Table of Contents

INTRODUCTION

What Is Luminescence?

A Brief History of Fluorescence and Phosphorescence

Photoluminescence of Organic and Inorganic Species: Fluorescence or Phosphorescence?

Various De-Excitation Processes of Excited Molecules

Fluorescent Probes, Indicators, Labels, and Tracers

Ultimate Temporal and Spatial Resolution: Femtoseconds, Femtoliters, Femtomoles, and Single-Molecule Detection

PART I: PRINCIPLES

ABSORPTION OF ULTRAVIOLET, VISIBLE, AND NEAR-INFRARED RADIATION

Electronic Transitions

Transition Probabilities: The Beer - Lambert Law, Oscillator Strength

Selection Rules

The Franck -Condon Principle

Multiphoton Absorption and Harmonic Generation

CHARACTERISTICS OF FLUORESCENCE EMISSION

Radiative and Nonradiative Transitions between Electronic States

Lifetimes and Quantum Yields

Emission and Excitation Spectra

STRUCTURAL EFFECTS ON FLUORESCENCE EMISSION

Effects of the Molecular Structure of Organic Molecules on Their Fluorescence

Fluorescence of Conjugated Polymers (CPs)

Luminescence of Carbon Nanostructures: Fullerenes, Nanotubes, and Carbon Dots

Luminescence of Metal Compounds, Metal Complexes, and Metal Clusters

Luminescence of Semiconductor Nanocrystals (Quantum Dots and Quantum Rods)

ENVIRONMENTAL EFFECTS ON FLUORESCENCE EMISSION

Homogeneous and Inhomogeneous Band Broadening - Red-Edge Effects

General Considerations on Solvent Effects

Solvent Relaxation Subsequent to Photoinduced Charge Transfer (PCT)

Theory of Solvatochromic Shifts

Effects of Specific Interactions

Empirical Scales of Solvent Polarity

Viscosity Effects

Fluorescence in Gas Phase: Supersonic Jets

EFFECTS OF INTERMOLECULAR PHOTOPHYSICAL PROCESSES ON FLUORESCENCE

EMISSION

Introduction

Overview of the Intermolecular De-Excitation Processes of Excited Molecules Leading to Fluorescence Quenching

Photoinduced Electron Transfer

Formation of Excimers and Exciplexes

Photoinduced Proton Transfer

FLUORESCENCE POLARIZATION: EMISSION ANISOTROPY

Polarized Light and Photoselection of Absorbing Molecules

Characterization of the Polarization State of Fluorescence (Polarization Ratio and Emission Anisotropy)

Instantaneous and Steady-State Anisotropy

Additivity Law of Anisotropy

Relation between Emission Anisotropy and Angular Distribution of the Emission Transition Moments

Case of Motionless Molecules with Random Orientation

Effect of Rotational Motion

Applications

EXCITATION ENERGY TRANSFER

Introduction

Distinction between Radiative and Nonradiative Transfer

Radiative Energy Transfer

Nonradiative Energy Transfer

Determination of Distances at a Supramolecular Level Using FRET

FRET in Ensembles of Donors and Acceptors

FRET between Like Molecules: Excitation Energy Migration in Assemblies of Chromophores

Overview of Qualitative and Quantitative Applications of FRET

PART II: TECHNIQUES

STEADY-STATE SPECTROFL UOROMETRY

Operating Principles of a Spectrofl uorometer

Correction of Excitation Spectra

Correction of Emission Spectra

Measurement of Fluorescence Quantum Yields

Possible Artifacts in Spectrofl uorometry

Measurement of Steady-State Emission Anisotropy: Polarization Spectra

TIME-RESOLVED FLUORESCENCE TECHNIQUES

Basic Equations of Pulse and Phase-Modulation Fluorimetries

Pulse Fluorimetry

Phase-Modulation Fluorimetry

Artifacts in Time-Resolved Fluorimetry

Data Analysis

Lifetime Standards

Time-Resolved Polarization Measurements

Time-Resolved Fluorescence Spectra

Lifetime-Based Decomposition of Spectra

Comparison between Single-Photon Timing Fluorimetry and Phase-Modulation Fluorimetry

FLUORESCENCE MICROSCOPY

Wide-Field (Conventional), Confocal, and Two-Photon Fluorescence Microscopies

Super-Resolution (Subdiffraction) Techniques

Fluorescence Lifetime Imaging Microscopy (FLIM)

Applications

FLUORESCENCE CORRELATION SPECTROSCOPY AND SINGLE-MOLECULE FLUORESCENCE

SPECTROSCOPY

Fluorescence Correlation Spectroscopy (FCS)

Single-Molecule Fluorescence Spectroscopy

PART III: APPLICATIONS

EVALUATION OF LOCAL PHYSICAL PARAMETERS BY MEANS OF FLUORESCENT PROBES

Fluorescent Probes for Polarity

Estimation of 'Microviscosity', Fluidity, and Molecular Mobility

Temperature

Pressure

CHEMICAL SENSING VIA FLUORESCENCE

Introduction

Various Approaches of Fluorescence Sensing

Fluorescent pH Indicators 412 Transfer (PET)

Design Principles of Fluorescent Molecular Sensors Based on Ion or Molecule Recognition

Fluorescent Molecular Sensors of Metal Ions

Fluorescent Molecular Sensors of Anions

Fluorescent Molecular Sensors of Neutral Molecules

Fluorescence Sensing of Gases

Sensing Devices

Remote Sensing by Fluorescence LIDAR

AUTOFL UORESCENCE AND FLUORESCENCE LABELING IN BIOLOGY AND MEDICINE

Introduction

Natural (Intrinsic) Chromophores and Fluorophores

Fluorescent Proteins (FPs)

Fluorescent Small Molecules

Quantum Dots and Other Luminescent Nanoparticles

Conclusion

MISCELLANEOUS APPLICATIONS

Fluorescent Whitening Agents

Fluorescent Nondestructive Testing

Food Science

Forensics

Counterfeit Detection

Fluorescence in Art

APPENDIX: CHARACTERISTICS OF FLUORESCENT ORGANIC COMPOUNDS

INDEX

About the Author

Bernard Valeur received his engineering diploma from the Ecole Superieure de Physique et de Chimie Industrielles de Paris (E.S.P.C.I.) and his PhD degree from the Universite 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 Metiers (Paris) in 1979, where he is emeritus professor since 2008. Professor Valeur is a member of the laboratory Photophysique et Photochimie Supramoleculaires et Macromoleculaires at the Ecole Normale Superieure de Cachan since 1996. From 1995 to 2000 he served as an elected member of the French Comite National de la Recherche Scientifique. He is the winner of the 2012 Gregorio Weber Award for Excellence in Fluorescence Theory and Applications and 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. Mario Nuno Berberan-Santos graduated in chemical engineering from Instituto Superior Tecnico (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 Metiers (Paris, France), and at Laboratoire pour l'Utilisation du Rayonnement Electromagnetique (Univ. Paris-Sud, Orsay, France). He is full professor of Physical Chemistry at IST, and was invited full professor at the Ecole Normale Superieure 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.

Reviews

"The strength of the book lies in its clear and understandable presentation, and in the thoroughness of the descriptions of fluorescence applications, enabling one to quickly appreciate the many questions and problems in the field of fluorescence. Molecular Fluorescence is more a textbook than a monograph, and therefore it is of special interest for students and beginners in the field, and be recommended."
—Angewandte Chemie (international edition), 2002; Vol. 41 No. 16