| Chemiluminescence (CL) method is known to be a powerful analytical technique that possesses high sensitivity, wide linear range, rapidity, simple instrumentation, simple operation and so on. It has been widely applied in inorganic and organic species in different fields such as biotechnology, pharmacology, molecular biology, clinical medicine and environmental detection. Chemiluminescent reagent is the basis of CL analysis. To reaseach and develop new chemiluminescent reagent or to find new chemiluminescent reagent from the known commercialized reagent and to establish new CL system is very important to improve analytical sensitivity and widen application range of CL analysis.The transition metal in highest oxidation state such as Ag(Ⅲ),Cu(Ⅲ),Ni(Ⅳ) can exist stably in the alkaline medium by suitable multi-tooth ligand complexing. They are all strong oxidant with higher stability under the appropriate condition, its complex ion can produce free radicals because of its unique structure. They have been widely used in the study of inorganic, organic reaction kinetics and oxidation mechanism. Unfortunately, they are less applied in analytical chemistry, bis(hydrogenperiodato) argentate(Ⅲ) complex anion is more less research and its application in chemiluminescence analysis.This study starts from the applications of transition metal in highest oxidation state complex in CL analysis, the chemiluminescence characteristics of them is explored. This research is made up of two aspects, one aspect is the establishment of the Ag (Ⅲ) complex-chemiluminescence system and the investigatation of preliminary mechanism of the reactions, the other aspect is its application in pharmaceutical analysis. The main content of this article is as follows:1 Chemiluminescence characteristics and mechanism of transition metal in highest oxidation stateThe chemiluminescence characteristics of the transition metals in highest oxidation state complex in acid medium is explored. For the first time the CL mechanism of the Ag (Ⅲ) complex-Fluoroquinolones in acid medium is studied. At the same time the preliminary mechanism of the reactions is also investigated.2 Application of Ag (Ⅲ) complex chemiluminescence system in pharmaceutical and body fluids analysisA novel chemiluminescence reaction system with bis(hydrogenperiodato) argentate(Ⅲ) complex anion (Ag(Ⅲ) complex, [Ag(HIO6)2]5-) with flow injection technique is developed for the determination norfloxacin(NFLX), enoxacin(ENX),ofloxacin (OFLX) and lofloxacin(LOFLX) in the pharmaceutical and body fluids. Under the optimize experimental conditions, the CL intensity is proportional to the concentration of the drugs in the rang 1.3×10-8-5.4×10-6 g mL-1 for NFLX,2.5×10-8-3.3×10-6g mL-1 for ENX,2.2×10-8-4.5×10-6g mL-1 for OFLX and 1.9×10-8-4.9×10-6g mL-1 for LOFLX. The limit of detection (s/n=3) is 3.1×10-9 g mL-1 for NFLX,2.3×10-8 g mL-1 for ENX,5.3×10-9 g mL-1 for OFLX and 1.1×10-8 g mL for LOFLX. These new method can perform simple, sensitive, rapid and practical.3 Application of Ag (Ⅲ) complex chemiluminescence system in determination of fluoroquinolone in milk and body fluids.Based on the novel chemiluminescence reaction system-Ag(Ⅲ)-H2SO4; A high sensitivity detection for enrofloxacin (ENLX), lomefloxacin (LMFX) and pefloxacin (PFLX) is achieved in food, pharmaceutical and human body fluids. The detection limit is 9.1×10-9 g mL-1 for ENLX,3.1×10-9 g mL-1 for LMFX and 4.4×10-9 g mL-1 for PFLX. the CL intensity is proportional to the concentration of the drugs in the range 3.0×10-8-3.7×10-6 g mL-1 for LMFX,4.0×10-7-3.0×10-6g mL-1 for ENLX and 1.5×10-7-2.8×10-6g mL-1 for PFLX. The proposed method offers the advantages of sensitivity, simplicity and rapidity for the three drugs determination. The proposed methods are applied successfully to the determination of these compounds in real samples. The chemiluminescence characteristics of them is also explored and compared.4 Enhanced effect on CL emission of [Ag(HIO6)2]5--luminol system and Hydroxycamptothecin analysis.A novel chemiluminescence method is developed for the determination of 10-Hydroxycamptothecin (HCPT) based on CL reaction between [Ag(HIO6)2]5- and luminol in alkaline solution. The enhanced degree of CL emission is proportional to HCPT concentration. The effect of the reaction conditions on CL emission is examined. Under optimal conditions, the linear ranges for HCPT is 2.0×10-8-8.0×10-6 g mL-1, the detection limits is 6.5×10-9 g mL-1 with a relative standard deviation of 2.1% for the determination of 1.6×10-7 g mL-1 of HCPT (n=11). For spiked urine samples and spiked serum samples the recoveries of HCPT were in the range of 97.0-108% and the results are satisfactory. A possible mechanism of enhanced CL emission was also suggested.5 Quenching effect on CL emission of [Ag(HIO6)2]5- -luminol system and sulfanilamides analysis.A simple, sensitive, rapid and novel CL method is proposed for the determination of sulfonamides based on CL reaction between [Ag(HIO6)2]5- and luminol in alkaline solution. The quenching effect of sulfonamides on CL emission of [Ag(HIO6)2]5- -luminol system is found. The quenching degree of CL emission is proportional to sulfonamides concentration. The effects of the reaction conditions on CL emission and quenching are examined. Under optimal conditions, the detection limits (s/n=3) are 7.2×10-9,1.7×10-8,8.3×10-9 g mL-1 for sulfadiazine, sulfameter, and sulfadimethoxine respectively. For spiked urine samples and spiked serum samples the recoveries of sulfanilamides are in the range of 91.3%-112% with the RSDs of 1.6-2.8% (n=5)and the results are satisfactory. A possible mechanism of CL emission and quenching effect was also suggested.
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