Molecular Fluorescence Principles and Applications
, by Valeur, Bernard; Berberan-Santos, Má; rio Nuno
- ISBN: 9783527328376 | 3527328378
- Cover: Hardcover
- Copyright: 5/29/2012
This second edition of the well-established bestseller is completely updated and revised with approximately 30% additional material, including two new chapters on applications, which has seen the most significant developments. The comprehensive overview written at an introductory level covers fundamental aspects, principles of instrumentation and practical applications, while providing many valuable tips. For complex, physical, food and photochemists, molecular physicists, lecturers and students of chemistry and physics, and molecular biologists.
Bernard Valeur received his engineering diploma from the ?cole Sup?rieure de Physique et de Chimie Industrielles de Paris (E.S.P.C.I.) and his PhD degree from the Universit? Pierre-et-Marie-Curie (Paris, France), followed by postdoctoral research at the University of Illinois at Urbana-Champaign (USA). After being an associate professor at E.S.P.C.I, he became full professor of physical chemistry at the Conservatoire National des Arts et M?tiers (Paris) in 1979, where he is emeritus professor since 2008. Professor Valeur is a member of the laboratory Photophysique et Photochimie Supramol?culaires et Macromol?culaires at the ?cole Normale Sup?rieure de Cachan since 1996. From 1995 to 2000 he served as an elected member of the French Comit? National de la Recherche Scientifique. He is the author of over 170 articles or book chapters, five books, and the editor of one book. In addition, he is a member of several editorial boards.
M?rio Nuno Berberan-Santos graduated in chemical engineering from Instituto Superior T?cnico (IST, Technical University of Lisbon, Portugal). After a brief stay at the National Research Council of Canada (Ottawa), he received his PhD in chemistry from IST in 1989. He was a post-doctoral fellow with Bernard Valeur at Conservatoire National des Arts et M?tiers (Paris, France), and at Laboratoire pour l'Utilisation du Rayonnement Electromagn?tique (Univ. Paris-Sud, Orsay, France). He is full professor of Physical Chemistry at IST, and was invited full professor at the ?cole Normale Sup?rieure de Cachan (France). He is a member of several editorial advisory boards and is president of the Portuguese Chemical Society (2010-2012). He has authored over 180 publications, including 150 papers in scientific journals, several book chapters, and was the editor of one book.
M?rio Nuno Berberan-Santos graduated in chemical engineering from Instituto Superior T?cnico (IST, Technical University of Lisbon, Portugal). After a brief stay at the National Research Council of Canada (Ottawa), he received his PhD in chemistry from IST in 1989. He was a post-doctoral fellow with Bernard Valeur at Conservatoire National des Arts et M?tiers (Paris, France), and at Laboratoire pour l'Utilisation du Rayonnement Electromagn?tique (Univ. Paris-Sud, Orsay, France). He is full professor of Physical Chemistry at IST, and was invited full professor at the ?cole Normale Sup?rieure de Cachan (France). He is a member of several editorial advisory boards and is president of the Portuguese Chemical Society (2010-2012). He has authored over 180 publications, including 150 papers in scientific journals, several book chapters, and was the editor of one book.
Preface to the First Edition XV
Preface to the Second Edition XVII
Acknowledgments XIX
Prologue XXI
1 Introduction 1
1.1 What Is Luminescence? 1
1.2 A Brief History of Fluorescence and Phosphorescence 2
1.3 Photoluminescence of Organic and Inorganic Species: Fluorescence or Phosphorescence? 191.4 Various De-Excitation Processes of Excited Molecules 20
1.5 Fluorescent Probes, Indicators, Labels, and Tracers 21
1.6 Ultimate Temporal and Spatial Resolution: Femtoseconds, Femtoliters, Femtomoles, and Single-Molecule Detection 23
General Bibliography: Monographs and Books 25
Part I Principles 31
2 Absorption of Ultraviolet, Visible, and Near-Infrared Radiation 33
2.1 Electronic Transitions 33
2.2 Transition Probabilities: The Beer–Lambert Law, Oscillator Strength 39
2.3 Selection Rules 46
2.4 The Franck–Condon Principle 47
2.5 Multiphoton Absorption and Harmonic Generation 49
Bibliography 51
3 Characteristics of Fluorescence Emission 53
3.1 Radiative and Nonradiative Transitions between Electronic States 53
3.2 Lifetimes and Quantum Yields 613.3 Emission and Excitation Spectra 67
Bibliography 744 Structural Effects on Fluorescence Emission 75
4.1 Effects of the Molecular Structure of Organic Molecules on Their Fluorescence 75
4.2 Fluorescence of Conjugated Polymers (CPs) 924.3 Luminescence of Carbon Nanostructures: Fullerenes, Nanotubes, and Carbon Dots 93
4.4 Luminescence of Metal Compounds, Metal Complexes, and Metal Clusters 96
4.5 Luminescence of Semiconductor Nanocrystals (Quantum Dots and Quantum Rods) 103
Bibliography 105
5 Environmental Effects on Fluorescence Emission 109
5.1 Homogeneous and Inhomogeneous Band Broadening – Red-Edge Effects 109
5.2 General Considerations on Solvent Effects 110
5.3 Solvent Relaxation Subsequent to Photoinduced Charge Transfer (PCT) 112
5.4 Theory of Solvatochromic Shifts 117
5.5 Effects of Specifi c Interactions 119
5.6 Empirical Scales of Solvent Polarity 1245.7 Viscosity Effects 129
5.8 Fluorescence in Solid Matrices at Low Temperature 1355.9 Fluorescence in Gas Phase: Supersonic Jets 137
Bibliography 138
6 Effects of Intermolecular Photophysical Processes on Fluorescence Emission 141
6.1 Introduction 141
6.2 Overview of the Intermolecular De-Excitation Processes of Excited Molecules Leading to Fluorescence Quenching 143
6.3 Photoinduced Electron Transfer 1596.4 Formation of Excimers and Exciplexes 162
6.5 Photoinduced Proton Transfer 168Bibliography 179
7 Fluorescence Polarization: Emission Anisotropy 181
7.1 Polarized Light and Photoselection of Absorbing Molecules 181
7.2 Characterization of the Polarization State of Fluorescence (Polarization Ratio and Emission Anisotropy) 184
7.3 Instantaneous and Steady-State Anisotropy 1877.4 Additivity Law of Anisotropy 188
7.5 Relation between Emission Anisotropy and Angular Distribution of the Emission Transition Moments 190
7.6 Case of Motionless Molecules with Random Orientation 191
7.7 Effect of Rotational Motion 1997.8 Applications 207
Bibliography 210
8 Excitation Energy Transfer 213
8.1 Introduction 213
8.2 Distinction between Radiative and Nonradiative Transfer 218
8.3 Radiative Energy Transfer 219
8.4 Nonradiative Energy Transfer 221
8.5 Determination of Distances at a Supramolecular Level Using FRET 2358.6 FRET in Ensembles of Donors and Acceptors 243
8.7 FRET between Like Molecules: Excitation Energy Migration in Assemblies of Chromophores 250
8.8 Overview of Qualitative and Quantitative Applications of FRET 252
Bibliography 258
Part II Techniques 263
9 Steady-State Spectrofl uorometry 265
9.1 Operating Principles of a Spectrofl uorometer 265
9.2 Correction of Excitation Spectra 268
9.3 Correction of Emission Spectra 268
9.4 Measurement of Fluorescence Quantum Yields 269
9.5 Possible Artifacts in Spectrofluorometry 271
9.6 Measurement of Steady-State Emission Anisotropy: Polarization Spectra 277
Appendix 9.A Elimination of Polarization Effects in the Measurement of Fluorescence Intensity 281
Bibliography 283
10 Time-Resolved Fluorescence Techniques 285
10.1 Basic Equations of Pulse and Phase-Modulation Fluorimetries 286
10.2 Pulse Fluorimetry 292
10.3 Phase-Modulation Fluorimetry 298
10.4 Artifacts in Time-Resolved Fluorimetry 302
10.5 Data Analysis 305
10.6 Lifetime Standards 312
10.7 Time-Resolved Polarization Measurements 314
10.8 Time-Resolved Fluorescence Spectra 318
10.9 Lifetime-Based Decomposition of Spectra 318
10.10 Comparison between Single-Photon Timing Fluorimetry and Phase-Modulation Fluorimetry 322
Bibliography 323
11 Fluorescence Microscopy 327
11.1 Wide-Field (Conventional), Confocal, and Two-Photon Fluorescence Microscopies 328
11.2 Super-Resolution (Subdiffraction) Techniques 333
11.3 Fluorescence Lifetime Imaging Microscopy (FLIM) 340
11.4 Applications 342
Bibliography 346
12 Fluorescence Correlation Spectroscopy and Single-Molecule Fluorescence Spectroscopy 349
12.1 Fluorescence Correlation Spectroscopy (FCS) 349
12.2 Single-Molecule Fluorescence Spectroscopy 360
Bibliography 372
Part III Applications 377
13 Evaluation of Local Physical Parameters by Means of Fluorescent Probes 379
13.1 Fluorescent Probes for Polarity 379
13.2 Estimation of “Microviscosity,” Fluidity, and Molecular Mobility 384
13.3 Temperature 398
13.4 Pressure 402
Bibliography 404
14 Chemical Sensing via Fluorescence 409
14.1 Introduction 409
14.2 Various Approaches of Fluorescence Sensing 410
14.3 Fluorescent pH Indicators 412
14.4 Design Principles of Fluorescent Molecular Sensors Based on Ion or Molecule Recognition 420
14.5 Fluorescent Molecular Sensors of Metal Ions 427
14.6 Fluorescent Molecular Sensors of Anions 436
14.7 Fluorescent Molecular Sensors of Neutral Molecules 445
14.8 Fluorescence Sensing of Gases 453
14.9 Sensing Devices 458
14.10 Remote Sensing by Fluorescence LIDAR 460
Appendix 14.A. Spectrophotometric and Spectrofluorometric pH Titrations 462
Single-Wavelength Measurements 462
Dual-Wavelength Measurements 463
Appendix 14.B. Determination of the Stoichiometry and Stability Constant of Metal Complexes from Spectrophotometric or Spectrofl uorometric Titrations 465
Definition of the Equilibrium Constants 465
Preliminary Remarks on Titrations by Spectrophotometry and Spectrofl uorometry 467
Formation of a 1 : 1 Complex (Single-Wavelength Measurements) 467
Formation of a 1 : 1 Complex (Dual-Wavelength Measurements) 469
Formation of Successive Complexes ML and M2L 470
Cooperativity 471
Determination of the Stoichiometry of a Complex by the Method of Continuous Variations (Job’s Method) 471
Bibliography 473
15 Autofluorescence and Fluorescence Labeling in Biology and Medicine 479
15.1 Introduction 479
15.2 Natural (Intrinsic) Chromophores and Fluorophores 480
15.3 Fluorescent Proteins (FPs) 491
15.4 Fluorescent Small Molecules 493
15.5 Quantum Dots and Other Luminescent Nanoparticles 497
15.6 Conclusion 501
Bibliography 502
16 Miscellaneous Applications 507
16.1 Fluorescent Whitening Agents 507
16.2 Fluorescent Nondestructive Testing 508
16.3 Food Science 511
16.4 Forensics 513
16.5 Counterfeit Detection 514
16.6 Fluorescence in Art 515
Bibliography 518
Appendix: Characteristics of Fluorescent Organic Compounds 521
Epilogue 551
Index 553
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