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ISBN: 0-8247-0464-9 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10 9 8 7 6 5 4 3 2 1 PRINTED IN THE UNITED STATES OF AMERICA Preface For more than 30 years, the phenomenon of luminescence—originally a curiosity in the physical laboratory—has been the basis of a well-established and widely applied spectrometric branch of analytical chemistry. Specifically, chemilumines- cence (CL)-based analysis is growing rapidly, offering a simple, low-cost, and sensitive means of measuring a variety of compounds. Owing to elegant new instrumentation and, especially, to new techniques, some of which are entirely new and some borrowed from other disciplines, CL and bioluminescence (BL) can now be routinely applied to solve diverse qualitative and quantitative analyti- cal problems. Although luminescence phenomena date back beyond 300 b.c., the devel- opment of CL and BL analytical applications is relatively recent. Simple measur- ing devices and the high versatility for the determination of a wide variety of species have enabled CL-based detection to develop into a highly sensitive and most useful analytical technique. The first application of CL as an analytical tool was carried out in the early 1950s, employing several substances such as luminol, lophine, and lucigenin as volumetric indicators. Investigations on the potential of CL for analytical routine applications date from the 1970s for gas-phase and from the 1980s for liquid-phase reactions. In trace analysis for inorganic com- pounds, CL is one of the most sensitive techniques, compared to atomic absorp- tion spectrometry (AAS), inductively coupled plasma-optical emission spectrom- etry (ICP-OES), and inductively coupled plasma-mass spectrometry (ICP-MS). Together with classical CL reactions, new strategies have been proposed, consid- ering not only the effect of inorganic ions as oxidants, reductants, catalysts, or inhibitors but also the use of coupling reactions, time-resolved techniques, and iii iv Preface solid-surface analysis. Also, in organic analysis the number of reactions produc- ing CL cited in the literature is increasing annually. For example, the inherent power of applying the peroxyoxalate CL system to a vast number of natively fluorescing species or fluorophores formed after chemical derivatization broadens the scope of this relatively new detection technique. In drug analysis, CL has become a powerful tool in recent years, due to the discovery of new CL systems based on the direct oxidation of molecules with different common oxidants in acid or alkaline media. Since the discovery in 1947 of the essential role of ATP in the BL reactions by which fireflies produce light, simple and very sensitive methods for its deter- mination have been applied in such areas as medicine, biology, agriculture, indus- try, and environmental sciences. In the past few years, BL applications have in- creased, mainly in the biomedical field, owing to the further development of gene technology and the use of different new methods to study BL at the molecular level. As an example, CL precursors have been used from the 1970s to the present as sensitive substitute labels for isotopic labeling, replacing radioisotopes and providing a new strategy, considerably better in terms of sensitivity and safety, in immunoassay. In this sense, increasing interest has been focused on CL prod- ucts for life sciences research. For example, isoluminol derivatives and acridin- ium esters have proved to be successful in the development of commercial kits in clinical diagnostics. In the 1980s, the discovery of the light-yield enhancement when firefly luciferase was accidentally added to a mixture of horseradish peroxi- dase, luminol, and hydrogen peroxide marked the beginning of a very successful analytical era for immunoassay and diverse blotting applications (protein, DNA, and RNA). More recently, a new technology using novel acridan esters as chemi- luminogenic signal reagents has demonstrated its suitability in immunoassay. The characteristics of CL emission make this phenomenon suitable as a detecting tool in flow injection, gas, and column liquid chromatographic separat- ing systems. Continuous-flow CL-based detection of several analytes has been widely applied by several groups for the determination of diverse biological and pharmaceutical compounds. In combination with HPLC separations, several CL reactions have been used, including peroxyoxalates, firefly luciferase, lucigenin, and luminol, the peroxyoxalate reaction being most commonly used for postcol- umn detection in conventional and microcolumn LC setups. Applications in ana- lytical research, biotechnology, and quality control areas are currently being amply described. A recent trend in analytical chemistry involves the application of CL as a detection system in combination with capillary electrophoresis as prior separation methodology, providing excellent analytical sensitivity and selectivity and allowing the resolution and quantification of various analytes in relatively com- plex mixtures. Until the 1990s, chemiluminometric detection was not applied after capillary electrophoretic separation, but fast developments from some im- Preface v portant research groups have been noticed in the past few years; hence, further developments are expected. Immobilization techniques have been applied in the preparation of immobi- lized CL reagents, with specific advantages such as reusability, improved stabil- ity, and increased efficiency. These strategies have been applied in the develop- ment of CL sensors, which today constitute the most important tools in analytical chemistry because of the high sensitivity offered. Optical fibers have been used to transfer light in order to improve the quality of detection, and new types of flow-through cells have been introduced in the construction of CL sensors. Also, selectivity has been considerably improved by the utilization of enzymatic or antigen–antibody reactions. It is clear that the need for improving detection technology is related to the general trend in analytical chemistry to miniaturize, and thus reduce, waste volumes of organic solvents in separational setups and, by using more aqueous systems, study smaller samples at increasingly lower concentrations. As the CL technique may provide solutions for these specific challenges, the instrumentation for CL measurements and the coupling with a selective physical or chemical interface to achieve selective measurements are likewise being explored. In this way, disadvantages of direct CL-based techniques (e.g., lack of selectivity, sensi- tivity to various physicochemical factors) are avoided. As an example, in recent years a CL-based detection system using electrophoretically mediated microanal- ysis (EMMA) has been described, allowing the detection of enzymes at the zepto- mole level in both open tubular capillaries and channels in microfabricated de- vices. The degree of scientific interest toward the application of CL in the various disciplines of analytical chemistry may be illustrated by the growing position that is being attributed to this physicochemical phenomenon in the luminescence- based analytical symposia that have been organized over the globe since the early 1980s, series that appear about to receive increasing interest by the scientific community in the decade to come. Moreover, in the past two decades the number of published papers in prestigious analytical journals and in related dedicated journals such as the Journal of Biological and Chemical Luminescence has con- siderably grown. All these considerations encouraged us to produce a multiauthored book focussing on the importance and versatility of CL in the actual scientific context through the different perspectives related to its potential as an analytical tech- nique. Our aim was to provide the reader with a wide overview of chemical reactions producing light, with emphasis on the analytical uses of the phenome- non and its recent applications, in a style accessible to readers at various levels (researchers, industrial workers, undergraduates, and graduates, as well as Ph.D. students). With this purpose, we have organized the available information on the various aspects of CL into different chapters, each produced by authors with vi Preface recognized international expertise in the specific areas. In our modest opinion, a comprehensive volume was built up in this way, useful to students at the various university levels; chemists; pharmacists; biologists; medical doctors; technicians in food, clinical, toxicological, and environmental disciplines; quality control managers—primarily in chemical analytical laboratories—and, in general, re- searchers applying luminescence-based techniques. The selection of essential topics and expert authors was not an easy task. We tried to include the most representative applications of CL and BL in analyti- cal chemistry. The contributors were invited to elaborate on the subjects ac- cording to their knowledge and experience in the field, and we think we have succeeded in unifying the contents of the overall volume. We heartily thank the contributing authors for agreeing to collaborate on this project; their efforts led to the comprehensive structure of this book. Apart from an overview on the historical evolution of luminescence phe- nomena, and more specifically of CL and BL, the volume treats the physicochem- ical nature of these reactions, the basic principles, the evolution in instrumenta- tion—from the use of simple PMTs to the implementation of CCD cameras and the development of imaging technology—and general applications in organic and inorganic analysis, considering the use of organized media so as to enhance sensitivity. Different analytical CL approaches related to the intrinsic kinetic na- ture of CL emission and specific analytical topics such as the recently applied electrogenerated CL, the relative unknown possibilities offered by photosensi- tized CL used in medical and industrial routine analysis, and the wide uses of CL detection in the gas phase—mainly in atmospheric research—have been in- cluded. Optimization and applications of CL detection in flow injection and liquid chromatographic analysis and the relatively new use of CL in capillary electro- phoresis are extensively described. Particular interest is attached to the univer- sally applied peroxyoxalate CL reactions, as well as to the applications of new acridan esters in immunoassay. Obviously, the related applications of BL and CL imaging techniques in analytical chemistry, and the increasing importance of these techniques in DNA analysis—including the recent strategies in the devel- opment of CL sensors—are also presented. It is our wish to encourage the analytical community to discover more about this most exciting analytical technique and to consider it a powerful alternative in the resolution of a variety of analytical challenges. Ana M. Garcı ´ a-Campan ˜ a Willy R. G. Baeyens Contents Preface iii Contributors xi 1. Historical Evolution of Chemiluminescence 1 Ana M. Garcı ´ a Campan ˜ a, Willy R. G. Baeyens, and Manuel Roma ´ n-Ceba 2. Chemiluminescence-Based Analysis: An Introduction to Principles, Instrumentation, and Applications 41 Ana M. Garcı ´ a-Campan ˜ a, Willy R. G. Baeyens, and Xinrong Zhang 3. The Nature of Chemiluminescent Reactions 67 Stephen G. Schulman, Joanna M. Schulman, and Yener Rakiciog ˘ lu 4. Recent Evolution in Instrumentation for Chemiluminescence 83 Dan A. Lerner 5. Applications of Chemiluminescence in Organic Analysis 105 Yener Rakiciog ˘ lu, Joanna M. Schulman, and Stephen G. Schulman vii viii Contents 6. Application of Chemiluminescence in Inorganic Analysis 123 Xinrong Zhang, Ana M. Garcı ´ a-Campan ˜ a, and Willy R. G. Baeyens 7. Mechanism and Applications of Peroxyoxalate Chemiluminescence 141 Malin Stigbrand, Tobias Jonsson, Einar Ponte ´ n, Knut Irgum, and Richard Bos 8. Kinetics in Chemiluminescence Analysis 175 Dolores Pe ´ rez-Bendito and Manuel Silva 9. Electrogenerated Chemiluminescence 211 Andrew W. Knight 10. Applications of Bioluminescence in Analytical Chemistry 247 Stefano Girotti, Elida Nora Ferri, Luca Bolelli, Gloria Sermasi, and Fabiana Fini 11. The Role of Organized Media in Chemiluminescence Reactions 285 Jose ´ Juan Santana Rodrı ´ guez 12. Chemiluminescence in Flow Injection Analysis 321 Antony C. Calokerinos and Leonidas P. Palilis 13. Gas-Phase Chemiluminescence Detection 349 James E. Boulter and John W. Birks 14. Chemiluminescence Detection in Liquid Chromatography 393 Naotaka Kuroda, Masaaki Kai, and Kenichiro Nakashima 15. Chemiluminescence Detection in Capillary Electrophoresis 427 Ana M. Garcı ´ a-Campan ˜ a, Willy R. G. Baeyens, and Norberto A. Guzman 16. Bioanalytical Applications of Chemiluminescent Imaging 473 Aldo Roda, Patrizia Pasini, Monica Musiani, Mario Baraldini, Massimo Guardigli, Mara Mirasoli, and Carmela Russo 17. Photosensitized Chemiluminescence: Its Medical and Industrial Applications for Antioxidizability Tests 497 Igor Popov and Gudrun Lewin Contents ix 18. Application of Novel Acridan Esters as Chemiluminogenic Signal Reagents in Immunoassay 529 Gijsbert Zomer and Marjorie Jacquemijns 19. Chemiluminescence and Bioluminescence in DNA Analysis 551 Masaaki Kai, Kazuko Ohta, Naotaka Kuroda, and Kenichiro Nakashima 20. Recent Developments in Chemiluminescence Sensors 567 Xinrong Zhang, Ana M. Garcı ´ a-Campan ˜ a, Willy R. G. Baeyens, Raluca-Ioana Stefan, Hassan Y. Aboul-Enein, and Jacobus F. van Staden Abbreviations 593 Index 601 . CL imaging techniques in analytical chemistry, and the increasing importance of these techniques in DNA analysis—including the recent strategies in the. CHEMILUMINESCENT SYSTEMS 12 4. THE FIRST ANALYTICAL USES OF BIOLUMINESCENCE AND CHEMILUMINESCENCE 22 4.1 Chemiluminescence in the Gas Phase 22 4.2 Chemiluminescent