CRC Handbook of Organic Photochemistry and Photobiology, Third Edition - Two Volume Set

Contents......Page 5
Preface......Page 10
Editors......Page 12
Contributors......Page 13
1.1 Introduction......Page 20
Radiation Sources......Page 23
Reactor Design......Page 28
Upscaling/Downscaling......Page 30
1.3 Large-Scale Preparative Photochemistry and Means of Safety......Page 31
Electrical Incidents......Page 32
Temperature Control......Page 33
ATEX or NEC Certification......Page 34
References......Page 35
2.1 Vacuum-Ultraviolet and UV Excilamps in Photoscience......Page 39
Plasma Displays and Artificial Lighting......Page 44
Photomedicine......Page 45
Surface Modification......Page 46
Surface Cleaning......Page 48
Photo-CVD......Page 49
2.4 Analytical Photochemistry.......Page 50
Surface Disinfection......Page 51
Advanced Oxidation Processes......Page 52
Acknowledgments......Page 57
References......Page 58
3.2 From Conventional Batch to Micro Flow Photoreactors......Page 67
3.3 Photochemical Reactions in Microreactors......Page 69
Homogeneous Reactions......Page 70
Heterogeneous Reactions......Page 80
Catalytic Reactions......Page 82
Microphotochemistry in Industry......Page 85
References......Page 86
4.1 Introduction......Page 91
Norrish Type II......Page 92
Coumarin Derivatives......Page 93
7-Nitroindolines......Page 94
PPGs for Carboxylic Acids......Page 96
PPGs for Amines......Page 97
PPGs for Alcohols......Page 99
PPGs for Thiols......Page 102
4.4 Conclusion......Page 104
References......Page 105
5.1 Introduction......Page 112
[2 + 2] Photocycloadditions......Page 113
Photocycloadditions of Higher Order......Page 116
Photocycloadditions of Aromatic Compounds......Page 118
5.3 Photochemical Rearrangements......Page 119
5.4 Photochemical Electron Transfer–Mediated Transformations......Page 122
5.5 Photo-Oxygenation......Page 126
5.6 Photochemically Supported Organometallic Reactions......Page 129
5.7 Further Reactions......Page 132
5.8 Conclusions......Page 133
References......Page 134
6.1 Introduction......Page 142
6.2 Photochirogenesis with Circularly Polarized Light......Page 143
Photochirogenesis in Organic Solution......Page 145
Photochirogenesis in Chiral Ionic Liquid......Page 159
Photochirogenesis in Supercritical Fluid......Page 160
Photochirogenesis in Nanosized Cavity of Zeolite and Mesoporous Silica......Page 161
Cyclodextrin-Mediated Photochirogenesis......Page 166
Photochirogenesis with Biomolecule......Page 172
Photochirogenesis in Liquid Crystal......Page 173
Photochirogenesis in Polymer......Page 175
Photochirogenesis in Other Organized Media......Page 176
6.5 Photochirogenesis in Single Crystal......Page 178
6.6 Conclusions......Page 181
References......Page 182
7.2 Asymmetric Induction by Small Molecule Chiral Templates......Page 194
Stoichiometric Reagents......Page 195
Catalytic Reagents......Page 199
Cyclodextrins......Page 201
Self-Assembled Supramolecular Hosts......Page 203
Biological Templates......Page 204
7.4 Asymmetric Photosensitization......Page 205
Axial to Point Chirality Transfer......Page 206
Chiral Memory Effect......Page 208
7.6 Asymmetric Aminocatalysis.......Page 210
References......Page 212
8.1 Introduction......Page 217
Monocyclic Cyclopropanes......Page 218
Bicyclic Cyclopropanes: 1,2-Chirality Transfer......Page 219
Spiro[2.2]pentanes......Page 222
8.3 1-Indanones and Dihydrobenzo[c]furans......Page 223
References......Page 225
9.1 Introduction......Page 228
Solvent-Free Reactions......Page 231
Photoreactions in Polymeric Matrix......Page 232
Solid-State Photoreactions......Page 233
Photoreactions in Eco-Friendly Solvents......Page 235
Sunlight-Induced Syntheses......Page 242
9.3 Perspectives and Conclusions......Page 247
References......Page 248
10.2 Photochemistry and Green Chemistry......Page 251
10.3 Early Solar Studies......Page 252
Non-Concentrating Reactors......Page 253
Concentrating Reactors......Page 254
Reactions Using Moderately Concentrated Sunlight......Page 255
Synthesis in Low- to Non-Concentrating Reactors......Page 257
10.6 Concluding Remarks......Page 259
References......Page 260
Supercritical CO2......Page 262
Supercritical Methane, Ethane, and Other Hydrocarbons......Page 266
Polyethylene and Polypropylene Films......Page 267
Nafion Membranes......Page 271
11.4 Photochemistry in Ionic Liquids......Page 272
11.5 Photochemistry in Microemulsions, Micelles, Vesicles, and Dendrimer Voids......Page 277
11.6 Photochemistry in Liquid Crystals and Organogels......Page 280
11.7 Conclusions......Page 282
References......Page 283
12. Cryogenic Matrix Photochemistry......Page 289
12.1 Photochemical Generation or Photochemistry of Free Radicals......Page 290
Carbenes......Page 291
Nitrenes......Page 292
σ,σ-, σ,π-, and π,π-Diradicals......Page 294
12.3 Tri-, Tetra-, and Oligoradicals......Page 295
12.5 Photochemistry of Heterocycles......Page 297
12.7 Conclusion......Page 299
References......Page 300
13.1 Introduction......Page 304
Fundamentals......Page 306
Thermodynamic Aspects......Page 309
Quantum Yield, Surface Area, Temperature, and Light Intensity......Page 310
Photocorrosion......Page 313
Pristine Semiconductor Photocatalysts......Page 314
Grafted Semiconductor Photocatalysts......Page 315
Dealkylation, Cyclization, and Hydroalkylation......Page 317
Dehydrodimerization of Cyclic Enol or Allyl Ethers and Olefins......Page 319
Linear Addition of Cyclic Enol/Allyl Ethers and Olefins to 1,2-Diazenes......Page 324
Linear Addition of Cyclic Enol/Allyl Ethers and Olefins to Imines......Page 328
References......Page 334
14.1 Introduction......Page 340
14.2 Photochemically Initiated Radical Polymerizations......Page 341
Intramolecular Radical Reactions......Page 343
Intermolecular Radical Reactions......Page 344
14.4 Radical Reactions Induced by Photofragmentation......Page 349
14.5 Photosensitized Radical Reactions......Page 354
References......Page 355
15.1 Introduction......Page 357
15.2 Mechanism......Page 358
Reaction with Carbanions......Page 359
Reaction with Tin Nucleophiles......Page 360
Reaction with Sulfur Nucleophiles......Page 362
Ring Closure Reactions......Page 363
Vinyl Halides......Page 369
Aliphatic Substrates with EWG at the α-Carbon......Page 371
Cycloalkyl, Bridgehead, and Neopentyl and Related Halides......Page 374
References......Page 376
16.1 Introduction......Page 379
16.2 Effect of Halide Substituents on the Photophysical Parameters of Aromatics......Page 380
16.3 General Scheme of Photoreactivity......Page 382
Rearrangement......Page 383
Cycloaddition and Addition......Page 384
Mechanism......Page 385
Unimolecular Fragmentation in the Gas Phase......Page 386
Fragmentation in Solution and in Matrix......Page 387
Assisted Photoreduction......Page 389
16.6 Reactions via the Radical Anion......Page 390
Chain Processes......Page 391
16.8 ArSN1 Arylation Reactions......Page 392
Direct Irradiation......Page 396
Photocatalysis......Page 397
References......Page 398
17.1 Introduction......Page 402
Nitrobenzyl Phosphates......Page 404
Benzoin Phosphates......Page 407
Phenacyl Phosphates......Page 408
Coumarylmethyl Phosphates......Page 409
Aryl Phosphates......Page 411
17.3 Photochemistry of Sulfonate Esters......Page 415
Aliphatic Sulfonates......Page 416
Aryl Sulfonates......Page 419
References......Page 424
18. Stabilized Carbocations Generated by Photoheterolysis......Page 427
18.3 Fluorenyl, Dibenzosuberenyl, and Xanthyl Cations......Page 430
Fluoren-9-yl Cation......Page 431
Intermediates of Photopinacol Rearrangement......Page 432
Dibenzosuberenol......Page 433
Xanthenol......Page 434
Photoheterolysis of Acridanes......Page 435
Acridane Photoswitch for Switchable Rotaxanes......Page 438
Photoswitchable Hosts with Acridane Subunits......Page 441
7-Methoxy-Aryl Cycloheptatriene as Precursors of Aryl Tropylium Ions......Page 443
Rotaxanes with the Cycloheptatriene Switch......Page 445
18.8 Concluding Remarks......Page 448
Overview......Page 452
Hydrogen Donors......Page 454
Photomediators......Page 456
Unsaturated Systems......Page 458
19.2 Photochemical Addition Reactions of Cycloalkanes......Page 459
19.3 Photomediated Addition Reactions of Cyclic Ethers......Page 462
19.4 Photomediated Addition Reactions of 1,3-Dioxolanes and Related Systems......Page 468
19.5 Photomediated Addition Reactions of Aldehydes and Related Systems......Page 474
19.6 Photomediated Addition Reactions of Alcohols......Page 483
References......Page 491
20.1 Introduction......Page 496
20.2 Photocycloaddition of Alkenes to Benzene Derivatives......Page 497
20.3 Photocycloaddition of Alkenes to Naphthalene Derivatives and Related Arenes......Page 501
20.4 Photodimerization of Anthracene Derivatives and Related Compounds......Page 504
20.5 Photocycloaddition of Heteroaromatic Compounds with Unsaturated Compounds......Page 507
20.6 Photocycloaddition and Photoalkylation of Aromatic Rings with Cyclopropanes......Page 511
References......Page 512
21.2 Discovery and Mechanism......Page 517
21.3 Regioselectivity in the Di-π-Methane Rearrangement......Page 519
21.4 Reality of Diradical Intermediates in the Di-π-Methane Rearrangements......Page 520
21.5 Reaction Stereochemistry......Page 521
21.6 Multiplicity Dependence of Regioselectivity......Page 523
21.7 Detailed Reactivity of Intermediate Diradicals in the Barrelene to Semibullvalene Rearrangement......Page 524
21.8 Aryl-Vinyl Di-π-Methane Rearrangements......Page 525
21.9 Triplet Reactivity......Page 527
21.10 Reaction Rates......Page 528
References......Page 530
22.2 Historical Perspective......Page 532
22.3 Reactive Excited State......Page 533
22.4 Theoretical Aspects......Page 535
22.5 Mechanistic Details......Page 536
22.6 Selectivity, Scope, and Limitations......Page 538
22.7 Synthetic Potential......Page 543
Synthesis of Tricyclo[3.3.0.0.0]octane-3-One......Page 547
Synthesis Fluorenylcyclopropane Derivative......Page 548
Acknowledgments......Page 549
23.1 Cycloaromatization Reactions: Introduction......Page 554
Experimental Studies of Photochemical Bergman Cyclization......Page 556
Relation between Photo-Bergman Cyclization and Other Photochemical Reactions of Alkynes: Photo-Bergman Cyclization as Interrupted [2 + 2] Cycloaddition......Page 562
23.3 MO Analysis of Cycloaromatization Reactions......Page 564
MO Analysis of Photochemical Bergman Cyclization......Page 566
Factors Controlling Photo-Bergman Cyclizations......Page 568
Excited States Involving Coordinated Metal Ions......Page 576
Intramolecular Electron Transfer......Page 579
23.6 H-Abstraction Ability of Diradicals Produced in Thermal and Photochemical Bergman Cyclizations......Page 580
23.7 Photophysical Properties of Enediynes......Page 581
23.8 DNA Cleavage by Photochemically Activated Enediynes......Page 583
Acknowledgment......Page 589
References......Page 590
24.1 Introduction......Page 598
Early Examples......Page 599
More Recent Examples......Page 600
24.3 Complications in HT Photoisomerization Studies......Page 604
Glass Effects......Page 605
Regioselectivity......Page 606
24.4 HT versus OBF......Page 607
Acknowledgment......Page 608
References......Page 609
25.1 Fulgimides and Their Parent Fulgides: Structure–Property Relationships......Page 611
Thienyl-, Pyrryl-, and Oxazolylfulgides and –Fulgimides......Page 614
3-Indolylfulgides and 3-Fulgimides......Page 616
2-Indolylfulgides and 2-Fulgimides......Page 619
25.2 Synthetic Methods for the Preparation of Fulgides and Fulgimides......Page 620
25.4 Fulgides and Fulgimides for Optical Recording Media......Page 622
Photoswitchable Energy Transfer Systems......Page 623
Photoswitch- Linker- Conjugates for SAMs on Metal and Semiconductor Surfaces......Page 624
References......Page 625
26.1 Introduction......Page 631
26.2 Cyclization Reactions......Page 634
26.3 Trapping of Ground-State Oxygen......Page 638
26.4 Cycloaddition Reactions......Page 639
26.5 Other Addition Reactions......Page 643
26.6 Photodienols to Release Nucleophiles......Page 645
Reference......Page 649
27.2 The Reaction......Page 657
27.3 Reactions of Carbonyl Compounds with Enolethers and Enolthioethers......Page 660
Silyl Enol Ethers......Page 663
Enamines......Page 665
Furan......Page 666
Other Pentaatomic Heterocycles......Page 675
Pyrimidines......Page 676
27.6 Intramolecular Reactions......Page 677
References......Page 680
28.1 Introduction......Page 686
28.2 Photoreduction......Page 687
28.3 Excited Singlet State and Ground State Reactions......Page 688
28.4 Triplet State Reactions of BQs and NQs......Page 689
28.5 Photoreactions of AQs......Page 693
28.6 Properties of Semiquinone Radicals......Page 696
28.7 Effects of Water on the Quinone Photoprocesses......Page 697
28.8 Effects of Quenchers......Page 699
28.9 Triplet State Reactions Involving Singlet Oxygen or O2?– Radicals......Page 700
28.10 Effects of Side Groups......Page 702
28.11 Biological Aspects......Page 704
References......Page 705
29.2 PDC of Electron-Rich Arylacetic Acids......Page 718
Trifluoromethylphenylacetic and Mandelic Acids......Page 719
Nitrophenylacetic Acids......Page 720
Keto-Substituted Phenylacetic Acids......Page 721
References......Page 726
30.1 Introduction......Page 730
30.3 [4+2]-Cycloaddition......Page 731
Substrates......Page 732
Synthetic Applications......Page 742
Chemoselectivity and Diasteroselectivity......Page 752
Chemiluminescent Properties......Page 754
Synthetic Applications......Page 756
References......Page 759
31.2 Mechanistic Studies......Page 768
Theoretical and Computational Methods......Page 769
Kinetic Isotope Effects......Page 770
Recent Experimental Developments: The Use of Hypersensitive Probes......Page 771
Regioselectivity......Page 772
Diastereoselectivity......Page 777
Stereoselectivity......Page 781
References......Page 782
32. Photooxygenations of Sulfur Compounds......Page 791
Sulfides......Page 792
Mechanism of Sulfoxide Formation......Page 793
Mechanism of Sulfone Formation......Page 799
Mechanism of Cleavage Product Formation......Page 800
Disulfides, Sulfenate Esters, and Sulfenamides......Page 801
Sulfide Photooxygenations in Heterogeneous Media......Page 803
32.3 Type I Sulfur Photooxygenations......Page 806
Acknowledgment......Page 807
References......Page 808
33. Porphycenes: Spectroscopy, Photophysics, and Tautomerism......Page 811
Condensed Phase Studies......Page 818
Coherent Double Hydrogen Tunneling in Isolated Porphycenes......Page 822
Tautomerization in Single Molecules of Porphycenes......Page 824
References......Page 827
34.1 Introduction......Page 832
General Concepts and Theoretical Background......Page 833
Photophysics of Metallated Tetrapyrroles......Page 834
Chlorophylls and Related Pigments......Page 837
Light-Harvesting Complexes and Reaction Center Models......Page 838
Introduction......Page 839
Donor–Acceptor Electron Transfer Compounds......Page 840
Heteroligand Systems......Page 846
Porphyrins......Page 849
Photoinduced Ring-Opening Reactions......Page 851
Reactions of Chlorophyll......Page 852
Nanomaterials: Molecular Electronic Devices......Page 854
Hydrogen Production......Page 856
Dye Industry......Page 857
Tetrapyrrole-Based Photocatalysts......Page 858
Titanium Dioxide?Based Tetrapyrrole Photocatalysts......Page 859
Photodynamic Therapy and Singlet Oxygen Production......Page 861
Acknowledgments......Page 865
References......Page 866
35.1 Introduction......Page 881
35.2 Particle Growth......Page 882
35.3 Photochemical Preparation of Nanoparticles......Page 883
35.4 Part I: PI1—Photoinduced Nanoparticle Synthesis via Unimolecular Cleavage......Page 884
Nanoparticle Synthesis Mediated by Photorelease of Ketyl Radicals......Page 885
35.5 Part II: Photosensitized Generation of Metal Nanoparticles via Ketone Photoreduction......Page 893
Acetone......Page 894
Benzophenone......Page 895
Xanthones......Page 896
Polymers......Page 897
Nanoparticle Generation from Inorganic Free Radicals......Page 900
Direct Photoreduction by Excited-State Species......Page 901
Fluorescent Nanoparticles......Page 902
Photochemical Control over Particle Morphology......Page 903
35.7 Conclusions......Page 905
References......Page 906
36.1 Introduction......Page 911
36.2 Fundamentals of Water Splitting on Semiconductor Photocatalysts......Page 912
UV Active Semiconductors......Page 914
Visible Light–Driven Photocatalysts......Page 920
Key Factors in Determining Photocatalyst Activity......Page 925
Transient Spectroscopy of Charge Carriers......Page 926
36.5 Conclusions......Page 928
References......Page 929
37.1 Introduction......Page 934
Activated Carbon......Page 935
37.2 Integrated Photocatalytic Adsorbents......Page 936
Photocatalyst Choice......Page 937
Doping/TiO2 Modification......Page 948
Wet......Page 949
Dry......Page 951
37.4 Substrate for Photodegradation......Page 952
37.5 Mathematical Models......Page 953
37.6 Regeneration......Page 955
37.7 IPCAs and Photocatalytic Reactor Design......Page 956
References......Page 957
38.1 Introduction: From Switches to Basic Logic Operations......Page 962
38.2 Molecular Mimics for Basic Logic Gates: A Brief Overview......Page 965
Inhibit INH–Implication IMP......Page 967
Exclusive OR XOR–Exclusive NOR XNOR......Page 968
38.3 Advanced Molecular Logic Circuits......Page 969
Half-Adders......Page 970
Half-Subtractors......Page 972
Multiplexers/Demultiplexers and Encoders/Decoders......Page 973
38.4 Molecular Logic with Memory Effect: Sequential Logic Devices......Page 975
38.5 Molecular Logic for Bioinspired Applications......Page 976
38.6 Conclusions......Page 977
References......Page 978
39.1 Introduction......Page 980
Micelles......Page 981
Cyclodextrins......Page 982
Photophysics as an Analytical Method......Page 983
Photophysics as a Perturbation Method......Page 987
Photophysics with Immobile Excited States......Page 988
Photophysics with Mobile Excited States......Page 992
References......Page 998
40.1 Introduction......Page 1001
Introduction......Page 1002
Photodegradation of Metoclopramide......Page 1003
Photodegradation of Primaquine......Page 1004
Photodegradation of Flurbiprofen......Page 1005
Photodegradation of Memoquin......Page 1006
Photodegradation of Montelukast......Page 1007
Introduction......Page 1008
Cyclodextrins......Page 1009
Titanium Dioxide......Page 1011
Photostability of Formulations......Page 1013
Photostability of Sunscreens......Page 1017
Introduction......Page 1020
Prochlorperazine......Page 1021
References......Page 1022
41. Computational Photochemistry and Photobiology......Page 1027
41.1 Introduction......Page 1028
41.2 Computational.Photochemistry......Page 1030
Photochemical Reaction Paths and the Branching Plane......Page 1032
Minimum Energy Conical Intersections and the Intersection Space......Page 1034
Complexity of Conical Intersections......Page 1035
Photochemical Trajectories......Page 1037
Photochemistry in Solution and in Proteins......Page 1041
41.3 Computational Photobiology......Page 1045
41.4 Conclusions and Perspectives......Page 1048
References......Page 1050
42.1 Introduction......Page 1055
Time-Resolved Techniques......Page 1056
42.3 Protocols for the Study of DNA Helices......Page 1057
DNA Helices......Page 1058
Steady-State Measurements......Page 1062
Time-Resolved Measurements......Page 1063
42.6 Fluorescence of DNA Helices......Page 1068
Energy Transfer......Page 1069
Fluorescence Decays......Page 1071
References......Page 1073
43.1 Introduction......Page 1078
43.3 Photophysics......Page 1079
43.6 Reciprocity......Page 1080
43.7 Fundamental Derivations......Page 1081
43.9 Derivation of Action Spectrum from Fluence–Response Curves......Page 1082
43.10 Additional Fitting Functions......Page 1085
43.11 Null and Threshold Action Spectra......Page 1086
References......Page 1087
Vacuum UV 10—190 nm......Page 1089
44.3 Absorption of UV by Cells......Page 1090
Differences in Effect with Wavelength......Page 1092
44.7 Polychromatic Action Spectra......Page 1095
44.8 Effectiveness Spectra......Page 1096
References......Page 1097
45.1 Introduction......Page 1100
45.2 Photodynamic Sensitization of Biological Systems: Photophysical Aspects......Page 1101
45.3 Kinetics of Photosensitized Reactions......Page 1103
45.4 Initial Photooxidation Products of Photodynamic Processes......Page 1105
45.5 Photosensitization in Complex Biological Systems......Page 1106
45.6 Conclusions......Page 1108
References......Page 1109
46.1 Introduction......Page 1111
Photomorphogenesis: Light Control of Growth and Morphology......Page 1112
Light-Mediated Movement Responses in Higher Plants......Page 1113
Effects of and Protection against Solar UV Radiation in Higher Plants......Page 1114
Photoinhibition......Page 1115
Orientation by Light......Page 1116
Defense Systems against Excessive Solar Radiation in Microorganisms......Page 1117
46.4 Ecological Consequences of the Photoenvironment......Page 1119
46.5 Excessive Light Stress......Page 1120
References......Page 1121
Discovery and Biological Context of the Photoactive Yellow Protein......Page 1130
Xanthopsins: The Family of PYPs......Page 1131
47.2 Structure......Page 1133
Xanthopsins Compared......Page 1134
Chromophore and Its Binding Pocket......Page 1135
Basic Photocycle......Page 1137
Photocycle Interpretation......Page 1138
47.4 Photocycle of Photoactive Yellow Protein......Page 1140
Initial Events......Page 1141
Signaling State Formation......Page 1142
Ground-State Recovery......Page 1145
47.5 Future Perspective......Page 1146
References......Page 1147
Historical Perspective......Page 1153
Chromophore......Page 1155
Chromophore Primary Reactions and the Surrounding Environment......Page 1158
48.3 Dark Steps of the Transduction Chain......Page 1160
48.4 Concluding Remarks......Page 1161
References......Page 1162
49.1 Introduction......Page 1165
BR and BR-Like Proton-Pumping Rhodopsins......Page 1166
Halorhodopsin......Page 1169
49.3 Photosensory Rhodopsins......Page 1170
Sensory Rhodopsin I and Sensory Rhodopsin II......Page 1171
Signal Transfer Mechanism of the SRII?HtrII Complex......Page 1172
Signal Transfer Mechanism of the SRI?HtrI Complex......Page 1174
49.4 New Types of Microbial Rhodopsins......Page 1177
Rhodopsins with Auxiliary Carotenoid Antenna......Page 1178
Anabaena Sensory Rhodopsin......Page 1179
References......Page 1180
50.1 Introduction......Page 1186
50.2 Biological Time and the Origin of Circadian Rhythmicity......Page 1187
50.3 Localization of Photoreceptorial Systems within Receptorial Clocks......Page 1188
50.4 Mammalian Receptor Clocks......Page 1191
50.5 Timing by Opsins......Page 1192
50.7 Melanopsin: A Key Photopigment in Circadian Vision......Page 1193
50.9 Conclusions......Page 1195
References......Page 1196
51.1 Introduction......Page 1202
51.2 Dietary Sources of Vitamin A......Page 1203
51.3 Structure and Function of Visual Pigments......Page 1204
Classic Visual Cycle......Page 1205
Cone-Specific Visual Cycle......Page 1206
Cones Expressing High Levels of S-Opsin Are More Susceptible to Degeneration......Page 1208
References......Page 1210
52.1 Introduction......Page 1215
52.2 Domain Structure of Phytochrome......Page 1216
52.3 Conformational Changes during Photoactivation......Page 1217
Transcriptional Control of Light-Responsive Genes through Phytochromes......Page 1218
Phosphorylation and Dephosphorylation in Phytochrome Signaling......Page 1219
52.5 Descriptive Model for Phytochrome Function in Plant Light Signaling......Page 1220
References......Page 1222
53.1 Introduction......Page 1227
Chromophores: RB, FMN, FAD......Page 1228
Photosensing Units: Cry, LOV, and BLUF Domains......Page 1229
53.3 From BL to Signaling......Page 1232
Conveying Signals: Intraprotein Pathways of Signal Transduction......Page 1233
Dimers or More: When and Why?......Page 1236
Delivering Signals: Partners of BL Receptors during Signal Transduction......Page 1238
Cry: From Photomorphogenesis to Single-Strand DNA Repair......Page 1241
LOV Proteins: From Phototropism to Infectivity Regulation......Page 1242
BLUF Proteins: From Phototaxis to Biofilms......Page 1243
Cry as “Photomagnetoreceptors?......Page 1244
BL Sensors as Tools for Cellular Studies: From Reporters to Engineered Regulators......Page 1245
From the Lab to Real World: The Wonder of Metagenomics in the BL World......Page 1246
References......Page 1247
54.1 Introduction......Page 1255
54.3 Mechanisms of Bioluminescence......Page 1256
Bioluminescence Colors......Page 1259
Biodiversity......Page 1260
Biological Functions......Page 1262
Photoecology......Page 1264
Bacteria......Page 1265
Dinoflagellates......Page 1267
Coelenterate Photoprotein System Hydrozoa......Page 1268
Beetles......Page 1269
Other Bioluminescent Systems......Page 1270
54.6 Origin and Evolution of Bioluminescent Systems......Page 1271
54.7 Bioluminescence Applications and Perspectives: Bioindication from the Molecular to the Global Level......Page 1272
References......Page 1273
55.1 Introduction......Page 1278
Natural System......Page 1281
Artificial Model......Page 1283
Biological Paragon......Page 1286
Biomimetic Systems......Page 1289
Oxygen Evolution......Page 1292
Carbon Fixation......Page 1296
Hydrogen Production......Page 1299
55.5 Protonmotive Force in Artificial Systems......Page 1302
55.6 Efficiency of Solar Energy Conversion......Page 1304
55.7 Conclusions......Page 1305
References......Page 1306
56.1 Introduction......Page 1314
Structure and Chromophore Formation......Page 1315
Optical Features of Chemical Model of wtGFP Chromophore......Page 1317
Optical States and Mechanism of Fluorescence Emission in wtGFP......Page 1319
Chromophore Structure and Formation......Page 1320
Optical Properties of FPs: Mechanism of Spectral Tuning......Page 1322
56.4 pH Dependence of Optical Response in avGFP Mutants......Page 1327
56.5 Conclusions......Page 1332
References......Page 1333
57.2 UVC and UVB Photochemistry of DNA......Page 1338
Excited States of DNA Bases......Page 1339
Structure and Properties of the Photoproducts......Page 1341
Formation of the Photoproducts within DNA......Page 1344
Photooxidation......Page 1347
Formation of CPDs......Page 1351
Nucleotide Excision Repair......Page 1353
Other Excision Enzymes for Dimeric Photoproducts......Page 1356
Base Excision Repair......Page 1357
Radical Repair......Page 1360
References......Page 1363
58.1 Introduction......Page 1382
58.3 UVA as an Oxidative Stress......Page 1383
DNA Damage......Page 1385
Mutagenesis and Cancer......Page 1387
Membrane Damage Effects on Fluidity and Lipid Oxidation Products......Page 1392
Photooxidation of Proteins and Enzyme Damage......Page 1393
Cell Death: Necrosis and Apoptosis......Page 1396
UVA-Generated Signaling Intermediates......Page 1397
Protein Kinases and Phosphatases......Page 1398
Transcription Factors......Page 1401
Gene Induction and Significance......Page 1402
58.6 Disease and UVA Sensitivity......Page 1406
References......Page 1407
59.1 Introduction......Page 1424
Biosynthetic Pathway......Page 1425
Latitude and Season......Page 1426
Impact of Photoprotective Measures......Page 1427
Recommended Intake......Page 1428
Other Aspects of Musculoskeletal Health......Page 1429
Vitamin D Status......Page 1430
Vitamin D Status in the General Population......Page 1431
How Much Sunlight Is Needed?......Page 1432
References......Page 1433
60.1 Introduction......Page 1438
Carotenoids......Page 1439
Vitamin E Tocopherols and Vitamin C Ascorbate......Page 1444
Polyphenols......Page 1445
60.3 Conclusions......Page 1448
References......Page 1449
61.1 Introduction......Page 1452
61.2 UV Radiation......Page 1453
61.5 Inflammation and Erythema......Page 1454
61.8 Immunosuppression......Page 1455
Skin Carcinogenesis......Page 1456
61.14 Acute Ocular Effects......Page 1457
61.16 Photoprotection......Page 1458
References......Page 1459
62.1 Introduction......Page 1463
Action Mechanisms......Page 1464
Treatment Principles......Page 1465
Clinical Indications......Page 1466
Principles of Treatment......Page 1468
Adverse Events......Page 1469
Principles of Treatment......Page 1470
Clinical Indications......Page 1471
References......Page 1473
63.1 Introduction......Page 1477
63.2 Measurement of Immune Function......Page 1478
trans-Urocanic Acid......Page 1479
Cellular......Page 1481
Molecular......Page 1483
UVA versus UVB......Page 1484
Role of Heme Oxygenase-1......Page 1485
Bioactive Phytochemicals......Page 1486
Estrogen Receptor Er Signaling......Page 1487
Neonatal UV Exposure......Page 1488
63.8 Conclusions......Page 1489
References......Page 1490
64.1 Introduction and Background......Page 1499
64.2 Photochemistry of PDT......Page 1500
64.3 Requirements for PDT to Become Clinically Successful......Page 1501
ALA–PDT......Page 1502
Chlorins and Bacteriochlorins......Page 1503
64.5 Targeted PDT......Page 1504
Direct Cytotoxicity......Page 1505
Indirect Immune System Effects......Page 1506
Light Sources......Page 1507
Challenges in Clinical Development of PDT......Page 1508
Barrett’s Esophagus and Early, Localized Cancer......Page 1509
Advanced Cancers......Page 1510
64.10 Clinical PDT: Antimicrobial Therapy......Page 1511
References......Page 1513
65.1 Introduction......Page 1517
Photosensitizers and Their Subcellular Localization......Page 1518
Light-Induced Macromolecule Delivery......Page 1519
Peptides and Proteins......Page 1520
Targeted Macromolecules: Immunotoxins......Page 1521
Oligonucleotides......Page 1522
65.4 In Vivo PCI Studies......Page 1523
References......Page 1525
66.1 Introduction......Page 1529
66.2 Clinical and Experimental Data on Humans......Page 1530
66.3 In Vitro Phototoxicity Testing......Page 1534
Ketoprofen......Page 1535
Norfloxacin......Page 1537
References......Page 1539
67.1 Introduction......Page 1544
Photodynamic Processes: Basic Mechanisms......Page 1545
Photodynamic Inactivation of Microbial Cells......Page 1547
General Features of the Approach......Page 1549
Photodynamic Treatment of Water from Fish-Farming Plants......Page 1551
Future Perspectives......Page 1553
References......Page 1554
A......Page 1558
B......Page 1560
C......Page 1561
D......Page 1564
E......Page 1565
F......Page 1567
H......Page 1568
I......Page 1569
K......Page 1570
M......Page 1571
N......Page 1572
O......Page 1573
P......Page 1574
R......Page 1581
S......Page 1582
T......Page 1584
U......Page 1585
W......Page 1586
Y......Page 1587
Color Inserts......Page 1588