The principles of fluorescence spectroscopy are by now well established, and, after a rather lengthy gestation period, the technique is now routinely applied to a broad spectrum of problems, ranging from mechanistic photo­ chemistry to chemical analyses in biomedical and environmental systems of structure and function in biological macromolecules. Phosphor­ to probes escence spectrometry and chemiluminescence are also well-known tech­ niques; they are somewhat less well established than fluorescence (at least in analytical chemistry), but they too are receiving greatly increased appli­ cation to both laboratory and "real" problems. This is not to imply that luminescence spectroscopy, viewed in its broadest sense, is a static field. In fact, recent advances in instrumentation make it feasible to apply fluorescence to problem areas in which its use five years ago would have been unthinkable. Advances in hardware generate advances in application, and very significant progress is being recorded in the application of fluorescence (and its close relatives, phosphorescence and chemiluminescence) in the biochemical, biomedical, and environmental spheres.

Inhalt

of Volume 1.- 1 Fluorescence Spectroscopy with On-Line Computers: Methods and Instrumentation.- A. Introduction.- 1. Computerization in Fluorescence Spectroscopy.- 2. Practical Considerations.- a. Terminology and Hardware.- b. Components External to the Interface.- 3. Criteria for Selection of Components.- a. The Computer.- b. Selection of Interface Components.- 4. Computer Programming (Software).- 5. A Systems Approach to the Design of On-Line Instrument Systems.- B. A Simple On-Line Data-Acquisition and Control System.- 1. The Hardware System.- 2. The Software System.- C. Integrated-Computerized Instrument Systems for Fluorescence Spectroscopy.- 1. Fluorescence Emission and Excitation Spectra.- 2. Polarization of Fluorescence.- 3. Fluorescence Lifetime Measurements.- D. Glossary.- References.- 2 Digital and Analog Measurements in Fluorescence Spectroscopy.- A. Introduction.- B. Definitions and Nomenclature.- 1. Analog and Digital Domains.- 2. Suitability of Digital and Analog Presentations for Fluorescence Measurements.- C. Comparison of Electronic Methodology in Two Modern Spectrofluorometers.- 1. Introduction.- 2. A Computer-Centered Spectrofluorometer.- 3. An Analog-Compensated Spectrofluorometer.- D. Photon Counting and Lock-in Amplification.- 1. Introduction.- 2. Principles of Photon Counting.- 3. Principles of Phase-Sensitive Detection.- 4. Practical Results Comparing Photon Counting with Lock-in Amplification.- E. Principles and Applications of Digital Integration.- 1. Digital Integration of Fluorescence Signals.- 2. Application in Case of Photodecomposition.- 3. Digital ATP Photometers for Biological Measurements.- F. Other Electronic Techniques for Fluorometry.- 1. Source Intensity Correction.- 2. Wavelength Encoding.- 3. Transient Fluorescence Measurements.- 4. Future Electronic Impacts on Luminescence Measurements.- References.- 3 Modulation and Derivative Techniques in Luminescence Spectroscopy: Approaches to Increased Analytical Selectivity.- A. Introduction.- B. Derivative Techniques in Luminescence Spectrometry.- C. Wavelength-Modulation Techniques in Luminescence Spectrometry.- D. Conclusion.- References.- 4 Dye Lasers: Fundamentals and Analytical Applications.- A. Introduction.- 1. Historical Background.- 2. Fundamentals.- a. General Aspects of Lasers.- b. Dye Lasers.- c. Wavelength Tuning.- B. Instrumentation.- 1. Components.- a. Excitation Sources.- b. Optics.- c. Detection Methods.- 2. Laser-Active Compounds.- 3. Commercial Units.- C. Analytical Applications.- 1. Dye Lasers as Sources.- a. Atomic and Molecular Absorption.- b. Intracavity Quenching of Dye Lasers.- c. Atomic and Molecular Luminescence.- 2. Laser Fluorescence as a Signal.- D. Conclusion.- References.- 5 Laser-Excited Fluorescence Techniques in Air Pollution Monitoring.- A. Introduction.- B. Measurement of Atmospheric NO2 Levels.- 1. Spectroscopic Properties of NO2.- 2. Laser NO2 Monitor.- 3. Modifications for Monitoring NO.- 4. Improved Laser NO2 Monitor (442 nm Excitation).- C. Fluorescence of Atmospheric Aerosols.- 1. Method of Monitoring Aerosol Fluorescence.- 2. Fluorescence Detection of Pollutants in the Presence of Aerosols and NO2.- 3. Discrimination against Broadband Interference by a Two-Wavelength Method.- 4. Fluorescence Identification of Aerosols.- D. Fluorescence Determination of SO2.- 1. Spectroscopic Properties of SO2: Absorption, Fluorescence, and Quenching of Fluorescence.- 2. Prototype System for Determination of Ambient SO2.- 3. Fluorescence Detection of Nitric Oxide.- E. Assessment of the Fluorescence Method.- 1. Comparison of Laser versus Lamp Excitation.- 2. Calculated Detectability of a Laser SO2 Monitor.- 3. Remote Sensing of Atmospheric Pollutants by Fluorescence.- 4. Fluorescence Measurement of Atmospheric Hydroxyl Radical Concentrations.- F. Application of Novel Laser Techniques.- 1. Tunable and Pulsed Lasers.- 2. Mode-Locked Lasers.- G. Conclusions and Future Projections.- References.- 6 Chemiluminescence Techniques in Air Pollutant Monitoring.- A. Introduction.- B. Monitors in Present Use.- 1. Types of Monitors and Their Applications.- a. Compound-Specific Detectors.- b. Element-Specific Detectors.- 2. Compound-Specific Monitors Based on the Reaction NO + O3 ? NO2 + O2 + hv.- a. NO and O3.- b. NO2, NOx (= NO + NO2).- c. NH3 and Amines.- d. Multifunctional Monitors and Monitor Calibration.- 3. O3 Monitors Based on Other Reactions.- a. Homogeneous Chemiluminescence.- b. Heterogeneous Chemiluminescence.- C. Compound-Specific Monitoring Methods in Development or under Consideration.- 1. Application of the Reaction O + NO ? NO2 + hv.- a. NOx.- b. NO2 by the Photofragment Technique.- 2. NO2 by an O3 Chemiluminescence-Based Photofragment Technique.- 3. Application of Other Reactions.- a. Reactive Hydrocarbons.- b. SO2.- c. PAN.- D. Conclusion.- Appendix: Pertinent Rate Coefficients.- References.- 7 Chemiluminescence Analysis in Water Pollution Studies.- A. Introduction.- B. ATP Analysis.- C. Iron(II) Analysis.- D. Phosphorus Analysis.- E. Future Developments in Chemiluminescence Analysis.- 1. Liquid-Phase CL.- a. Coupling Enzyme Reactions to CL.- b. Chemical Excitation of Fluorescence.- c. Coupling of CL to Separation Methods.- 2. Flame CL.- References.- 8 Internal-Reflection Techniques in Fluorescence Spectroscopy.- A. Introduction.- B. Single-Internal-Reflection Studies.- C. Multiple-Internal-Reflection Fluorescence (MIRF).- D. Optical Materials and Geometries for Internal-Reflection Elements (IRE).- E. MIRF with a Commercial Spectrophotofluorometer.- References.- Author Index.