【作者】 王朝阳；

【导师】 郑行望；

【作者基本信息】 陕西师范大学 ， 分析化学， 2007， 硕士

【摘要】 本论文由综述和研究报告两部分组成。综述部分主要介绍了无机氧化剂在化学发光分析中的应用进展。研究报告部分对次溴酸根-联氨-荧光素、鲁米诺-铁氰化钾、鲁米诺-高碘酸钾-高锰酸钾化学发光反应体系中氧化剂次溴酸根、铁氰化钾、高碘酸钾和高锰酸钾进行了比较广泛的研究，发现了电位调控化学发光现象，同时优化了反应条件，建立了测定联氨、硫离子、维生素C的化学发光分析新方法，从而从理论和实践上构建了一个提高氧化剂在化学发光体系中的氧化效率的新思路。化学发光分析方法具有灵敏度高、分析速度快、线形范围宽、仪器设备简单便宜、易于实现自动化等优点，已被成功地应用于生命科学、材料科学、临床医学及环境检测等领域。一般就化学发光分析的基本原理而言，化学发光信号的产生是以氧化还原反应为基础，并基于反应中的某些物质分子（如反应物、反应产物、反应中间体等）吸收化学反应所释放的能量，使相关分子产生电子激发态，激发态不稳定返回基态将能量以光的形式释放而产生发光的现象。因此，化学发光反应的分析特性与氧化还原反应的性质和特征等有着极为重要的关系。据此，许多有意义的研究思路如电致初生态试剂技术、新型氧化剂的合成与应用以及氧化还原反应介质或溶剂的调控等都曾致力于化学发光分析中氧化剂的氧化能力的调控，极大的提高了以氧化-还原反应为基础的化学发光分析的分析特性。但是，以调节某一氧化剂的氧化电位为研究基础，研究其化学发光行为，并据此而提高化学发光分析灵敏度的研究思路至今在国内外还很少报道。作者从化学发光反应的本质出发，提出运用电位调控技术来优化化学发光反应过程中的氧化剂的性能，对其氧化能力进行了有效的控制，以期有利于化学发光分析方法分析特性的提高。以次溴酸根-联氨-荧光素、鲁米诺-铁氰化钾化学发光体系为代表，作者对基于电位调控技术来提高化学发光反应过程中氧化剂的性能进行了研究，探索了这一研究思路的可行性。研究内容包括：一、在碱性条件下，BrO^-／Br^-电对中BrO^-氧化联氨的弱化学发光信号可以基于能量转移化学发光原理被荧光素所增敏。据此发现，并和流动注射技术相结合，建立了测定联氨的化学发光新方法。在最佳实验条件下，该方法对联氨的测定线性范围为3.0×10^-5-4.0×10^-8g．mL^-1，检出限（3σ）为1×10^-8g．mL^-1；对8.0×10^-7g．mL^-1联氧进行11次平行测定，其相对标准偏差为1.3％。将本法用于水样中联氨的回收试验分析并与标准方法进行了对照，结果满意。二、基于碱性条件下，硫离子对鲁米诺-铁氰化钾化学发光体系的增敏作用，建立了快速、简便、灵敏度高的流动注射化学发光分析法测定硫离子的新方法。研究发现，体系中氧化剂铁氰化钾的氧化性可基于在溶液中引入亚铁氰化钾而在一定范围内调控，进而能够有效地氧化硫离子而产生更强的化学发光且获得良好的分析特性。据此发现，不但建立了测定硫离子的化学发光分析新方法，而且还为提高化学发光分析方法的分析特性提出了新思路。在优化的实验条件下，测定硫离子的线性范围3.6×10^-6-1.2×10^-8mol．L^-1；检出限6×10^-9mol．L^-1，RSD小于3％（n=11）。本法成功的测定了湖水中硫离子的含量，采用标准加入法进行回收试验，结果满意。三、碱性条件下，维生素C对鲁米诺-高碘酸钾化学发光体系有很强的增敏作用。研究发现，向体系中加入强氧化剂高锰酸钾后，维生素C的对体系的增敏信号进一步增强且获得良好的分析特性。据此发现，建立了测定维生素C的鲁米诺-高碘酸钾-高锰酸钾化学发光分析新方法。在优化的实验条件下，测定维生素C的线性范围2.0×10^-8-1.8×10^-10g．mL^-1；检出限5×10^-11g．mL^-1，RSD=2.9％（n=11）。本法成功地用于测定了药剂中维生素C的含量，结果满意。更多还原

【Abstract】 Two sections are included in this thesis.One was the review,and theother was the research work.In the first part,the applications of some inorganic oxidantsin Chemiluminescence（CL） analysis are reviewed.The focus of the part is to summarizethe analytical application.In the second part, it was found that, by adjusting oxidationability of oxidants such as hypobromite,ferricyanide and periodate,the oxidation abilityof the oxidants can be easily controlled and presented the better analytical performancesin CL analysis.Moreover, the experimental conditions of the CL reactions wereoptimized and the feasibility of applicatipn of the present reactions to the determinationof hydrazine,sulfide and ascorbic acid was evaluated.For the first time, sensitive CLmethods for the detection hydrazine,sulfide and ascorbic acid based on potentialadjustment technique and flow-injection chemiluminescence has been developed.Potential adjustment technique is a promising alternative approach for the improvementof the sensitivity of CL analysis.CL analysis method has its advantages of high sensitivity, rapid analytical speed,wide linear range, simplicity and low cost of instrumentation, suitable for automationand has been successfully applied in life science, material science,clinical medicine andenvironmental monitoring, etc.As we know, chemiluminescence is probably bestdescribed as the emission of light by molecules that are electronically excited by virtueof their precursor’ participation in a highly exergonic chemical reaction, almostinvariably an oxidation-reduction reaction, generally, the nature of chemiluminescentreactions is oxidation-redution reactions.So, the analytical performances of CL systemsare closely related to the characteristics of oxidation-reduction reactions. Generallyspeaking, great efforts have been made to improve the sensitivity of CL analysis byadjusting the oxidation ability of oxidants, mainly from three aspects. Firstly. manyideas of on-line electrogenerating nascent state CL reagent were devoted to improve thesensitivity of the CL analysis. Secondly, exploiting and using some new oxidants as CLoxidants can also obtain better analytical performances. Thirdly, adjusting the medium（solvent and PH） of oxidation-reduction reactions could improve the oxidation ability of oxidants in the open literature, and the CL signal could be enhanced greatly, whichfinally resulted in the increased sensitivity.However, up to now, none of the reportsconcems the use of the potential adjustment technique to improve the analyticalperformance of CL analysis.Consideration of the nature of chemiluminescent reactions,we successfully usepotential adjustment technique to improve the analytical performance of the oxidants inCL analysis. Represented by the CL systems such as hydrazine- hypobromite-fluorescein.and luminol-ferricyanide CL system, sensitive CL methods based onpotential adjustment technique and flow-injection chemiluminescence has beendeveloped. Our actual research work includes the following aspects:Firstly, a rapid and sensitive flow-injection chemiluminescence method for thedetermination of hydrazine is described. The method is based on the strongchemiluminescence signal generated from the oxidation of hydrazine by hypobromite inalkaline medium and in the presence of both bromide and fluorescein. In the optimumexperimental conditions, the proposed CL method for hydrazine offered the linear rangeof determination is 3.0×10^-5-4.0×10^-8g.mL^-1 with the relative standard deviation of 1.3%(C=8.0×10^-7g.mL^-1, n=11) and the detection limit is 1×10^-8g.mL^-1（3σ）. Therecommended method has been successfully used for analysis of lake water sampleswith satisfactory results.Secondly, ferricyanide can react with luminol to produce weak CL in alkalinesolution,and the CL reaction can be catalyzed by sulfide. It was found that, by adjustingthe ratio of c（ferrocyanide） to c（ferricyanide）, the oxidation ability of ferricyanide canbe easily controlled and presented the better analytical performances in theluminol-ferricyanide CL system. The experiment shows that the sensitivity of the CLmethod was improved greatly and low detection limit was obtained. Based on thesefindings, a sensitive flow-injection CL method for sulfide was developed. In theoptimum analytical conditions, the proposed CL method for sulfide offered the linearrange of determination is 3.6×10^-6-1.2×10^-8 mol.L^-1 with the relative standard deviationof 2.7% for 1.0×10^-7 mol.L^-1 sulfide （n=11）.and the detection limit is 6×10^-9 mol.L^-1.The recommended method has been successfully used for analysis of lake watersamples with satisfactory results.Thirdly, ascorbic acid can be determined by its enhancement on the light emissionproduced by the oxidation of luminol by potassium periodate in the basic medium. Increase in the sensitivity of the determination was achieved by introducing potassiumpermanganate into the reaction mixture. The proposed procedure described in this paperwas based on its greatly enhancing effect on the luminol-complex oxidants, consistingof periodate and permanganate system.The proposed procedure allows quantitation ofascorbic acid in the range 2.0×10^-8 tol.8×10^-10g.mL^-1with a correlation coefficient of0.9993 （n=5） and relative standard deviation （R.S.D.） of 2.9% （n=11） at 1.0×10^-9g.mL^-1.The detection limit （3×blank） was 5×10^-11g.mL^-1 The method is successfully used todetermine in Vitamin C tablets.更多还原