| Electrogenerated chemiluminescence (ECL) analysis not only owns theadvantages of the conventional chemiluminescence analysis, such as excellentsensitivity, wide linear range and simple optical requirement for instruments, but alsooffers some additional advantages. For example, the ECL reaction can be easilyregulated and manipulated by the applied potential. However, the selectivity of ECLmethods is poor due to the use of high electrolytic potential. In addition, the analyticalapplication fields of the ECL analysis are narrow. To overcome these drawbacks, thecombination of the ECL analysis with different separation techniques, such as highperformance liquid chromatogram (HPLC) and capillary electrophoresis (CE) etc.,were developed to improve performances of the ECL analysis and to broaden theanalytical application fields of the ECL analysis. In this paper, based on the ionassociation reaction of analyte with an appropriate cationic dye, by means of thechemically modified electrode (CME) technique (modifying a suitable modifier in thecarbon paste electrode), we investigated the properties of ECL by using this chemicallymodified carbon paste electrode (CMCPE).Two parts are included in the thesis: review and the research paper.In the first part of this thesis, the definiens, property, future prospect of ECLanalysis are reviewed. Then, the developing history and fabrication of CME and thedefiniens, property, developing of modifier and possible advancement of CMCPE arementioned. In addition to these, the combination with the CME technique and thefuture prospect of the ECL analysis are also given in this part.The second part of this thesis is experiment part, including:â… . Electrogenerated Chemiluminescence Analysis of Ion-associated Complex ofButyl Rhodamine B with Sodium Dodecyl Benzene Sulfonate and Its Application:It was found that a hydrophobic ion-associated complex, formed bybutyl-rhodamine B with sodium dodecyl benzene sulfonate (SDBS), could beselectively extracted in the bulk of the paraffin oil-based carbon paste electrode (CPE)in 0.02 mol/L HCl medium. Then, while the CPE was immersed in 0.1 mol/L NaOHmedium and 1.3 V electrolytic potential was applied to CPE, stronger ECL signal wasproduced due to the electro-oxidation of butyl-rhodamine B. And this ECL intensity was linear with the concentration of SDBS. Based on these findings, a selective andsensitive ECL method for SDBS was developed. Under the optimum experimentalconditions, the SDBS concentration in the range of 2.0×10-6～8.0×10-3 g/L wasproportional to the relative ECL intensity. The detection limit of the proposed methodWas 5×10-7 g/L.â…¡. Determination of Phosphate in Water by means of a New ElectrogeneratedChemiluminescence Technique Based on the Combination of Liquid-liquid Extractionwith Benzene Modified Carbon Paste Electrode:It was found that the hydrophobie ion-associated complex of themolybdophosphoric heteropoly acid with protonated butyl-rhodamine B (BRhB) couldbe formed and was further selectively extracted into the bulk of the paraffin oil-basedCPE. At the same time, compared with other modifiers, the benzene modified CPEcreated a suitable ECL reaction microenviroument for electro-oxidation BRhB toproduce the stronger ECL signal when a 1.30V electrolytic potential was applied to theCPE in the alkaline medium. Based on these findings, a selective and sensitive ECLmethod for indirectly detecting phosphate was developed. Under the optimumexperimental conditions, the ECL intensity was linear with the concentration ofphosphate in the range of 2.0×10-10～1.0×10-8 g/mL. The detection limit was 8×10-11g/mL.â…¢. A Highly Selective Electrogenerated Chemiluminescence Method for DetectingIsoniazid with C18 Modified Carbon Paste Micro-electrode.It was found that isoniazid could be selectively extracted into the bulk of carbonnanotubes-based microelectrode which was modified by C18-bonded silica (C18). At thesame time, carbon nanotubes created a favorable electrocatalytic behavior for ECLreaction of luminal and isoniazid to produce the stronger ECL signal when a 0.40Velectrolytic potential was applied to the electrode in the alkaline medium. Based onthese findings, a selective and sensitive ECL method for indirectly detecting·isoniazidwas developed. Under the optimum experimental conditions, the ECL intensity waslinear with the concentration of isoniazid in the range of 5.0×10-8～9.0×10-6 g/mL. Thedetection limit was 8×10-9 g/mL. |
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