| Chemiluminescence (CL) is defined as a process producing electromagnetic (ultraviolet, visible or near-infrared) radiation as a result of a chemical reaction (usually an oxidation) in which one of the reaction products occurs in an excited state and emits light when returning to its ground state. Chemiluminescence analysis has been great developed due to its attracting features including simple cheap optical systems requiring no light sources, high sensitivity, low detection limit, wide linear dynamic range and inexpensive instruments. Up to now, the CL analysis has been widely applied in clinical, biological and environmental fields and is becoming one of the most powerful techniques for use in analytical chemistry. The predominant development of CL analysis nowadays is focused on the development of new CL system, the combination with other techniques such as flow injection (FI), capillary electrophoresis (CE), high performance liquid chromatography (HPLC) and so on. while the uses of established CL reaction systems still attract much interest.This thesis includes two parts. Part one is a review, which reports the development of CL during 2005 and 2008.Part two is research report. The sensitivity and the linear range of CL system were improved, and the corresponding compounds were determined with flow injection CL method. The research results obtained in the thesis are listed as follows:1. A simple chemiluminescence method using flow injection has been developed for the determination of clindamycin, based on the inhibitory effect of clindamycin on the chemiluminescence generated from luminol - potassium ferricyanide system in alkaline medium. It was found that the decrement of chemiluminescence intensity was linear with the logarithm of clindamycin concentration over the range from 0.7 ng/mL to 1000 ng/mL. The detection limit was 0.2 ng/mL with a relative standard deviation of less than 5.0% in seven repeated measurements. At a flow rate of 3.0 mL/min, a complete analytical process could be performed within 0.5 min, including sampling and washing. The proposed procedure was applied successfully to the determination of clindamycin in pharmaceutical preparations and human urine without any pre-treatment process. 2. A simple flow injection chemiluminescence method with synergistic enhancement has been investigated for the rapid and sensitive determination of puerarin. The method is based on the enhancing effect of puerarin on the chemiluminescence emission generated by the oxidation of glyoxal with potassium permanganate in a sulfuric acid medium. The optimization of chemical variables influencing the chemiluminescence response of the method has been carried out by applying experimental design, using the proposed flow-injection manifold. Under the optimal conditions, the enhanced chemiluminescence intensity was linear with the concentration of puerarin over the range from 10.0 ng/mL to 7.0μg/mL (R~2 = 0.9972) with a detection limit (3a) of 3.0 ng/mL. At a flow rate of 3.0 mL/min, a complete analytical process could be performed within 0.5 min, including sampling and washing, with a relative standard deviation of less than 3.0%. The proposed method was applied successfully in the assay of puerarin in pharmaceutical injection and human urine. The mechanism of chemiluminescence reaction was discussed briefly.3. A sensitive, simple and inexpensive chemiluminescence method using flow injection is described for the determination of beta-lactamase inhibitors sulbactam sodium in pharmaceutical preparations and added to blood serum. The method is based on the inhibitory effect of sulbactam on the chemiluminescence reaction between luminol and peroxy-acetic acid in alkaline medium. Under the optimal conditions, the decrement of chemiluminescence intensity was linear with sulbactam concentration over the range from 5.0 ng/mL to 1000 ng/mL with the detection limit of 2.0 ng/mL (3a). The method has been successfully applied to the determination of sulbactam in two kinds of pharmaceutical preparations and serum samples.4. A simple chemiluminescence method based on N-bromosuccinimide - 2, 7 -dichlorofluorescein (NBS - 2, 7-dichlorofluorescein) system with flow injection has been developed for the determination of diacerein in pharmaceutical preparations, the chemiluminescence in alkaline medium. It was found that diacerein could inhibit sensitively the chemiluminescence intensity generated between N-bromosuccinimide and 2, 7-dichlorofluorescein reaction and the decrement of chemiluminescence intensity was linear with the logarithm of diacerein concentration over the range from 1.0 ng/mL to 1000 ng/mL. The detection limit was 0.3 ng/mL with a relative standard deviation of less than 5.0% in ten repeated measurements. At a flow rate of 3.0 mL/min, a complete analytical process could be performed within 0.5 min, including sampling and washing. The proposed procedure was applied successfully to the determination of diacerein in pharmaceutical preparations without interference from its potential impurities. The degradation of diacerein was also investigated briefly.5. The CL behavior of six benzoic acid derivatives in cerium (IV)-tween 80 system was investigated by flow-injection. Strong CL was observed when cerium (IV) reacted with tween 80 in sulfuric acid medium in the presence of benzoic acid. This reaction system has been established as a simple, rapid and highly sensitive flow injection CL analysis for o-hydroxybenzoic acid, p-hydroxybenzoic acid and o-amimobenzoic acid, and their detection limit (3σ) were 0.3 ng/mL, 3 ng/mL and 0.3 ng/mL, respectively. A simple flow injection chemiluminescence method was established for the rapid and sensitive determination of benzoic acid derivatives. |
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