Preface ........................................................ xi
Abbreviations ................................................ xiii
Part I Introduction ........................................... 1
1 Philosophy of bioinorganic photochemistry .................... 3
Part II Fundamentals .......................................... 13
2 Light and matter ............................................ 15
2.1 Nature of light ........................................ 15
2.2 Accessible light sources ............................... 16
2.3 Interaction between light and matter ................... 17
3 Formation and properties of electronic excited states ....... 19
3.1 Wave mechanics and quantum numbers ..................... 20
3.2 Electronic excitation .................................. 21
4 Photophysical deactivation of electronic excited states ..... 25
4.1 Spontaneous deactivation ............................... 25
4.2 Quenching .............................................. 27
4.3 Coordination and organometallic compounds .............. 29
5 Kinetics of the excited-state decay ......................... 35
6 Photochemical reactions ..................................... 41
6.1 Photochemical reaction channels ........................ 42
6.2 Intramolecular photoreactions .......................... 43
6.2.1 Photodissociation and photoionization ........... 44
6.2.2 Photoisomerization .............................. 46
6.3 Intermolecular photoreactions .......................... 47
6.4 The coordination compound specificity .................. 49
6.4.1 Ligand field photochemistry ..................... 50
6.4.2 Photochemistry from LC or LLCT states ........... 51
6.4.3 Inner-sphere charge transfer photochemistry ..... 52
6.4.4 Outer-sphere charge transfer photochemistry ..... 55
6.5 Photosensitized reactions .............................. 58
6.6 Homogeneous photocatalysis ............................. 63
7 Photochemistry and photophysics of supramolecular
systems and nanoassemblies .................................. 77
7.1 From molecules through clusters to crystals ............ 77
7.2 Metallic nanoparticles: metals in the embryonic
state .................................................. 78
7.3 Formation and decay of the excited states of
semiconductors ......................................... 85
7.3.1 Optical excitation of semiconductors ............ 85
7.3.2 Electrons and hole trapping ..................... 87
7.3.3 Radiative vs non-radiative decay ................ 88
7.3.4 Surface-molecule interaction: general
description ..................................... 90
7.3.5 Heterogeneous photocatalysis .................... 93
Part III Natural photoprocesses involving inorganic
compounds ............................................ 107
8 From interstellar space to planetary atmospheres ........... 109
8.1 Homogeneous systems: from interstellar space to
planetary atmospheres and primitive soup models ....... 110
8.2 Heterogeneous photochemistry in ice phases ............ 121
9 Solar radiation and terrestrial environment ................ 127
9.1 Solar radiation ....................................... 127
9.2 Atmospheric photochemistry ............................ 129
9.3 Photochemistry in the hydrosphere and soil ............ 138
9.3.1 Nitrate photochemistry ......................... 139
9.3.2 Role of humic substances ....................... 140
9.3.3 Photocatalysis by FeIII/FeII complexes .......... 141
9.3.4 Photocatalysis by CuII/CuI complexes ............ 144
9.3.5 Photocatalysis by chromium compounds ........... 145
9.4 Photochemical self-cleaning in the environment ........ 148
10 Heterogeneous (photo)catalysis and biogenesis on Earth ..... 157
10.1 (Photo)catalysis on chalcogenide semiconductors ....... 157
10.2 Photocatalytic nitrogen fixation ...................... 159
10.3 Photocatalytic carbon dioxide reduction ............... 160
10.4 'Fossils' of prebiotic catalysts: metal clusters in
active centres of metalloenzymes ...................... 161
11 Foundation and evolution of photosynthesis ................. 169
11.1 Photosynthetic structures ........................ 172
11.2 Aerobic photosynthesis ........................... 174
11.2.1 Photosystem II (PSII) .......................... 176
11.2.2 Photosystem I (PSI) ............................ 177
11.3 Light harvesting antennae (LHC) ....................... 177
11.3.1 Chlorophyll .................................... 179
11.3.2 Bacteriochlorophyll ............................ 179
11.4 Electron transfer pathways in PSII and PSI ............ 179
11.5 Oxygen-evolving complex (OEC) ......................... 183
11.5.1 Inorganic species in OEC ...................... 185
Part IV Photochemistry and photophysics in bioinspired
systems: studies and modelling ....................... 189
12 Photoenzymes ............................................... 191
12.1 Natural photoenzymes .................................. 191
12.2 Modified natural proteins/enzymes ..................... 194
12.3 Artificial photoenzymes ............................... 197
12.4 Towards mimicking the photosynthetic processes ........ 200
12.4.1 Light harvesting antennae ...................... 200
12.4.2 Charge-separation systems ...................... 202
12.4.3 Biomimetic reaction centres .................... 203
13 Photoinduced electron transfer in proteins ................. 209
13.1 Photochemical methodology ............................. 210
13.1.1 Photoactive ruthenium complexes ................ 210
13.1.2 Metal-substituted haemoproteins ................ 215
13.1.3 Photoinduced ligand dissociation ............... 216
13.2 Biochemical applications .............................. 217
13.2.1 Mechanisms of electron transfer ................ 217
13.2.2 Cross-linking of proteins ...................... 218
13.2.3 Analyzing intermediates and testing new
inhibitors ..................................... 219
13.2.4 Folding of proteins ............................ 219
14 Nucleic acid photocleavage and charge transport ............ 227
14.1 Mechanisms and strategies for advanced
metallophotocleavers .................................. 227
14.1.1 Ruthenium complexes ............................ 228
14.1.2 Rhodium complexes .............................. 232
14.1.3 Other metal complexes .......................... 234
14.1.4 Di-and trinuclear complexes .................... 237
14.2 Photoinduced DNA-mediated charge transport ............ 238
Part V Towards applications ................................. 247
15 Light and biomatter ........................................ 249
16 Fluorescent and chromogenic sensing and labelling .......... 257
16.1 Cations as targets in biochemical sensing ............. 259
16.1.1 Cations common in biological systems ........... 262
16.1.2 Fluorescent detection of toxic cations ......... 268
16.2 Fluorescent and chromogenic sensing of anions ......... 270
16.2.1 Common anions .................................. 270
16.2.2 Toxic anions ................................... 274
16.3 Optical detection of neutral molecules ................ 278
16.4 Nanoparticles in biochemical sensing and labelling .... 283
17 Therapeutic strategies ..................................... 293
17.1 Photobiostimulation ................................... 295
17.2 Photoactivation of drugs .............................. 297
17.3 Photodynamic therapy .................................. 303
17.3.1 Mechanisms of PDT and PTT ...................... 304
17.3.2 Photosensitizers ............................... 305
17.3.3 Inorganic photosensitizers ..................... 307
17.3.4 Supporting role of metal ions in photodynamic
therapy ........................................ 312
17.3.5 Combination of polypyrrolic photosensitizers
and metallopharmaceuticals ..................... 313
17.3.6 Recent PDT development ......................... 313
17.4 Nanomedical methods ................................... 316
18 Photodynamic inactivation of microorganisms ................ 335
18.1 Bacteria .............................................. 337
18.2 Viruses ............................................... 338
18.3 Fungi ................................................. 340
18.4 Parasites ............................................. 340
18.5 Perspectives .......................................... 341
19 Photodelivery and phototargeting ........................... 345
20 Phototoxicity and photoprotection .......................... 353
20.1 Chemical and physical photoprotection ................. 353
20.2 Inorganic sunscreens .................................. 355
21 Photocatalysis in environmental protection ................. 359
21.1 Development of homo- and heterogeneous methods ........ 359
21.2 Homogeneous photocatalysis ............................ 360
21.3 Heterogeneous photocatalysis .......................... 363
21.3.1 Water and air detoxification ................... 363
21.3.2 Photocatalytic CO2 reduction ................... 365
21.3.3 Other applications of photocatalysis ........... 366
21.4 New ideas in pollution abatement ...................... 367
21.4.1 New emerging techniques ........................ 367
21.4.2 Renewable energy resources ..................... 368
Index ......................................................... 377
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