Chemiluminescence in Analytical Chemistry

ISBN: 0-8247-0464-9

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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, chemiluminescence (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 analytical problems.

Although luminescence phenomena date back beyond 300 B.C., the development of CL and BL analytical applications is relatively recent. Simple measuring 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 compounds, CL is one of the most sensitive techniques, compared to atomic absorption spectrometry (AAS), inductively coupled plasma-optical emission spectrometry (ICP-OES), and inductively coupled plasma-mass spectrometry (ICP-MS). Together with classical CL reactions, new strategies have been proposed, considering not only the effect of inorganic ions as oxidants, reductants, catalysts, or inhibitors but also the use of coupling reactions, time-resolved techniques, and

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solid-surface analysis. Also, in organic analysis the number of reactions producing 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 determination have been applied in such areas as medicine, biology, agriculture, industry, and environmental sciences. In the past few years, BL applications have increased, 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 products for life sciences research. For example, isoluminol derivatives and acridinium 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 peroxidase, 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 chemiluminogenic 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 separating 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 postcolumn detection in conventional and microcolumn LC setups. Applications in analytical 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 complex mixtures. Until the 1990s, chemiluminometric detection was not applied after capillary electrophoretic separation, but fast developments from some im-

Preface

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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 immobilized CL reagents, with specific advantages such as reusability, improved stability, and increased efficiency. These strategies have been applied in the development 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, sensitivity to various physicochemical factors) are avoided. As an example, in recent years a CL-based detection system using electrophoretically mediated microanalysis (EMMA) has been described, allowing the detection of enzymes at the zeptomole level in both open tubular capillaries and channels in microfabricated devices.

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 luminescencebased 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 considerably 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 technique. Our aim was to provide the reader with a wide overview of chemical reactions producing light, with emphasis on the analytical uses of the phenomenon 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

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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, researchers 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 analytical chemistry. The contributors were invited to elaborate on the subjects according 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 phenomena, and more specifically of CL and BL, the volume treats the physicochemical 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 nature of CL emission and specific analytical topics such as the recently applied electrogenerated CL, the relative unknown possibilities offered by photosensitized 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 included.

Optimization and applications of CL detection in flow injection and liquid chromatographic analysis and the relatively new use of CL in capillary electrophoresis are extensively described. Particular interest is attached to the universally 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 development 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

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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