| Chemiluminescence(CL) is defined as the emission of light from anelectronically excited state species which is produced during the course of a chemicalreaction. The advantages of CL analysis include high sensitivity, wide linear range,rapidity, simple instrumentation, easy automation and continuous analysis. CL analysishas been successfully explored for the analysis of a great number of important inorganicand organic substances at trace and ultra trace level in various fields includingbiotechnology, pharmacology, molecular biology, clinical medicine and environmentaldetection, and becomes one of most active investigative fields in the molecularspectroscopic analysis. Current research in CL analysis is mainly concentrated on twodirections. One direction is to discover new CL reactions to broaden the analytical scopeof the CL analysis. Another direction is to combine the established CL systems withnewly developing techniques to increase the applied value of CL analysis.The foundation of CL analysis is the CL reaction. Discovering new CL reactionsshould be the headspring of CL analysis. Usually, CL is emitted during anoxidation-reduction reaction. Many familiar oxidizing agents have been explored as theuseful oxidant for liquid phase CL analysis. These CL systems can be classified by theoxidants used as hydrogen peroxide system, cerium (Ⅳ) system, periodate system,hypohaliteas system as well as KMnO4 system, and so on. Among them, the research onthe KMnO4 CL system is a very active field. Now, the number of substances includinginorganic and organic species which can react with KMnO4 to emit CL exceeds 100.Based on these CL reactions, many sensitive CL methods were developed for thedetermination of drugs, toxicological, and biological substances, etc.During our recent works, it was found that injecting some substances into thereaction mixture of a CL reaction can result in a new CL reaction. This CL phenomenonis named as post-chemiluminescence (PCL) reaction since it occurs after the finish of aCL reaction. PCL reaction is a very peculiar CL phenomenon existed in most of CLreaction. Now, PCL phenomenon is unacquainted and mysterious CL phenomenon formany people, but it has potential value for fostering a new investigative field by lucubrating of this phenomenon.In the part of literature, the CL historical, the CL basic principle, the CLinstrumentation and the commonly used CL systems was firstly summarized.Subsequently, the CL systems with KMnO4 as the oxidant and their analyticalapplications were thoroughly reviewed.In the part of text, the PCL behaviour of more than 80 substances including drugs,environmental pollutants and inorganic anion in KMnO4 CL system was studied indetail. The involved CL systems include KMnO4-luminol system, KMnO4-lucigeninsystem, KMnO4-fluorescein system, KMnO4-HCHO system, as well as KMnO4-sulphitesystem. The experimental results indicated 40 substances can result in PCL inKMnO4-luminol system, but in other four CL systems, no PCL phenomenon wasobserved. The new CL methods were established for the 23 substances based on thesePCL reactions observed. Meanwhile, we also find the CL reaction of naproxen withKMnO4 and sulphite in neutral aqueous medium and the enhancement of ibuprofen onKMnO4-sulphite system, based upon these two CL reactions, we developed new CLmethods for the determination of naproxen and ibuprofen. The established CL methodswere successfully applied to the determination of analytes in pharmaceuticalpreparations and biological fluids. The major contents are described as follows.Strong CL signal was produced when four phenothiazine drugs, namely,chlorpromazine hydrochloride, perphenazine hydrochloride, fluphenazine hydrochlorideand thioridazine hydrochloride, was injected into the reaction mixture of luminol withKMnO4. Based on these observations, a new flow injection (FI) CL method wasdeveloped for the determination of above-mentioned drugs. The linear ranges of themethod were 2.0×10-9～1.0×10-6 g/mL chlorpromazine hydrochloride, 4.0×10-9～3.0×10-6g/mL perphenazine hydrochloride, 2.0×10-9～5.0×10-6 g/mL fluphenazine hydrochlorideand 5.0×10-9～1.0×10-6 g/mL thioridazine hydrochloride. The detection limits were4×10-10 g/mL chlorpromazine hydrochloride, 7×10-10 g/mL perphenazine hydrochloride,2×10-9 g/mL fluphenazine hydrochloride and 7×10-10 g/mL thioridazine hydrochloride.The proposed method was applied to the determination of chlorpromazinehydrochloride in injections and in mental patient's urine samples and the satisfactoryresults were achieved. The possible CL reaction mechanism was suggested by the studyof the reaction kinetics, CL spectra, florescence spectra, UV-vis absorbance spectra and other experiments.A new FI-CL method has been developed for the determination of sixβ-lactamantibiotics including amoxicillin, cefadroxil, cefoperazone sodium, cefazolin sodium,cefradine and ceftriaxone sodium. When above-mentioned antibiotic was injected intothe emerged stream of KMnO4 with alkaline luminol, strong CL signal was recorded.The method allows the measurements of 1.0×10-7～5.0×10-5 g/mL amoxicillin,1.0×10-7～8.0×10-5 g/mL cefadroxil, 1.0×10-6～3.0×10-5 g/mL cefoperazone sodium,1.0×10-6～3.0×10-5 g/mL cefazolin sodium, 3.0×10-6～5.0×10-5 g/mL cefradine and3.0×10-6～5.0×10-5 g/mL ceftriaxone sodium. The detection limits are 5×10-8 g/mLamoxycillin, 5×10-8 g/mL cefadroxil, 4×10-7 g/mL cefoperazonum sodium, 4×10-7 g/mLcefazolin sodium, 8×10-7 g/mL cefradine and 8×10-7 g/mL ceftriaxone sodium. Therelative standard deviations (RSD) in 11 repeated measurements are less than 2%. Theproposed method was successfully applied to the determination of amoxicillin inpharmaceutical preparation. The reaction mechanism was also briefly discussed basedon the study of CL spectra, fluorescence spectra and ultraviolet-visible absorbancespectra.It was found that strong CL signal was generated when injecting omeprazole intothe reaction mixture of KMnO4 and luminol. The experimental conditions that affectedthe CL reaction were optimized and a new FI-CL was developed for the determinationof omeprazole. The CL intensity is linearly related to the concentration in the range of2.0×10-8～1.0×10-5 g/mL. The detection limit is 3×10-9 g/mL omeprazole and the RSD(n=11) were 1.0% and 2.6% for 1.0×10-7 g/mL and 1.0×10-6 g/mL omeprazole solutions,respectively. The proposed method was successfully applied to the determination ofomeprazole in enteric-coated in capsules with satisfactory results.The experimental conditions for 12 substances including ketotifen fumarate,codeine phosphate, dimenhydrinate, ranitidine, colchicines, enalapril maleate,cloperastine, prednisone acetate, phlorglucinol, resorcinol, sulphite and sulfide wereoptimized. The analytical parameters of the methods were presented.A simple, rapid and sensitive FI-CL method is described for the determination ofnaproxen. It was found that strong CL signal was generated when naproxen was mixedwith KMnO4 and Na2SO3 in neutral aqueous medium. Under the optimum experimental conditions, the CL intensity was linearly related to the concentration of naproxen from4.0×10-9 to 1.0×10-6 g/mL (r=0.9993). The detection limit was 2×10-9 g/mL naproxen,the RSD for 1.0×10-7 g/mL naproxen solution was 1.5% (n=11) and the samplingfrequency was 120/h. The method was applied to the determination of naproxen inpharmaceutical preparation with satisfactory results. The mechanism of CL reaction wasdiscussed briefly.A simple and rapid FI-CL method is described for the determination of ibuprofen.Strong CL signal was detected when a mixture of the analyte and sulphite was injectedinto acidic KMnO4. The CL signal is proportional to the concentration of ibuprofen inthe range of 1.0×10-7～1.0×10-5 g/mL. The detection limit is 2×10-8 g/mL ibuprofen, theRSD is 1.8% (5.0×10-7 g/mL ibuprofen solution, n=11) and the sample measurementfrequency is 120/h. The proposed method was successfully applied to the determinationof ibuprofen in pharmaceutical preparations and in spiked urine samples. Themechanism of the CL reaction is also discussed.The thorough investigation of the PCL phenomena existed in KMnO4 CL system ishelpful to broaden the content and scope of the CL research, enrich the theory of CLanalysis, thoroughly understand essence of CL reaction and boost the development ofCL research.
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