Nitroxides (eBook)

Preface 6
Contents 8
About the Author 11
1 Nitroxides: 170 Years of History 12
1.1 Long Preamble of a Tale (1845–1960) 12
1.2 “Golden” Decade (1962–1972) 14
1.3 New Era 19
1.4 Concluding Remarks 23
References 25
2 Nitroxide Basic Physical Properties 32
2.1 Introduction 32
2.2 Spin Electron–Spin Nuclear Interactions in Nitroxides 34
2.3 Relationships Between the Structure and Properties of Nitroxide 36
References 44
3 Nitroxide Chemical Reactions 46
3.1 Introduction 46
3.2 Nitroxide Redox Potential 47
3.3 Oxoammonium Cation Reactions 53
3.4 Nitroxide Cross-Coupling Reactions 58
3.5 Nitroxides in Electrocatalysis 61
3.6 Nitroxides as Radical Scavenger 65
3.7 Nitroxide Reaction with Typical Antioxidants 69
3.8 Nitroxide Redox Behavior in Biological Systems 74
References 76
4 ESR and NMR as Tools for Nitroxides Studies 81
4.1 Introduction 81
4.2 Spin Electron–Spin Electron Interactions. Distance Determination 83
4.2.1 Spin Electron–Spin Nuclear Interactions 92
References 98
5 Nitroxide Biradicals 103
5.1 Introduction—Historical Notes 103
5.2 Electron Spin Exchange in Nitroxide Biradicals 106
5.3 X-Ray Structures and DFT Calculations 110
5.4 Intramolecular Dynamics in Biradicals 117
5.5 Applications of Biradicals 122
References 123
6 Fluorophore–Nitroxide (Profluorescent Nitroxide) Probes 129
6.1 Introduction 129
6.2 Structure and Synthesis of Dual Fluorophore–Nitroxide Compounds 130
6.2.1 Profluorescent Nitroxides as Redox Probes 138
6.3 Fluorescence Detection of Free Radicals 152
6.4 Photophysical and Photochemical Properties of Fluorescence–Nitroxide 153
6.4.1 Dual Compounds for Photoswitching Magnetic Materials 153
6.4.2 Photophysical Effects in Paramagnetic Complexes Bearing Nitroxides 156
6.4.3 Factors Affected on Intramolecular Fluorescence Quenching, Electron Transfer, and Photoreduction in Dual Compounds 159
References 166
7 Nitroxide-Mediated Polymerization 171
7.1 Introduction 171
7.2 Mechanism of the Nitroxide-Mediated Polymerization 172
7.3 Nitroxide-Mediated Polymerization Kinetics 175
7.4 Surface and Dispersed Systems 178
7.5 NMP in Creation of Complex Macromolecular Architectures 182
7.6 NMP and Polymer Materials 184
7.7 Nitroxide on Inorganic Templates 186
7.8 NMP for Organic Electronics and Other Devices 187
7.9 NMP and Materials for Biomedical Applications 189
7.10 NMP Miscellaneous Applications 191
References 191
8 Nitroxides as Materials 197
8.1 Introduction 197
8.2 Nitroxide Bearing Liquid Crystals 198
8.3 Nitroxide Crystal Structure Materials 207
8.4 Nitroxides in Electric Batteries 210
8.5 Nitroxide Single-Crystal Molecular Magnet 216
References 222
9 Nitroxides in Disease 226
9.1 Introduction 226
9.2 Nitroxides in Cancer 226
9.2.1 Cells 226
9.2.2 Animals 234
9.3 Miscellaneous 235
References 239
10 Spin Labeling 243
10.1 Introduction 243
10.2 Nitroxide Labeling 244
10.2.1 Proteins and Peptides 244
10.2.2 Lipid Membranes 257
10.2.3 Nucleic Acids 259
10.3 Spin Tools 263
10.3.1 Background 263
10.3.2 Spin Oximetry 265
10.3.3 Spin pH Meter 266
10.3.4 Spin Redox Probe 266
10.3.5 SH Moiety Assay 268
10.3.6 Spin Imaging 269
10.3.7 Molecular Dynamics. Spin Viscose Meter 272
10.3.8 Spin Polarity Meter 275
10.4 Alternative Spin Labeling 275
References 283
11 Nitroxides Miscellaneous Application 290
11.1 Multispin Nitroxides 290
11.1.1 Spin Trapping 292
11.2 Spin Label-Spin Probe Method 296
11.2.1 Fundamentals 296
11.2.2 Nitroxide in Investigation of Electrostatic Effects 298
11.3 Immersion Depth of Nitroxide Fragment 302
11.4 Nitroxides in Cotton and Cellulose Physicochemistry and Technology 304
11.5 Spin Cascade 309
11.6 Nitroxides in Matrices 311
References 313
Index 318