Preface ........................................................ XI
1. Stilbenes Preparation and Analysis .......................... 1
1.1. General ............................................... 1
1.2. Classical Methods and Their Development ............... 2
1.2.1. Aldol-Type Condensation ....................... 2
1.2.2. Siegrist Method ............................... 3
1.2.3. Wittig Reaction ............................... 4
1.2.4. Heck Reaction ................................. 5
1.2.5. Negishi-Stille Coupling ....................... 7
1.2.6. Barton-Kellogg-Staudinger Reaction ............ 8
1.2.7. McMurry Reaction .............................. 8
1.2.8. Perkin Reaction ............................... 9
1.3. Miscellaneous Chemical Methods of Stilbene
Synthesis .................................... 10
1.3.1. Palladium-Catalyzed Reactions ................ 10
1.3.2. Horner-Wadsworth-Emmons and Wittig-Horner
Olefination Reactions ........................ 13
1.3.3. Other Synthetic Reactions .................... 13
1.4. Physically Promoted Reactions ........................ 19
1.5. Synthesis of Stilbene Dendrimers ..................... 19
1.6. Stilbene Cyclodextrin Derivatives .................... 23
1.7. Stilbenes on Templates ............................... 25
1.8. Stilbenes Analysis ................................... 28
1.8.1. Methods Using Liquid and Gas
Chromatography ............................... 28
1.8.2. Miscellaneous Analytical Methods ............. 33
References ................................................. 35
2. Stilbene Chemical Reactions ................................ 43
2.1. Halogenation of Stilbenes ............................ 43
2.2. Oxidation of Stilbenes ............................... 46
2.2.1. Epoxidation .................................. 46
2.2.2. Other Oxidation Reactions .................... 48
2.3. Stilbene Reduction ................................... 51
2.4. Other Reactions ...................................... 52
2.4.1. Vinyl Lithiation ............................. 52
2.4.2. Carbolization ................................ 52
2.4.3. Addition Reactions ........................... 53
2.4.4. Substituted Groups Reactions ................. 54
2.5. Stilbenes in Polymerization .......................... 56
2.5.1. Radical Polymerization ....................... 56
2.5.2. Anionic Polymerization ....................... 57
2.6. Complexation ......................................... 58
2.6.1. Complexation with Small Molecules ............ 58
2.6.2. Complexation with Proteins ................... 60
2.6.2.1. Tubulins ........................... 60
2.6.2.2. Antibodies ......................... 60
References ................................................. 62
3. Stilbene Photophysics ...................................... 67
3.1. General .............................................. 67
3.2. Stilbene Excited States .............................. 67
3.2.1. Excited Singlet State ........................ 67
3.2.2. Excited Triplet State ........................ 69
3.3. Absorption Spectra ................................... 71
3.3.1. Singlet-Singlet Absorption Spectra ........... 71
3.3.2. Triplet-Triplet Absorption Spectra ........... 71
3.3.3. Two-Photon Absorption and Fluorescence ....... 72
3.4. Fluorescence from Excited Singlet States ............. 76
3.4.1. Fluorescence Behavior and Hammett
Relationships ................................ 76
3.4.1.1. Excitation to the Franck-Condon
State .............................. 76
3.4.1.2. Radiative Deactivation ............. 78
3.4.2. Miscellaneous Data on Stilbenes
Fluorescence ................................. 80
3.4.2.1. Stilbenes in Solution .............. 80
3.4.2.2. Stilbene Dendrimer Fluorescence .... 84
3.4.2.3. Stilbenes on Templates and
in Proteins ........................ 86
3.5. Interactions Involving Triplet State and
Phosphorescence ...................................... 90
3.6. Fluorescence of Excimers and Exciplexes .............. 92
3.7. Energy Transfer ...................................... 93
3.8. Intramolecular Charge Transfer ....................... 95
References ................................................. 95
4. Stilbene Photoisomerization ................................. 99
4.1. General .............................................. 99
4.2. Mechanisms of Photoisomerization .................... 101
4.2.1. Ideas, Concepts, and Theoretical
Calculations ................................ 101
4.2.1.1. Through Double-Bond Twisting
(Saltiel) Mechanism ............... 102
4.2.1.2. Single-Bond Twisting Mechanism .... 105
4.2.1.3. Planar Intramolecular Charge
Transfer Precursor Mechanism ...... 105
4.2.1.4. Double-Bond Twisting Mechanism
in Linear Quinoid Structure ....... 106
4.2.1.5. A Volume-Conserving Mechanism ..... 108
4.2.1.6. Media "Melting " Mechanism:
Photoisomerization in Rigid
Surroundings ...................... 110
4.2.1.7. Nonvertical Energy Transfer ....... 110
4.2.1.8. A Dual Thermal Bond Activation
Mechanism ......................... 112
4.2.2. Experimental and Theoretical Studies of
the Photoisomerization Mechanisms ........... 113
4.3. Effect of Substituents and Polarity ................. 117
4.4. Viscosity Effect .................................... 119
4.5. Miscellaneous Experimental Data on
Photoisomerization .................................. 121
4.5.1. Photoisomerization in Solutions ............. 121
4.5.1.1. Direct Photoisomerization ......... 121
4.5.1.2. Sensitized Photoisomerization ..... 124
4.5.1.3. Photoisomerization of
Stilbenophanes .................... 126
4.5.1.4. Stilbene Photoisomerization in
Dendrimers ........................ 126
4.5.1.5. Stilbene Photoswitching
Processes ......................... 128
4.5.1.6. Stilbene Photoisomerization on
Templates ......................... 129
References ................................................ 131
5. Miscellaneous Stilbene Photochemical Reactions ............ 137
5.1. Photocyclization .................................... 137
5.2. Bimolecular Reactions ............................... 140
5.2.1. Photodimerization ........................... 140
5.2.2. Reactions with Alkenes and Dienes ........... 143
5.2.3. Reactions with Amines, Imines, Nitroso
Oxide, and Protic Solvents .................. 143
5.3. Photoreactions in Stilbene Dendrimers ............... 146
5.4. Reactions in Polymers and Other Matrices ............ 147
5.5. Reaction Using Two-Photon Excitation ................ 148
5.6. Charge Transfer Ionization .......................... 150
References ................................................ 156
6. Stilbene Materials ........................................ 159
6.1. Stilbene Lasers ..................................... 159
6.1.1. Dye Lasers .................................. 159
6.1.2. Stilbene Solid Lasers ....................... 160
6.2. Electro-Optic Materials ............................. 161
6.3. Electrophotographic Material ........................ 165
6.4. Light-Emitting Diodes ............................... 167
6.5. Materials for Nonlinear Optics ...................... 169
6.6. Light-Emitting Materials ............................ 175
6.7. Materials for Image-Forming Apparatuses ............. 177
6.8. Radioluminescence Materials: Scintillators .......... 180
6.9. Miscellaneous ....................................... 183
References ................................................ 185
7. Bioactive Stilbenes ....................................... 189
7.1. Resveratrol ......................................... 189
7.1.1. General ..................................... 189
7.1.2. Resveratrol Content in Biological Objects ... 190
7.1.3. Metabolism and Pharmacokinetics ............. 192
7.1.4. Antioxidant Activity ........................ 195
7.1.5. Resveratrol and Apoptosis ................... 197
7.1.6. Biochemical Effect .......................... 202
7.1.6.1. Enzymes ........................... 202
7.1.6.2. Cells and Animals ................. 204
7.1.6.3. Effects on Metabolism of
Estrogens ......................... 207
7.1.6.4. Signaling Pathway ................. 207
7.1.7. Resveratrol in Genetics ..................... 208
7.1.8. Effect on Aging ............................. 209
7.1.9. Miscellaneous ............................... 210
7.2. Combretastatin and Its Analogues .................... 213
7.2.1. Effect on Tubulin Polymerization ............ 215
7.2.2. Miscellaneous ............................... 216
7.3. Pterostilbene ....................................... 218
References ................................................ 219
8. Preclinic Effects of Stilbenes ............................ 225
8.1. Resveratrol ......................................... 225
8.1.1. Cancer Protection in Animal ................. 225
8.1.2. Cell Cancer Protection ...................... 227
8.1.3. Miscellaneous Effects ....................... 230
8.2. Combretastatin ...................................... 233
8.2.1. Effects on Cancer Cells ..................... 233
8.2.2. Xenografts and Tumors ....................... 239
8.2.3. Animals ..................................... 244
8.3. Pterostilbene ....................................... 250
8.3.1. Cells ....................................... 250
8.3.2. Animals ..................................... 251
References .................................................... 256
9. Stilbenes in Clinics ...................................... 261
9.1. General ............................................. 261
9.2. trans-Resveratrol ................................... 262
9.3. Combretastatin ...................................... 267
9.3.1. Vascular Damaging Agents .................... 267
9.3.2. Pharmacometrics of Stilbenes: Seguing
Toward the Clinic ........................... 268
9.4. Other Stilbenoids ................................... 273
References ................................................ 274
10. Stilbenes as Molecular Probes ............................. 277
10.1. General ............................................. 277
10.2. Theoretical Grounds ................................. 278
10.2.1. Local Properties of Medium .................. 278
10.2.1.1. Polarity .......................... 278
10.2.1.2. Molecular Dynamics ................ 278
10.2.2. Excited Energy Transfer ..................... 279
10.2.2.1. Fluorescence Resonance Energy
Transfer .......................... 279
10.3. Experimental Methods and Their Applications ......... 280
10.3.1. Probing Based on Solvatochromism ............ 280
10.3.2. Image and Structure Probing ................. 283
10.3.3. Methods Based on Accessibility of
Reactive Groups ............................. 287
10.3.4. Stilbene Probes Binding to Proteins ......... 288
10.3.5. Depth of Immersion of a Stilbene Probe
in Biomembranes ............................. 289
10.3.6. Fluorescence-Photochrome Method ............. 290
10.3.6.1. General ........................... 290
10.3.6.2. Molecular Dynamics of Proteins
and Biomembranes .................. 290
10.3.6.3. Molecular Dynamics of anti-DNP
Antibody Binding Site ............. 292
10.3.7. Systems Immobilized on Quartz Slides ........ 293
10.3.7.1. Sensoring for Surface
Microviscosity and Ascorbic
Acid .............................. 293
10.3.7.2. A Fluorescent-Photochrome Method
for the Quantitative
Characterization of Solid-Phase
Antibody Orientation .............. 296
10.3.8. Triplet-Photochrome Method .................. 297
10.3.9. Cascade Spin-Triplet-Photochrome Methods .... 299
10.3.10.Fluorescence-Photochrome Immunoassay ........ 301
10.3.11.Suppermolecules Containing Stilbene and
Fluorescent Quenching Groups ................ 303
References ................................................ 305
11. Modern Methods of Stilbene Investigations ................. 309
11.1. General ............................................. 309
11.2. Nanosecond Transient Absorption Spectroscopy ........ 310
11.3. Femtosecond Broadband Pump-Probe Spectroscopy ....... 312
11.4. Fluorescence Picosecond Time-Resolved Single
Photon Counting ..................................... 314
11.5. The Fluorescence Upconversion Spectroscopy .......... 318
11.6. Femtosecond Time-Resolved Fluorescence Depletion
Spectroscopy ........................................ 321
11.7. High-Speed Asynchronous Optical Sampling ............ 323
11.8. Multiphoton Excitation .............................. 323
11.9. Time-Resolved Vibrational Spectroscopy .............. 328
References ................................................ 332
12. Conclusions ............................................... 335
Index ......................................................... 337
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