Chemiluminescence in Analytical Chemistry
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2
Chemiluminescence-Based Analysis
An Introduction to Principles, Instrumentation, and Applications
Ana M. Garcı´a-Campan˜a
University of Granada, Granada, Spain
Willy R. G. Baeyens
Ghent University, Ghent, Belgium
Xinrong Zhang
Tsinghua University, Beijing, P. R. China
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INTRODUCTION |
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2. |
GENERAL PRINCIPLES |
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Mechanisms of Chemiluminescence Reactions |
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Requirements for Chemiluminescence Emission |
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2.3 |
Factors Influencing Chemiluminescence Emission |
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Characteristics of Chemiluminescence as Analytical |
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Technique |
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BASIC INSTRUMENTATION |
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Introduction of Sample and Reagents |
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Reaction Cell |
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Detector |
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Signal Conditioning, Manipulation, and Readout |
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MAIN CHEMILUMINESCENCE APPLICATIONS |
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CHEMILUMINESCENCE AND BIOLUMINESCENCE |
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ON THE INTERNET |
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General Websites |
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Images, Movies, and Demonstrations |
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Companies, Instruments, and Products |
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1. INTRODUCTION
Chemiluminescence (CL) is defined as the emission of electromagnetic radiation (usually in the visible or near-infrared region) produced by a chemical reaction.
Table 1 Classification of Luminescence Phenomena
Produced from irradiation
A.Photoluminescence: An excited state is produced by the absorption of ultraviolet, visible, or near-infrared radiation
Fluorescence: Short-lived emission from a singlet electronically excited state Phosphorescence: Long-lived emission from a triplet electronically excited state
B.Cathodoluminescence: Emission produced from irradiation of β-particles
C.Anodoluminescence: Emission produced from irradiation of α-particles
D.Radioluminescence: Emission produced from irradiation of γ-particles or X-rays
Produced from heating
A.Candoluminescence: Emission from incandescent solids
B.Thermoluminescence: Emission from solids and crystals on mild heating
C.Pyroluminescence: Emission from metal atoms in flames
Produced from structural rearrangements in solids
A.Triboluminescence: Emission from shaking, rubbing, or crushing crystals
B.Crystalloluminescence: Emission from crystallization
C.Lyoluminescence: Emission from dissolving crystals
Produced from electrical phenomena
A.Electroluminescence: Emission from electrical discharges
B.Galvanoluminescence: Emission during electrolysis
C.Sonoluminescence: Emission from exposure to ultrasonic sound waves in solution
D.Piezoluminescence: Emission from frictional charges separation at the crystal surface
Produced from chemical reactions
A.Bioluminescence: Emission from living organisms or biological systems
B.Chemiluminescence: Emission from a chemical reaction Electrochemiluminescence: Emission occurring in solution, from an electronically
excited state produced by high-energy electron transfer reactions Electrogenerated chemiluminescence: Emission produced at an electrode surface Oxyluminescence: Emission from polymers caused by oxidative processes
(presence of oxygen is required)
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When this emission originates from living organisms or from chemical systems derived from them, it is named bioluminescence (BL). Both phenomena are luminescence processes that have been traditionally distinguished from related emissions by a prefix that identifies the energy source responsible for the initiation of emission of electromagnetic radiation. Based on Wiedemann’s classification, which was discussed in Chapter 1, contemporary luminescence processes have been added to the list of luminescence phenomena, as can be seen in Table 1.
In CL, reactions generally yield one of the reaction products in an electronic excited state producing light on falling to the ground state. As can be seen in Figure 1, the process of light emission in CL is the same as in photoluminescence, except for the excitation process. In fluorescence and phosphorescence the electronically excited state is produced by absorption of ultraviolet or visible light, returning to the ground state (S0) from the lowest singlet excited state (S1) or from the triplet excited state (T1) (Fig. 1). A more extensive discussion of these processes has been included in Chapter 3.
Because the emission intensity is a function of the concentration of the chemical species involved in the CL reaction, measurement of emission intensities can be used for analytical purposes. An advantage of CL techniques is that it is possible to employ rather simple basic instrumentation, as the optical system requires no external light source. CL is often described as a dark-field technique: the absence of strong background light levels, such as found in spectrophotometry and fluorimetry, reduces noise signals and leads to improved detection limits. Instrumentation for CL measurements ranges from simple to very complex, that is, allowing the use of some fluorometers by turning off the excitation source, or applying the facilities offered by more sophisticated systems.
Figure 1 Jablonski diagram showing energy levels and transitions: F, fluorescence; C, chemiluminescence; P, phosphorescence; CD, collisional deactivation; IC, internal conversion; ISC, intersystem crossing; S0, ground singlet state; S1, S2, excited singlet states; T1, excited triplet state.
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However, some limitations must be considered in CL analysis, such as the dependence of the CL emission on several environmental factors that therefore must be controlled, the lack of selectivity because a CL reagent is not limited to just one unique analyte, and finally, like other mass flow detection approaches, since CL emission is not constant but varies with time (light flash composed of a signal increase after reagent mixing, passing through a maximum, then declining to the baseline), and this emission-versus-time profile can vary widely in different CL systems, care must be taken to detect the signal in flowing streams at strictly defined periods.
In this introductory chapter, the basic principles of CL will be presented, with a brief introduction to the essential instrumentation as well as some general aspects showing that this technique is suitable as a detection mode for analytical purposes. Details on each specific topic can be found later in this book.
2. GENERAL PRINCIPLES
2.1 Mechanisms of Chemiluminescence Reactions
In general, a chemiluminescent reaction can be generated by two basic mechanisms (Fig. 2). In a direct reaction, two reagents, usually a substrate and an oxidant in the presence of some cofactors, react to form a product or intermediate, sometimes in the presence of a catalyst. Then some fraction of the product or intermediate will be formed in an electronically excited state, which can subse-
Figure 2 Types of CL reactions. P, product; F, fluorescing substance.
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quently relax to the ground state with emission of a photon. The substrate is the CL precursor, which is converted into the electronically excited molecule, responsible for light emission or acting as the energy transfer donor in indirect CL. The catalyst, enzyme or metal ions, reduces the activation energy and provides an adequate environment for producing high CL efficiency out of the process. Cofactors sometimes are necessary to convert one or more of the substrates into a form capable of reacting and interacting with the catalyst, or to provide an efficient leaving group if bond cleavage is required to produce the excited emitter. On the contrary, indirect or sensitized CL is based on a process of transfer of energy of the excited specie to a fluorophore. This process makes it possible for those molecules that are unable to be directly involved in CL reactions to transfer their excess of energy to a fluorophore that in turn is excited, releasing to its ground state with photon emission. All of these paths lead to a great variety of practical uses of CL in solid, gas, and liquid phases.
2.2 Requirements for Chemiluminescence Emission
For a chemical reaction to produce light, it should meet some essential requirements:
1. The reaction must be exothermic to produce sufficient energy to form the electronically excited state. To predict whether the CL reaction will occur or not, it is possible to use the free energy (∆G):
∆G ∆H T∆S |
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where T is temperature, ∆H is enthalpy, and ∆S is entropy. Enthalpy is the actual energy source for generating the electronically excited state product. To initiate the chemical reaction the activation energy (∆HA) is absorbed. The available energy to produce the excited state (∆EEX) must be the difference between the reaction energy and the activation energy. If this difference is equal to or greater than the energy required for generating the excited state ∆EEX, the CL process will be produced:
Energy available ∆HA ∆HR ∆EEX |
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In many CL reactions, the entropy change is small, so ∆G and ∆H are very similar in magnitude and the energetic requirements can be established in terms of ∆G (Kcal.mol 1). In this sense, for CL to occur the reaction must be sufficiently exothermic such that:
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