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Molecular Fluorescence
Principles and Applications
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Molecular Fluorescence
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 photochemists and photophysicists, physical chemists, molecular physicists, biophysicists, biochemists and biologists, lecturers and students of chemistry, physics, and biology.
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Yes, you can access Molecular Fluorescence by Bernard Valeur, Mário Nuno Berberan-Santos in PDF and/or ePUB format, as well as other popular books in Physical Sciences & Industrial & Technical Chemistry. We have over one million books available in our catalogue for you to explore.
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1
Introduction
… ex arte calcinati, et illuminato aeri seu solis radiis, seu flammae fulgoribus expositi, lucem inde sine calore concipiunt in sese; … | [… properly calcinated, and illuminated either by sunlight or flames, they conceive light from themselves without heat; …] |
Licetus, 1640 (about the Bologna stone)
1.1 What Is Luminescence?
The word luminescence, which comes from the Latin (lumen = light) was first introduced as luminescenz by the physicist and science historian Eilhardt Wiedemann in 1888, to describe “all those phenomena of light which are not solely conditioned by the rise in temperature,” as opposed to incandescence. Luminescence is often considered as cold light whereas incandescence is hot light.
Luminescence is more precisely defined as follows: spontaneous emission of radiation from an electronically excited species or from a vibrationally excited species not in thermal equilibrium with its environment.1) The various types of luminescence are classified according to the mode of excitation (see Table 1.1).
Phenomenon | Mode of excitation |
Photoluminescence (fluorescence, phosphorescence, delayed fluorescence) | Absorption of light (photons) |
Radioluminescence | Ionizing radiation (X-rays, α, β, γ) |
Cathodoluminescence | Cathode rays (electron beams) |
Electroluminescence | Electric field |
Thermoluminescence | Heating after prior storage of energy (e.g., radioactive irradiation) |
Chemiluminescence | Chemical reaction (e.g., oxidation) |
Bioluminescence | In vivo biochemical reaction |
Triboluminescence | Frictional and electrostatic forces |
Sonoluminescence | Ultrasound |
Luminescent compounds can be of very different kinds:
- Organic compounds: aromatic hydrocarbons (naphthalene, anthracene, phenanthrene, pyrene, perylene, porphyrins, phtalocyanins, etc.) and derivatives, dyes (fluorescein, rhodamines, coumarins, oxazines), polyenes, diphenylpolyenes, some amino acids (tryptophan, tyrosine, phenylalanine), etc.
- Inorganic compounds: uranyl ion (
- Organometallic compounds: porphyrin metal complexes, ruthenium complexes (e.g.,
Fluorescence and phosphorescence are particular cases of luminescence (Table 1.1). The mode of excitation is absorption of one or more photons, which brings the absorbing species into an electronic excited state. The spontaneous emission of photons accompanying de-excitation is then called photoluminescence which is one of the possible physical effects resulting from interaction of light with matter, as shown in Figure 1.1. Stimulated emission of photons can also occur under certain conditions (see Chapter 3, Box 3.2). Additional processes, not shown, can take place for extremely high intensities of radiation, but are not relevant for luminescence studies.
1.2 A Brief History of Fluorescence and Phosphorescence
It is worth giving a brief account of the history of fluorescence and phosphorescence. The major events from the early stages to the middle of the twentieth century are reported in Table 1.2 together with the names of the associated scientists. The story of fluorescence started with a report by N. Monardes in 1565, but scientists focused their attention on light emission phenomena other than incandescence only in the nineteenth century. However, the major experimental and theoretical aspects of fluorescence and phosphorescence were really understood only after the emergence of quantum theory, already in the twentieth century (1918–1935, i.e., less than 20 years). As in many other areas of theoretical physics and chemistry, this was an exceptionally fecund period.
Year | Scientist | Observation or achievement |
1565 | N. Monardes | Emission of light by an infusion of the wood later called Lignum nephriticum (first report on the observation of fluorescence) |
1602 | V. Cascariolo | Emission of light by Bolognese stone (first detailed observation of phosphorescence) |
1640 | Licetus | Study of Bolognian stone. First definition as a nonthermal light emission |
1833 | D. Brewster | Emission of light by chlorophyll solutions and fluorspar crystals |
1842 | J. Herschel | Emission of light by quinine sulfate solutions (epipolic dispersion) |
1845 | E. Becquerel | Emission of light by calcium sulfide upon excitation in the UV |
First statement that the emitted light is of longer wavelength than the incident light. | ||
1852 | G. G. Stokes | Emission of light by quinine sulfate solutions upon excitation in the UV (refrangibility of light) |
1853 | G. G. Stokes | Introduction of the term fluorescence |
1858 | E. Becquerel | First phosphoroscope. First lifetime measurements. |
1867 | F. Goppelsröder | First fluorometric analysis (determination of Al(III) by the fluorescence of its morin chelate) |
1871 | A. Von Baeyer | Synthesis of fluorescein |
1888 | E. Wiedemann | Introduction of the term luminescence |
1905, 1910 | E. L. Nichols and E. Merrit | First fluorescence excitation spectrum of a dye |
1907 | E.L. Nichols and E. Merrit | Mirror symmetry between absorption and fluorescence spectra |
1919 | O. Stern and M. Volmer | Relation for fluorescence quenching |
1920 | F. Weigert | Discovery of the polarization of the fluorescence emitted by dye solutions |
1922 | S. I. Vavilov | Excitation-wavelength independence of the fluorescence quantum yield |
1923 | S. I. Vavilov and W. L. Levshin | First study of the fluorescence polarization of dye solutions |
1924 | S. I. Vavilov | First determination of fluorescence yield of dye solutions |
1924 | F. Perrin | Quantitative description of static quenching (active sphere model |
1924 | F. Perrin | First observation of alpha phosphorescence (E-type delayed fluorescence) |
1925 | F. Perrin | Theory of fluorescence polarization (influence of viscosity) |
1925 | W. L. Levshin | Theory of polarized fluorescence and phosphorescence |
1925 | J. Perrin | Introduction of the term delayed fluorescence |
Prediction of long-range energy transfer | ||
1926 | E. Gaviola | First direct measurement of nanosecond lifetimes by phase fluorometry (instrument built in Pringsheim’s laboratory) |
1926 | F. Perrin | Theory of fluorescence polarization (sphere) |
Perrin’s equation | ||
Indirect determination of lifetimes in solution. | ||
Comparison with radiative lifetimes | ||
1927 | E. Gaviola and P. Pringsheim | Demonstration of resonance energy transfer in solutions... |
Table of contents
- Cover
- Further Titles of Interest
- Title page
- Copyright page
- Preface to the First Edition
- Preface to the Second Edition
- Acknowledgments
- Prologue
- 1 Introduction
- Part I: Principles
- Part II: Techniques
- Part III: Applications
- Appendix: Characteristics of Fluorescent Organic Compounds
- Epilogue
- Index