Investigation And Application Of Novel Chemiluminescence Systems About Transition Metals In Highest Oxidation State Complex

The application of transition metals in highest oxidation state has been extensively studied since their existence was known in the beginning of the last century. Transition metals in highest oxidation state should be stabilized by chelating with suitable polydentate ligands. The known transition metals in highest oxidation state including [Ag(HIO6)2]5-, [Ag(H2TeO6)2]5-,[Cu(HIO6)2]5-, [Cu(H2Te06)2]5-,[Ni(HIO6)2(OH)2]6-, [Ni(HTeO4)6]2- and FeO42-. Transition metals in highest oxidation state complex have been considerably used in the analysis of several organic compounds and initiator of graft copolymerization due to their particular structure which focus on kinetics and mechanism of oxidation, the existence form of reaction active center and electron transfer reaction and so on.The application of Transition metals in highest oxidation state complex in analysis is summarized in Chapter 1. The research work of the dissertation is made up of three sections of novel chemiluminescence systems about transition metals in highest oxidation state complex.(I) The study of transition metals in highest oxidation state complex used as catalyter in luminol-H2O2 CL system and its application in chemiluminescence flow-through biosensorTransition metals in highest oxidation state complex (DPC, DPN, DPA) possess more excellent catalysis than previously reported (such as Co2+, Cu2+, Ni2+, Mn2+, Fe3+, Cr3+, KIO4, K3Fe(CN)6 and so on) in luminol-hydrogen peroxide CL system with low luminol concentration. It is important that the interference by these catalyzers in the H2O2 determination is absent with lower concentration of luminol and H2O2. The selectivity chemiluminescence reaction of luminol-H2O2-transition metals in highest oxidation state complex has been proposed for the determination H2O2 in rain water and artificial water.A novel enzyme reactor was prepared by calcium alginate fiber and amino modified nanosized mesoporous silica (CAF-AMNMS) as support. Combination the adsorption of enzyme on AMNMS with the cage effect of the polymer greatly increases catalytic activity and stability of immobilized enzyme. It was showed that the lifetime, stability and catalytic activity of enzyme reactor greatly improved by incorporating AMS into CAF to efficiently encapsulate enzyme. Glucose oxidase (GOD) was chosen as a model enzyme to explore the possibility of CAF-AMNMS as a matrix for enzyme immobilization in the design of a chemiluminescence (CL) flow-through biosensor. The detection limit of the flow-through biosensor combined with a novel luminol-dihydroxydiperiodatonickelate (DPN) CL system was lower than other reported CL biosensor. The proposed biosensor exhibits short response time, easy operation, long lifetime, high catalytic activity, high sensitivity and simple assembly. Then a novel enzyme reactor with co-immobilization ofβ-galactosidase and glucose in calcium alginate fiber and amino modified nanosized mesoporous silica (CAF-AMNMS) was prepared. The enzyme reactor was applied to prepare a chemiluminescence (CL) flow-through biosensor combined with a novel luminal-dihydroxydiperiodatonickelate (DPN) CL system we reported. The concentration range of linear response is 8×10-8-4×10-6 g mL-1 with the detection limit of 2.7×10-8 g mL-1 (3σ). It had been successfully applied to determine lactose in milk.(Ⅱ) Transition metals in highest oxidation state complex used as oxidant in luminol CL systemTransition metals in highest oxidation state complex (DPC, DPN, DPA) are good oxidants which can react with luminol to emit CL in alkaline medium. The CL intensity could be greatly enhanced by some compounds. In this system, using low concentration luminol can get excellent experimental result with higher selectivity than other luminol system. The possible mechanism of this system was first proposed based on the kinetic characteristic of the reaction, CL spectrum and UV spectra. Luminol-DPN-isoniazid CL system as the example, the oxidation reaction of MPN (main reactive form of the DPN) and isoizid proceeds via formation of three free radicals (isoniazid radical, diazene radical and isonicotinoyl) by two reversible one-electron transfer processes, at the same time, MPN oxidates luminol to form luminol radical. Luminol radical reacts with three radical from isoniazid to produce proxy anion. proxy anion decomposes to electronically excited 3-aminophthalate with loss nitrogen and then contributes CL emission by returning to ground state. Isoniazid, amikacin sulfate and dihydralazine sulfate have been determined based on the CL reaction.(1) New luminol chemiluminescence reaction using tetravalent nickel-periodate complex as a oxidant and its applications Here we report a new chemiluminescence (CL) reaction between luminol and tetravalent nickel-periodate complex (dihydroxydiperiodatonickelate, DPN) in alkaline medium. The CL intensity could be greatly enhanced by some compounds. The application of luminol-DPN system was studied using isoniazid as a model. In this system, luminol with very low concentration can get excellent experimental result with higher selectivity than other luminol system. It had been successfully applied to determine isoniazid in serum.(2) New luminol chemiluminescence reaction using dihydroxydiperiodatoargentate as oxidant for the determination of amikacin sulfateA new chemiluminescence (CL) reaction between luminol and dihydroxydiperiodatoargentate (K2 [Ag (H2IO6) (OH)2], DPA) was observed in alkaline medium. The CL intensity could be greatly enhanced by amikacin sulfate (AKS). So a new CL method for the determination of amikacin sulfate was built by combining with flow injection technology. The concentration range of linear response is 5.1×10-8-5.1×10-6mol L-1 with the detection limit of 1.9×10-8 mol L-1 (3σ). The proposed method had good reproducibility with the relative standard deviation 2.8%(n=7) for 5.1×10-7 mol L-1 of amikacin sulfate. It have been successfully applied to determine amikacin sulfate in serum.(3) Flow-injection chemiluminescence determination of dihydralazine sulfate in serum using luminol and dihydroxydiperiodatocuprate (Ⅲ) systemA novel flow-injection chemiluminescence (CL) method for the determination of dihydralazine sulfate (DHZS) is described. The method is based on the reaction of luminol and dihydroxydiperiodatocuprate (K2 [Cu (H2IO6) (OH)2], DPC) in alkaline medium to emit CL, which is greatly enhanced by DHZS. The optimum condition for the CL reaction was in detail studied using flow injection system. The experiments indicated that under optimum condition, the CL intensity was linearly related to the concentration of DHZS in the range of 7.0×10-9-8.6×10-7g mL-1 with a detection limit (3σ) of 2.1×10-9 g mL-1. The proposed method had good reproducibility with the relative standard deviation 3.1%(n=7) for 5.2×10-8 g mL-1 of DHZS. This method has the advantages of simple operation, fast response and high sensitivity. The special advantage of the system is that very low concentration of luminol can react with DPC catalyzed by DHZS to get excellent experiment results. And CL cannot be observed nearly when luminol with same concentration reacts with other oxidants, so luminol-DPC system has higher selectivity than other luminol CL systems. The method has been successfully applied to determine DHZS in serum.(Ⅲ) Direct oxidation by transition metals in highest oxidation state complex CL system possesses high selectivity which has been applied in determination of uric acid, lincomycin an adrenaline.Transition metals in highest oxidation state complex (DPC, DPN, DPA) are good oxidants in a medium with an appropriate pH value which can direct oxidate some compounds to emit CL. A flow injection CL method for the determination of uric acid, lincomycin and adrenaline based on the direct oxidation by transition metals in highest oxidation state complex CL system. The possible mechanism of direct oxidation CL system was first proposed based on the kinetic characteristic of the reaction, CL and fluorescence spectrum, UV spectra. In direct oxidation by transition metals in highest oxidation state complex CL system, uric, lincomycin react with DPA and DPN respectively by the oxidation of a single reversible two-electron transfer process to form excited complex of DPN-, DPA- analyte, then contributes CL emission by returning to ground state. But in DPN-adrenaline CL system, DPN oxidates adrenaline to produce excited 3,4-dihydroxyacetophenone which maximal fluorescence wavelength is located at 450 nm, then emit 450 nm CL by returning to ground state.(1) A novel flow-injection chemiluminescence determination of uric acid based on dihydroxydiperiodatoargentate (Ⅲ) oxidationA novel and high selectivity flow-injection chemiluminescence (FI-CL) system with dihydroxydiperiodatoargentate (Ⅲ) (DPA) is developed for the determination of uric acid for the first time. It is based on the reaction of dihydroxydiperiodatoargentate (Ⅲ) (DPA) with uric acid in alkaline medium to emit CL. With the peak height as a quantitative parameter applying optimum working conditions, the relative CL intensity was linear with the uric acid concentration in the range of 4.0×10-7-2.0×10-4 mol L-1 with a detection limit of 1.2×10-7 mol L-1(3σ). The relative standard deviation (RSD) was 2.1% for 5.0×10-5 mol L-1 uric acid (n=7). The proposed method hold higher selectivity than other CL methods and was applied to determination of uric acid in human serum. The possible CL reaction mechanism was also discussed briefly.(2) A novel chemiluminescence reaction system for the determination of lincomycin with dihydroxydiperiodatonickelate (Ⅳ)A sensitive and high selective chemiluminescence (CL) method was developed for the determination of lincomycin in acid medium using dihydroxydiperiodatonickelate (DPN) as oxidant. The mechanism leading to luminescence is discussed by comparing the spectra of fluorescence and CL. Relative CL intensity is linear in the range from 8.0×10-9-1.0×10-6 g mL-1, the limit of detection is 2.5×10-9g mL-1 (3a), and the relative standard deviation is 4.0% at 1.0×10-6g mL-1 of lincomycin (n=7). The method was successfully applied to determination of lincomycin in injections, human urine, and in serum samples.(3) A novel chemiluminescence reaction system for the determination of adrenaline with dihydroxydiperiodatonickelate (Ⅳ)A novel chemiluminescence (CL) system with dihydroxydiperiodatonickelate (Ⅳ) (DPN), for the first time, is developed for the determination of adrenaline. The possible CL emission mechanism was briefly discussed by comparing the fluorescence emission with CL spectra. Under the optimum conditions, the relative CL intensity was linear over the concentration ranging from 1.0×10-7 to 1.0×10-5 g mL-1 with a detection limit of 4.0×10-8 g mL-1(3σ) and relative standard deviation was 3.7 % for 2.0×10-6 g mL-1 adrenaline (n=11). The proposed method has been successfully applied to the determination of adrenaline in pharmaceutical preparations.