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[资源] Molecular Fluorescence-Principles and Applications(分子荧光，英文好书籍）

Molecular Fluorescence（书籍）

http://www.namipan.com/d/Molecul ... 99f3b5f02e755d25800

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[ Last edited by zhaoyongqiang on 2008-3-14 at 11:46 ]

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Contents
Preface xii
Prologue 1
1 Introduction 3
1.1 What is luminescence? 3
1.2 A brief history of fluorescence and phosphorescence 5
1.3 Fluorescence and other de-excitation processes of excited molecules 8
1.4 Fluorescent probes 11
1.5 Molecular fluorescence as an analytical tool 15
1.6 Ultimate spatial and temporal resolution: femtoseconds, femtoliters,
femtomoles and single-molecule detection 16
1.7 Bibliography 18
2 Absorption of UV–visible light 20
2.1 Types of electronic transitions in polyatomic molecules 20
2.2 Probability of transitions. The Beer–Lambert Law. Oscillator
strength 23
2.3 Selection rules 30
2.4 The Franck–Condon principle 30
2.5 Bibliography 33
3 Characteristics of fluorescence emission 34
3.1 Radiative and non-radiative transitions between electronic states 34
3.1.1 Internal conversion 37
3.1.2 Fluorescence 37
3.1.3 Intersystem crossing and subsequent processes 38
3.1.3.1 Intersystem crossing 41
3.1.3.2 Phosphorescence versus non-radiative de-excitation 41
3.1.3.3 Delayed fluorescence 41
3.1.3.4 Triplet–triplet transitions 42
3.2 Lifetimes and quantum yields 42
3.2.1 Excited-state lifetimes 42
Molecular Fluorescence: Principles and Applications. Bernard Valeur
> 2001 Wiley-VCH Verlag GmbH
ISBNs: 3-527-29919-X (Hardcover); 3-527-60024-8 (Electronic)
v
3.2.2 Quantum yields 46
3.2.3 Effect of temperature 48
3.3 Emission and excitation spectra 48
3.3.1 Steady-state fluorescence intensity 48
3.3.2 Emission spectra 50
3.3.3 Excitation spectra 52
3.3.4 Stokes shift 54
3.4 Effects of molecular structure on fluorescence 54
3.4.1 Extent of p-electron system. Nature of the lowest-lying transition 54
3.4.2 Substituted aromatic hydrocarbons 56
3.4.2.1 Internal heavy atom effect 56
3.4.2.2 Electron-donating substituents: aOH, aOR, aNHR, aNH2 56
3.4.2.3 Electron-withdrawing substituents: carbonyl and nitro compounds 57
3.4.2.4 Sulfonates 58
3.4.3 Heterocyclic compounds 59
3.4.4 Compounds undergoing photoinduced intramolecular charge transfer
(ICT) and internal rotation 62
3.5 Environmental factors affecting fluorescence 67
3.5.1 Homogeneous and inhomogeneous broadening. Red-edge effects 67
3.5.2 Solid matrices at low temperature 68
3.5.3 Fluorescence in supersonic jets 70
3.6 Bibliography 70
4 Effects of intermolecular photophysical processes on fluorescence
emission 72
4.1 Introduction 72
4.2 Overview of the intermolecular de-excitation processes of excited
molecules leading to fluorescence quenching 74
4.2.1 Phenomenological approach 74
4.2.2 Dynamic quenching 77
4.2.2.1 Stern–Volmer kinetics 77
4.2.2.2 Transient effects 79
4.2.3 Static quenching 84
4.2.3.1 Sphere of effective quenching 84
4.2.3.2 Formation of a ground-state non-fluorescent complex 85
4.2.4 Simultaneous dynamic and static quenching 86
4.2.5 Quenching of heterogeneously emitting systems 89
4.3 Photoinduced electron transfer 90
4.4 Formation of excimers and exciplexes 94
4.4.1 Excimers 94
4.4.2 Exciplexes 99
4.5 Photoinduced proton transfer 99
4.5.1 General equations 100
4.5.2 Determination of the excited-state pK 103
vi Contents
4.5.2.1 Prediction by means of the Fo¨rster cycle 103
4.5.2.2 Steady-state measurements 105
4.5.2.3 Time-resolved experiments 106
4.5.3 pH dependence of absorption and emission spectra 106
4.6 Excitation energy transfer 110
4.6.1 Distinction between radiative and non-radiative transfer 110
4.6.2 Radiative energy transfer 110
4.6.3 Non-radiative energy transfer 113
4.7 Bibliography 123
5 Fluorescence polarization. Emission anisotropy 125
5.1 Characterization of the polarization state of fluorescence (polarization
ratio, emission anisotropy) 127
5.1.1 Excitation by polarized light 129
5.1.1.1 Vertically polarized excitation 129
5.1.1.2 Horizontally polarized excitation 130
5.1.2 Excitation by natural light 130
5.2 Instantaneous and steady-state anisotropy 131
5.2.1 Instantaneous anisotropy 131
5.2.2 Steady-state anisotropy 132
5.3 Additivity law of anisotropy 132
5.4 Relation between emission anisotropy and angular distribution of the
emission transition moments 134
5.5 Case of motionless molecules with random orientation 135
5.5.1 Parallel absorption and emission transition moments 135
5.5.2 Non-parallel absorption and emission transition moments 138
5.6 Effect of rotational Brownian motion 140
5.6.1 Free rotations 143
5.6.2 Hindered rotations 150
5.7 Applications 151
5.8 Bibliography 154
6 Principles of steady-state and time-resolved fluorometric techniques 155
6.1 Steady-state spectrofluorometry 155
6.1.1 Operating principles of a spectrofluorometer 156
6.1.2 Correction of excitation spectra 158
6.1.3 Correction of emission spectra 159
6.1.4 Measurement of fluorescence quantum yields 159
6.1.5 Problems in steady-state fluorescence measurements: inner filter effects
and polarization effects 161
6.1.6 Measurement of steady-state emission anisotropy. Polarization
spectra 165
6.2 Time-resolved fluorometry 167
6.2.1 General principles of pulse and phase-modulation fluorometries 167
Contents vii
6.2.2 Design of pulse fluorometers 173
6.2.2.1 Single-photon timing technique 173
6.2.2.2 Stroboscopic technique 176
6.2.2.3 Other techniques 176
6.2.3 Design of phase-modulation fluorometers 177
6.2.3.1 Phase fluorometers using a continuous light source and an electro-optic
modulator 178
6.2.3.2 Phase fluorometers using the harmonic content of a pulsed laser 180
6.2.4 Problems with data collection by pulse and phase-modulation
fluorometers 180
6.2.4.1 Dependence of the instrument response on wavelength. Color
effect 180
6.2.4.2 Polarization effects 181
6.2.4.3 Effect of light scattering 181
6.2.5 Data analysis 181
6.2.5.1 Pulse fluorometry 181
6.2.5.2 Phase-modulation fluorometry 182
6.2.5.3 Judging the quality of the fit 183
6.2.5.4 Global analysis 184
6.2.5.5 Complex fluorescence decays. Lifetime distributions 185
6.2.6 Lifetime standards 186
6.2.7 Time-dependent anisotropy measurements 189
6.2.7.1 Pulse fluorometry 189
6.2.7.2 Phase-modulation fluorometry 192
6.2.8 Time-resolved fluorescence spectra 192
6.2.9 Lifetime-based decomposition of spectra 194
6.2.10 Comparison between pulse and phase fluorometries 195
6.3 Appendix: Elimination of polarization effects in the measurement of
fluorescence intensity and lifetime 196
6.4 Bibliography 198
7 Effect of polarity on fluorescence emission. Polarity probes 200
7.1 What is polarity? 200
7.2 Empirical scales of solvent polarity based on solvatochromic shifts 202
7.2.1 Single-parameter approach 202
7.2.2 Multi-parameter approach 204
7.3 Photoinduced charge transfer (PCT) and solvent relaxation 206
7.4 Theory of solvatochromic shifts 208
7.5 Examples of PCT fluorescent probes for polarity 213
7.6 Effects of specific interactions 217
7.6.1 Effects of hydrogen bonding on absorption and fluorescence
spectra 218
7.6.2 Examples of the effects of specific interactions 218
7.6.3 Polarity-induced inversion of n–p and p–p states 221
7.7 Polarity-induced changes in vibronic bands. The Py scale of polarity 222
viii Contents
7.8 Conclusion 224
7.9 Bibliography 224
8 Microviscosity, fluidity, molecular mobility. Estimation by means of fluorescent
probes 226
8.1 What is viscosity? Significance at a microscopic level 226
8.2 Use of molecular rotors 230
8.3 Methods based on intermolecular quenching or intermolecular excimer
formation 232
8.4 Methods based on intramolecular excimer formation 235
8.5 Fluorescence polarization method 237
8.5.1 Choice of probes 237
8.5.2 Homogeneous isotropic media 240
8.5.3 Ordered systems 242
8.5.4 Practical aspects 242
8.6 Concluding remarks 245
8.7 Bibliography 245
9 Resonance energy transfer and its applications 247
9.1 Introduction 247
9.2 Determination of distances at a supramolecular level using RET 249
9.2.1 Single distance between donor and acceptor 249
9.2.2 Distributions of distances in donor–acceptor pairs 254
9.3 RET in ensembles of donors and acceptors 256
9.3.1 RET in three dimensions. Effect of viscosity 256
9.3.2 Effects of dimensionality on RET 260
9.3.3 Effects of restricted geometries on RET 261
9.4 RET between like molecules. Excitation energy migration in assemblies
of chromophores 264
9.4.1 RET within apa ir of like chromophores 264
9.4.2 RET in assemblies of like chromophores 265
9.4.3 Lack of energy transfer upon excitation at the red-edge of the absorption
spectrum (Weber’s red-edge effect) 265
9.5 Overview of qualitative and quantitative applications of RET 268
9.6 Bibliography 271
10 Fluorescent molecular sensors of ions and molecules 273
10.1 Fundamental aspects 273
10.2 pH sensing by means of fluorescent indicators 276
10.2.1 Principles 276
10.2.2 The main fluorescent pH indicators 283
10.2.2.1 Coumarins 283
10.2.2.2 Pyranine 283
10.2.2.3 Fluorescein and its derivatives 283
10.2.2.4 SNARF and SNAFL 284
Contents ix
10.2.2.5 PET (photoinduced electron transfer) pH indicators 286
10.3 Fluorescent molecular sensors of cations 287
10.3.1 General aspects 287
10.3.2 PET (photoinduced electron transfer) cation sensors 292
10.3.2.1 Principles 292
10.3.2.2 Crown-containing PET sensors 293
10.3.2.3 Cryptand-based PET sensors 294
10.3.2.4 Podand-based and chelating PET sensors 294
10.3.2.5 Calixarene-based PET sensors 295
10.3.2.6 PET sensors involving excimer formation 296
10.3.2.7 Examples of PET sensors involving energy transfer 298
10.3.3 Fluorescent PCT (photoinduced charge transfer) cation sensors 298
10.3.3.1 Principles 298
10.3.3.2 PCT sensors in which the bound cation interacts with an electrondonating
group 299
10.3.3.3 PCT sensors in which the bound cation interacts with an electronwithdrawing
group 305
10.3.4 Excimer-based cation sensors 308
10.3.5 Miscellaneous 310
10.3.5.1 Oxyquinoline-based cation sensors 310
10.3.5.2 Further calixarene-based fluorescent sensors 313
10.3.6 Concluding remarks 314
10.4 Fluorescent molecular sensors of anions 315
10.4.1 Anion sensors based on collisional quenching 315
10.4.2 Anion sensors containing an anion receptor 317
10.5 Fluorescent molecular sensors of neutral molecules and
surfactants 322
10.5.1 Cyclodextrin-based fluorescent sensors 323
10.5.2 Boronic acid-based fluorescent sensors 329
10.5.3 Porphyrin-based fluorescent sensors 329
10.6 Towards fluorescence-based chemical sensing devices 333
Appendix A. Spectrophotometric and spectrofluorometric pH titrations 337
Appendix B. Determination of the stoichiometry and stability constant of metal
complexes from spectrophotometric or spectrofluorometric
titrations 339
10.7 Bibliography 348
11 Advanced techniques in fluorescence spectroscopy 351
11.1 Time-resolved fluorescence in the femtosecond time range: fluorescence
up-conversion technique 351
11.2 Advanced fluorescence microscopy 353
11.2.1 Improvements in conventional fluorescence microscopy 353
11.2.1.1 Confocal fluorescence microscopy 354
11.2.1.2 Two-photon excitation fluorescence microscopy 355
11.2.1.3 Near-field scanning optical microscopy (NSOM) 356

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11.2.2 Fluorescence lifetime imaging spectroscopy (FLIM) 359
11.2.2.1 Time-domain FLIM 359
11.2.2.2 Frequency-domain FLIM 361
11.2.2.3 Confocal FLIM (CFLIM) 362
11.2.2.4 Two-photon FLIM 362
11.3 Fluorescence correlation spectroscopy 364
11.3.1 Conceptual basis and instrumentation 364
11.3.2 Determination of translational diffusion coefficients 367
11.3.3 Chemical kinetic studies 368
11.3.4 Determination of rotational diffusion coefficients 371
11.4 Single-molecule fluorescence spectroscopy 372
11.4.1 General remarks 372
11.4.2 Single-molecule detection in flowing solutions 372
11.4.3 Single-molecule detection using advanced fluorescence microscopy
techniques 374
11.5 Bibliography 378
Epilogue 381
Index 383

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3楼2008-03-13 17:03:29

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