Investigation On The Application Of Chemiluminescence Related To The Transition Metals Copper In Highest Oxidation State Complex

The existence of the transition metal in highest oxidation state has been known for more than a century.The known transition metal in highest oxidation state including a copper in trivalent state existed as the form of[Cu(HIO₆)₂]^5-å’Œ[Cu(H₂TeO₆)₂]^5-,a nickel in tetravalent state existed as the form of[Ni(H₂TeO₆)₂]^2-,a silver in trivalent state as the form of[Ag(HIO₆)₂]^5-å’Œ[Ag(H₂TeO₆)₂]^5-,a iron in hexavalent state existed as the form of K₂FeO₄.Hitherto,a considerable amount of research has been reported on the reaction rate of transition metals in highest oxidation state or the existence form of reaction active center etc.It has been proved that these transition metal cations in highest oxidation state can be stabilized by chelation with suitable polydentate ligands for their unstable character in an aqueous solution.The complexes of transition metals in highest oxidation state have occupied a major place in chemistry due to their catalysis on some chemical reaction for the form of free radicals is related to their particular structure.While,these reported application were not in analytical chemistry.The polydentate chelates of transition metals in highest oxidation state took on character of strong oxidation and supemormal catalysis.The chemiluminescence reactions based on their strong oxidation have been reported.The glucose,amino acid,protein and some medicine have been determined based on the oxidation chemluminescence reaction of regent[Cu(HIO₆)₂]^5-or electro-generated[Cu(HIO₆)₂]^5-.While,the chemiluminescence research based on their catalysis effect has not been reported.In this dissertation,[Cu(HIO₆)₂]^5-showed a supemormal catalysis effect on the chemluminescence reaction of luminol and hydrogen peroxide.The quantum yield of the luminol-H₂O₂ chemiluminescence catalyzed by[Cu(HIO₆)₂]^5-exceeded it catalyzed by other catalyzer such as Cu²⁺,Co²⁺and Cr³⁺,which were once regarded as the strongest catalyzer of the chemiluminesce reaction.The catalysis of[Cu(HIO₆)₂]⁵ is also stronger than of other peroxidase.It is important that the interference by these catalyser in the H₂O₂ determination is absent at the lower concentration of luminol and H₂O₂.The detection limit of H₂O₂ reaches to 10^-11mol L^-1(3α).Base on the chemluminescen reaction liminol-H₂O₂-[Cu(HIO₆)₂]^5-,the ultrasensitive and highly selective chemiluminescence method have been proposed for determination of hydrogen peroxide in human's exhaled breath condensate,in aqueous cigarette smoke condensate and hydroxyl radical produced in ultrasonic aqueous solutions.These developed coupling CL methods also open the possibility of a rapid and sensitive analysis of free cholesterol and free dopamine in serum that produce H₂O₂ in enzymatic reactions.The dissertation also discuss the oxidative chemiluminsence of[Cu(HIO₆)₂]^5-,which contains the chemluminesence of luminol's oxidation by[Cu(HIO₆)₂]^5-and direct oxidation by[Cu(HIO₆)₂]^5-.On basis of these chemiluminesnce systerm,novel method for determination of lincomycin hydrochloride,amikacin sulfate,ergometrine maleate,dexamethasone sodium phosphate,micronomicin sulfate,tobramycin have been built.(1)A Sensitive Chemiluminescence Method for the Determination of H₂O₂ in Exhaled Breath CondensateIn this paper,a novel flow injection chemiluminescence(FI-CL)method is proposed for the determination of picomolarL^-1levels of hydrogen peroxide(H₂O₂)in exhaled breath condensate (EBC).This method is based on the oxidation of a low concentration of luminol(10^-7M)by H₂O₂ at a low concentration level(＜10^-8M)in an alkaline medium catalyzed by a complex, K₅[Cu(HIO₆)₂](DPC),which is not interfered by other metal ions or horseradish peroxidase(HRP). Under the optimum conditions,H₂O₂ was determined over the range of 1.0×10^-10to 1.0×10^-8mol L^-1with a detection limit of(3σ)of 4.1×10^-11mol L^-1.The relative standard deviation(RSD)was 3.2%for 5 nmol L^-1H₂O₂(n=7).The proposed method offers the advantages of ultra-sensitivity, selectivity,simplicity and rapidity for H₂O₂ determination.It was successfully applied to directly determine trace amounts of H₂O₂(nmol L^-1)in human's EBC of both rheum and healthy volunteers. A statistically significant difference was found between patients with rheum(n=11)and control subjects without rheum(n=11).(2)The determination of hydrogen peroxide generated from cigarette smoke with an ultrasensitive and highly selective chemiluminescence methodMonitoring hydrogen peroxide(H₂O₂)in aqueous cigarette smoke condensate(CSC)is helpful for interpreting the relationship between cigarette smoke and oxidative stress,inflammation and disease.It is also significative for elucidating the pathogenic effects of CSC.In this paper,a novel flow-injection chemiluminescence(FI-CL)method was well established for determination of H₂O₂ in the complex sample CSC which did not need pretreatment.The sensitive and selective method is based on the CL reaction of luminol with low concentration(10^-7mol L^-1)and H₂O₂ at low concentration level(＜10^-8mol L^-1)in analkaline medium catalyzed by a complex Ks[Cu(HIO₆)₂] (DPC),which has proved no interference of other metal ions or horseradish peroxidase(HRP).The proposed method had been used to determine trace amount of H₂O₂ with a limit of detection(3α)of 4.1×10^-11mol L^-1,which enables minimal amount of sample for analysis.A satisfactory result has been gained for the determination of H₂O₂ in CSC sample by use of the proposed method.The concentration of H₂O₂ in two reference cigarette(84 cm,Longfeng)smoke condensate have been determined at 4-6μmol L^-1level.(3)Measurement of hydroxyl radical production in ultrasonic aqueous solutions by a novel chemiluminescence methodMeasurement methods for ultrasonic fields are important for reasons of safety.The investigation of an ultrasonic field can be performed by detecting the yield of hydroxyl radicals resulting from ultrasonic cavitations.In this paper,a novel method is introduced for detecting hydroxyl radicals by a chemiluminescence(CL)reaction of luminol-hydrogen peroxide(H₂O₂)-K₅[Cu(HIO₆)₂](DPC). The yield of hydroxyl radicals is calculated directly by the relative CL intensity according to the corresponding concentration of H₂O₂.This proposed CL method makes it possible to perform an in-line and real-time assay of hydroxyl radicals in an ultrasonic aqueous solution.With flow injection(FI)technology,this novel CL reaction is sensitive enough to detect ultra trace amounts of H₂O₂ with a limit of detection(3α)of 4.1×10^-11mol L^-1.The influences of ultrasonic output power and ultrasonic treatment time on the yield of hydroxyl radicals by an ultrasound generator were also studied.The results indicate that the amount of hydroxyl radicals increases with the increase of ultrasonic output power(≤15 WmL^-1).There is a linear relationship between the time of ultrasonic treatment and the yield of H₂O₂.The ultrasonic field of an ultrasonic cleaning baths has been measured by calculating the yield of hydroxyl radicals.(4)Determination of free cholesterol based on a novel flow injection chemiluminescence method by immobilizing enzymeA novel flow injection chemiluminescence method is proposed for determination of cholesterol in this paper.The cholesterol oxidase was immobilized onto sol-gel and prepared as an enzymatic reaction column.The determination of Cholesterol was performed by quantitative determination of hydrogen peroxide produced from enzymatic reaction.The luminol-H₂O₂-metal chelate diperiodatocuprate(â…¢)system ensured the method high sensitive and selective.Free cholesterol was determined over the range of 5.0×10^-8mol L^-1to 5.0×10^-7mol L^-1with a limit of detection(3σ)of 1.9×10^-8mol L^-1.The relative standard deviation for 2.5×10^-7mol L^-1was 2.7%(n=7).The proposed method offered the advantages of sensitivity,selectivity,simplicity and rapidity for flee cholesterol determination,and was successfully applied to the direct determination of free cholesterol in serum.(5)A novel Chemiluminescence Method for determination of unbound Dopamine in Serum by using potato tissue as an enzyme supplyA novel chemiluminescence-flow injection method was proposed for determination of trace dopamine which is based on an ultrasensitive chemiluminescence system of luminol-H₂O₂-diperiodatocuprate coupled with a selective enzymatic reaction in a potato tissue. The linear range of calibration curve was 2.1×10^-10mol L^-1to 2.1×10^-6mol L^-1and the limit detection was 7.2×10^-11mol L^-1.The relative standard deviation for 3.0×10^-9mol L^-1of dopamine was 2.1%(n=7).The proposed method was successfully applied for the direct determination of inherent dopamine in human serum.(6)A novel Chemiluminescence systerm for determination of ergometrine maleate base on the oxidation of diperiodatocuprate(â…¢)in alkaline conditionBased on the chemiluminescence(CL)reaction between diperiodatocuprate(â…¢)and ergometrine maleate in alkaline medium,a new flow injection chemiluminescence(FI-CL)method for the determination of ergometrine maleate was proposed.The linear range of ergometrine maleate was 1×10^-8～1×10^-6gmL^-1with the detection limit of 3.1×10^-9gmL^-1(3σ),The proposed method had good reproducibility with the relative standard deviation 3.0%(n=7)for 5×10^-8gmL^-1 of ergometrine maleate.It had been successfully applied to determine ergometrine maleate in injection.The solution of ascorbic acid was found sensitization effect on the chemiluminescence system of periodatocuprate(â…¢)and ergometrine maleate,the detection limit can be reach to 1.1×10^-9gmL^-1(3σ).The periodatocuprate(â…¢)-ergometrine maleate-ascorbic acid chemiluminescence method had been successfully applied to determine ergometrine maleate in serum.(7)A novel Chemiluminescence method for determination of dexamethasone sodium phosphate base on the oxidation of diperiodatocuprate(â…¢)in alkaline conditionA new flow injection chemiluminescence(FI-CL)method for the determination of dexamethasone sodium phosphate was proposed,which was based on the chemiluminescence(CL) reaction of dexamethasone sodium phosphate' oxidized by diperiodatocuprate(â…¢)and in alkaline medium,.The linear range of dexamethasone sodium phosphate was 1×10^-7～1×10^-5gmL^-1with the detection limit of 3.2×10^-8gmL^-1(3σ).The proposed method had good reproducibility with the relative standard deviation 1.4%(n=7)for 5×10^-7gmL^-1of dexamethasone sodium phosphate.It had been successfully applied to determine dexamethasone sodium phosphate in serum.(8)A novel Chemiluminescence method for determination of micronomicin sulfate base on the oxidation of diperiodatocuprate(â…¢)in alkaline conditionA new flow injection chemiluminescence(FI-CL)method for the determination of micronomicin sulfate was proposed.It was based on the chemiluminescence(CL)reaction of micronomicin sulfate and diperiodatocuprate(â…¢)and in alkaline medium.The linear range of micronomicin sulfate was 1×10^-7～1×10(-5)gmL^-1with the detection limit of 4.3×10^-8gmL^-1(3σ).The proposed method had good reproducibility with the relative standard deviation 3.2%(n=7)for 5×10^-7gmL^-1of micronomicin sulfate.It had been successfully applied to determine micronomicin sulfate in serum.(9)A novel Chemiluminescence method for determination of lincomycin hydrochloridebase on luminol-diperiodatocuprate(â…¢)systerm in alkaline conditionBased on the chemiluminescence(CL)reaction between diperiodatocuprate(â…¢)and luminol sensed by lincomycin hydrochloride in alkaline medium,a new CL meathod for determination of lincomycin hydrochloride was built by combining with flow injection technology.The linear range of lincomycin hydrochloride concentration was 1×10^-85×10^-6gmL^-1with the detection limit of 3.5×10^-8gmL^-1(3σ).The proposed method had good reproducibility with the relative standard deviation 1.7%(n=7)for 5×10^-8gmL^-1of lincomycin hydrochloride and was very sensitive and simple.It had been successfully applied to determine lincomycin hydrochloride in serum. (10)A novel Chemiluminescence method for determination of amikacin sulfate base on luminol-diperiodatocuprate(â…¢)systerm in alkaline conditionA new chemiluminescence meathod for determination of amikacm sulfate was built by combining with flow injection technology.The chemiluminescence(CL)reaction of luminol with diperiodatoeuprate(â…¢)in alkaline medium can be enhanced by the present of amikacin sulfate. The concentration range of linear response is 4×10^-9～4×10^-6gmL^-1.The detection limit is 1.2×10^-9 gmL^-1(3σ)with a relative standard deviation of 2.1%for the determination of 8.0×10^-9gmL^-1of amikacin sulfate n=7.The propoed method had been proved a very sensitive and simple method which was successfully applied to determine amikacin sulfate in serum.