Photodynamic therapy (PDT).
See alsoPorphyrin-based
photosensitizers
cytotoxicity limits, 222– 224
photofrin, 221– 222
phototherapeutic index, 224
tumor regressions, 226– 228
Photo-Fenton reaction.SeeFenton
reaction
Photophysics, rhenium(I) diimine
complexes
electronic structure,
139 – 141electronic states, 141
energy diagram, electronic
states, 141f
photostability, 141
structure, 140f
photophysical relaxation process,
141 – 143broad band, 142
chemical modification, 141
energy gap law, 142– 143
phosphorous ligand, 142
UV/Vis absorption and emission
spectra, 142f
weak interactions, effects
bathochromic and hypsochromic
shifts, 146
phosphine ligands, 144– 145
photochemical ligand
substitution reaction, 144
UV/Vis absorption and emission
spectra, 144f
Photoresponsive biomolecules,
240 – 243
Photo-to-chemical energy-conversion
efficiency, 405f
p-hydroxy-benzylidene-imidazolinone
chromophore (HBDI), 240f
Porphyrin-based photosensitizers
absorption and emission
b-substituents, 198
irregular metalloporphyrins,
200 – 201
paramagnetic complexes, 201
Q band, 200
vibrational coupling effects, 198
design guidelines, 228t
meso-tetraphenylporphyrin
(TPP), 189
molecular and electronic structure
axial ligands, 196– 197
bacteriochlorins, 190
bacteriochlorophylla, 197– 198
bathochromic shift, 192– 193
energy levels, 192f
fundamental porphyrin
systems, 191f
HOMOs and LUMOs, 190– 192
metalloporphyrins, 196
oxidation potentials, 193
palladium and indium, 197
Q band, 197
redox potentialsvs.SCE and
optical characteristics, 194t
reduced porphyrins, 190
singlet state lifetimes, 198
photochemistry, 189
photodynamic therapy (PDT)
cytotoxicity limits, 222– 224
photofrin, 221 – 222
phototherapeutic index, 224
tumor regressions, 226– 228
photoinduced reactions, molecular
oxygen
bacteriochlorins, 219
chemical methods, 216– 217
energy balance, 217
molecular structures, 215f
photodecomposition quantum
yield, 220
quintet path, 213
transient absorption, 216
type I mechanism, 214
photosensitizers, 189
radiationless transitions
Born–Oppenheimer
approximation, 204– 205
Franck–Condon factor, 204– 205
Golden Rule, 204
heavy-atom effect, 207
lifetime, 203
total Hamiltonian, 203
structure and absorption
maxima, 188f
triplet state
cisNH intermediate, 209
photoacoustic calorimetry (PAC)
data, 208– 209436 INDEX