Explains the role of reactive intermediates in biological systems as well as in environmental remediation
With its clear and systematic approach, this book examined the broad range of reactive intermediate that can be generated in biological environments, detailing the fundamental properties of each reactive intermediate. Readers gain a contemporary understanding of how these intermediates react with different compounds, with an emphasis on amino acids, peptides, and proteins. The author not only sets forth the basic chemistry and nature of reactive intermediates, he also demonstrates how the properties of the intermediates presented in the book compare with each other.
Oxidation of Amino Acids, Peptides, and Proteins begins with a discussion of radical and non-radical reactive species as well as an exploration of the significance of reactive species in the atmosphere, disinfection processes, and environmental remediation. Next, the book covers such topics as:
- Thermodynamics of amino acids and reactive species and the effect of metal-ligand binding in oxidation chemistry
- Kinetics and mechanisms of reactive halogen, oxygen, nitrogen, carbon, sulfur and phosphate species as well as reactive high-valent Cr, Mn, and Fe species
- Reactivity of the species with molecules of biological and environmental importance
- Generation of reactive species in the laboratory for kinetics studies
- Oxidation of amino acids, peptides, and proteins by permanganate, ferryl, and ferrate species
- Application of reactive species in purifying water and treating wastewater
With this book as their guide, readers will be able to assess the overall effects of reactive intermediates in biological environments. Moreover, they’ll learn how to apply this knowledge for successful water purification and wastewater treatment.
Table of Contents
PREFACE TO SERIES xiii
INTRODUCTION xv
1 Reactive Species 1
1.1 Diseases 3
1.1.1 Neurodegenerative Diseases 3
1.1.1.1 Alzheimers Disease 5
1.1.1.2 Parkinson’s Disease 5
1.1.2 Metals in Human Diseases 6
1.2 Protein Structure 9
1.2.1 Oxidative Labeling 10
1.2.1.1 Carbonyl Labeling 10
1.2.1.2 Cysteine Residue Labeling 10
1.2.1.3 Reactive Species Labeling 10
1.2.1.4 Hydroxyl Radical Labeling 12
1.2.2 Other Techniques 13
1.3 Reactive Species 20
1.3.1 Halogen Species 20
1.3.2 Oxygen Species 21
1.3.3 Nitrogen Species 22
1.3.4 Sulfur Species 22
1.3.5 High-Valent Cr, Mn, and Fe Species 25
1.4 Reactive Species in Environmental Processes 26
1.4.1 Atmospheric Environment 26
1.4.2 Disinfection By-Products (DBP) 27
1.4.3 Oxidation Processes for Purifying Water 29
References 30
2 Acid–Base Properties 52
2.1 Dissociation Constants 54
2.2 Speciation 62
2.2.1 Protonation 62
2.2.2 Metal Complexes 63
2.2.2.1 Iron 64
2.2.2.2 Copper, Zinc, and Nickel 66
References 69
3 Halogenated Species 78
3.1 Hypohalogens 79
3.1.1 Hypochlorite 79
3.1.1.1 Kinetics of HOCl 79
3.1.1.2 Products of HOCl Oxidation 83
3.1.2 Hypobromite 88
3.1.2.1 Kinetics of HOBr 88
3.1.2.2 Products of HOBr Oxidation 89
3.1.3 Hypothiocyanous 90
3.1.3.1 Kinetics of HOSCN 91
3.1.3.2 Products of HOSCN Oxidation 92
3.2 Halamines 93
3.2.1 Hydrolysis of Halamines 93
3.2.2 Halogen Transfer by Halamines 94
3.2.3 Reduction of Halamines 96
3.3 Chlorine Dioxide 96
3.3.1 Generation of ClO2 101
3.3.2 Decomposition of ClO2 101
3.3.3 Reactivity of ClO2 104
3.3.3.1 Amino Acids, Peptides, and Proteins 104
3.4 Conclusions 109
References 110
4 Reactive Oxygen Species 122
4.1 Superoxide 122
4.1.1 Generation 122
4.1.2 Properties 123
4.1.3 Reactivity 125
4.1.4 Metalloenzymes 129
4.1.4.1 Manganese Superoxide Dismutase 131
4.1.4.2 Iron Superoxide Dismutase 134
4.1.4.3 Iron Superoxide Reductase (FeSOR) 135
4.2 Singlet Oxygen 140
4.2.1 Reactivity 142
4.3 Ozone 153
4.3.1 Reactivity 154
4.4 Hydroxyl Radical 162
4.4.1 Generation 162
4.4.2 Reactivity 164
4.4.2.1 Main-Chain Cleavage of Protein 165
4.4.2.2 Oxidation of Amino Acid Side Chains 169
Aliphatic Side Chains 169
Sulfur-Containing Side Chains 172
Acidic Side Chains 175
Basic Side Chains 175
Aromatic Side Chains 177
4.5 Conclusions 179
References 182
5 Reactive Inorganic Oxy-Species of C, N, S, and P 205
5.1 Carbon Species 206
5.1.1 Carbonate Radical 206
5.1.1.1 Generation and Properties 206
5.1.1.2 Reactivity 210
5.1.2 Peroxymonocarbonate 217
5.1.2.1 Reactivity 217
5.1.3 Carboxyl Radical 219
5.2 Nitrogen Species 220
5.2.1 Nitrogen Monoxide 220
5.2.2 Nitrogen Dioxide Radical 223
5.2.3 Peroxynitrite 224
5.2.3.1 Generation 224
5.2.3.2 Decomposition in Aqueous Solution 226
5.2.3.3 Reactivity with CO2 228
5.2.3.4 Reactivity with Inorganic and Organic Substrates 229
5.2.3.5 Reactivity with Proteins and Nonprotein Metal Centers 231
5.2.3.6 Reactivity with Amino Acids, Peptides, and Proteins 233
5.3 Sulfur Species 241
5.3.1 Oxysulfur Radicals 241
5.3.1.1 Generation 241
5.3.1.2 Reactivity 244
5.4 Phosphorous Species 246
5.4.1 Phosphate Radicals 246
5.4.1.1 Generation, Equilibria, and Spectral Characteristics 247
5.4.1.2 Reactivity 248
5.5 Conclusions 250
References 252
6 High-Valent Cr, Mn, and Fe Species 278
6.1 Chromium 279
6.1.1 Aqueous Chemistry of Oxo-Cr Compounds 280
6.1.1.1 Cr(III) 280
6.1.1.2 Cr(VI) 280
6.1.1.3 Cr(III) Superoxo and Hydroperoxo Complexes 281
6.1.1.4 Aqueous Cr(IV) Ion 281
Acid medium 281
Alkaline Medium 282
6.1.1.5 Cr(V) 283
6.1.2 Chromium(VI, V, and IV) Complexes 284
6.1.3 Reduction of Cr(VI/V/IV) by Substrates 285
6.1.4 Reactivity of Cr Species 286
6.1.4.1 Fe(II) Complexes 286
6.1.4.2 Hydrogen Peroxide 287
6.1.4.3 Carbohydrates 287
6.1.4.4 Hydroxy Acids 287
6.1.4.5 Ascorbic Acid 288
6.1.4.6 Catecholamines 288
6.1.4.7 Thiols 289
6.1.4.8 Non-Sulfur-Containing Amino Acids and Peptides 291
6.1.4.9 Proteins 291
6.1.4.10 NADPH/NADP 292
6.1.4.11 Nitric Oxide Synthase (NOS) 292
6.1.5 Mechanism 292
6.1.6 Carcinogenesis 295
6.1.7 Genotoxicity and Cytotoxicity 298
6.1.8 Conclusions 302
6.2 Manganese 302
6.2.1 Aqueous Chemistry of Oxo-Mn Compounds 305
6.2.1.1 Mn(III) 305
6.2.1.2 Mn(IV) 308
6.2.1.3 Mn(V) and Mn(VI) 308
6.2.2 Reactivity of Complexes of Hypervalent Mn 312
6.2.3 Oxidation by Mn(VII) 313
6.2.3.1 Amino Acids 314
6.2.3.2 Aminopolycarboxylates (APCs) 319
6.2.4 Conclusions 322
6.3 Iron 322
6.3.1 Iron(IV) and Iron(V) 325
6.3.1.1 Ferryl(IV) Ion 325
6.3.1.2 Iron(IV)- and Iron(V)-Oxo Complexes 330
6.3.1.3 Ferrate(IV) 338
6.3.1.4 Ferrate(V) and Ferrate(VI) 339
6.3.2 Reactivity of Ferrate(V) and Ferrate(VI) 340
6.3.2.1 Amines 341
6.3.2.2 Amino Acids 343
6.3.2.3 Aminopolycarboxylates 353
6.3.3 Conclusions 356
References 357
INDEX 383
