
Other Examples of Free Radical Formation in Pathophysiological Disorders	934	(1)
Free Radicals in Aging	934	(17)
The Latest Developments	934	(1)
The Mitochondrial Theory of Aging	935	(1)
References	936	(15)
Comments on Contemporary Methods of Oxygen and Nitrogen Free Radical Detection	951	(16)
Detection of Superoxide in Biological Systems	951	(9)
Cytochrome c Reduction	951	(2)
Spin-Trapping	953	(2)
Lucigenin-Amplified CL as a Sensitive and Specific Assay of Superoxide Detection	955	(2)
Other Chemiluminescent Methods of Superoxide Detection	957	(2)
Adrenochrome (Epinephrine) Oxidation	959	(1)
Nitroblue Tetrazolium Reduction	959	(1)
Fluorescent Methods	960	(1)
Interaction with Aconitase	960	(1)
Detection of Hydroxyl Radicals	960	(1)
Detection of Nitric Oxide	961	(1)
Detection of Peroxynitrite	961	(6)
References	962	(5)
Index	967