【作者】 郝亮；

【导师】 吕九如； 杜建修；

【作者基本信息】 陕西师范大学 ， 分析化学， 2007， 硕士

【摘要】 化学发光分析由于灵敏度高，线性范围宽，仪器设备简单，已被人们用于许多领域中无机物及有机物的分析。当前的化学发光分析研究主要有两个方向。一个方向是发现新的化学发光反应，以拓宽化学发光分析的应用范围。另一个方向是将已发现的化学发光体系同其它技术如高效液相色谱、毛细管电泳等相结合，以增加化学发光分析法的应用价值。化学发光分析的基础是化学发光反应。化学发光反应大多数是氧化还原反应，许多熟悉的氧化剂，如高锰酸钾、四价铈、次卤酸盐等都已先后被用作液相化学发光反应的氧化剂。近年来，单线态氧由于具有较高的反应活性，在许多研究领域引起了人们的关注。在一些化学发光反应中，单线态氧也被建议为反应中间体，在反应中起着十分重要的作用。但很少有人有意识地将单线态氧作为化学发光反应的氧化剂。N-溴代丁二酰亚胺-H₂O₂反应是一个人们熟知的可以产生单线态氧的反应，该反应产生单线态氧的量子产率高。本研究以这一反应为基础，探讨了此反应中产生的单线态氧作为化学发光反应氧化剂的可行性。本论文分为两部分，第一部分为综述，第二部分为研究报告。在综述部分，简单介绍了单线态氧的电子结构、特性及其产生方法；总结了单线态氧的主要检测方法以及单线态氧的应用。研究报告由四部分组成：1流动注射化学发光法测定呋喃西林发现了碱性溶液中，呋喃西林同N—溴代丁二酰亚胺和过氧化氢间的化学发光反应，建立了测定呋喃西林的流动注射化学发光方法。该方法测定呋喃西林的线性范围为1.0×10^-7～1.0×10^-5g／mL，检出限为2×10^-8g／mL，相对标准偏差为4.0％(6.0×10^-6g／mL呋喃西林溶液，n=11)。该方法被用于呋麻滴鼻液，血浆及尿样中呋哺西林的含量测定。同时，对这一反应可能的化学发光机理也进行了初步地探讨。2流动注射化学发光法测定丙米嗪丙米嗪与N—溴代丁二酰亚胺和过氧化氢在碱性溶液中混合时，可以产生强的化学发光信号。据此，建立了测定丙米嗪的流动注射化学发光法。该方法测定丙米嗪的检出限为5×10^-9g／mL，线性范围为1.0×10^-8～1.0×10^-6g／mL。对4.0×10^-7g／mL的丙米嗪溶液进行11次平行测定的相对标准偏差为1.5％。该方法被用于药物制剂，血浆及尿样中丙米嗪的含量测定。3流动注射化学发光法测定中药中的芦丁芦丁与N—溴代丁二酰亚胺和过氧化氢在碱性溶液中混合时，可以检测到弱的化学发光信号。表面活性剂十六烷基三甲基溴化铵的存在对这一反应的化学发光信号有增强作用。利用这一现象，建立了测定芦丁的流动注射化学发光法。该方法测定芦丁的检出限为7×10^-8g／mL，线性范围为1.0×10^-7～1.0×10^-5g／mL，对1.0×10^-6g／mL芦丁进行11次平行测定的相对标准偏差为2.2％。该方法被用于四种中药中芦丁的含量测定。4中性介质中流动注射化学发光法测定苯酚发现了在十六烷基三甲基溴化铵胶束存在条件下，苯酚与N-溴代丁二酰亚胺（NBS）和过氧化氢在近中性水溶液中的化学发光反应，建立了利用这一反应测定苯酚的流动注射化学发光法。该方法测定苯酚的线性范围为1.0×10^-7～1.0×10^-5g／mL，检出限为3×10^-8g／mL，相对标准偏差为2.0％(1.0×10^-6g／mL苯酚溶液，n=11)。该方法被用于苯酚滴耳液中苯酚的含量测定。更多还原

【Abstract】 Chemiluminescence （CL） analysis has received much attention for theanalysis of organic and inorganic species in a variety of fields for its high sensitivity,wide dynamic range and inexpensive instrumentation. Current research in CL analysis isfocused on two general directions. One direction is to discover new CL reactions andbroaden the analytical scope of CL analysis. The other direction is to combine theestablished CL systems with newly developing techniques, such as high performanceliquid chromatograph and capillary electrophoresis, to increase the applied value of CLmethod. The former is more important since it is the foundation of the CL analysis.Usually, CL is emitted during an oxidation-reduction reaction and many familiaroxidizing agents, such as potassium permanganate, cerium （Ⅳ）, hypohalites and relatedoxidants, and so on, have been explored as the useful oxidant for liquid phase CLanalysis. Due to its hight reactivity, recently year, singlet oxygen has attracted muchattention in many fields. In many CL reactions, singlet oxygen has been frequentlysuggested as the reaction intermediate and played important role in these reactions.However, there have been few papers with the intention of using these species as theoxidant in the CL analysis. It’s well known that singlet oxygen （¹O₂） can be produced inthe reaction between N-bromosuccinimide and hydrogen peroxide with high quantumyield. Based on this reaction, we explored the possibility of using singlet oxygen asoxidant in the CL analysis.This thesis consists of review and research section.In the first part, the electronic structure, properties and generate methods of singletoxygen was briefly introduced. Then the main detection methods and the utilization ofsinglet oxygen were summaried.The research section consists of four parts.Part one, we proposed a simple flow injection chemiluminescence （CL） method forthe determination of nitrofurazone. This method was was based on the reaction ofnitrofurazone with H₂O₂ and N-bromosuccinimide in alkaline condition. The CL signalwas proportional to the nitrofurazone concentration in the range 1.0×10^-7～1.0×10^-5g/mL. The detection limit was 2×10^-8g/mL nitrofurazone and the relative standard deviation was less than 4% (6.0×10^-6g/mL nitrofurazone, n=11). The proposedmethod was successfully applied to the determination of nitrofurazone in compoundfuracillin nasal drops, human plasma and urine samples. The CL reaction mechanismwas also discussed briefly.Part two, singlet oxygen generated in the reaction between N-bromosuccinimideand hydrogen peroxide was used for the chemiluminescence oxidation of imipramine.Strong chemiluminescence signal was observed when imipramine was mixed withN-bromosuccinimide and hydrogen peroxide in alkaline condition. The chemilumin-escence signal was linearly dependent on the concentration of imipramine in the rangeof 1.0×10^-8～1.0×10^-6g/mL. The detection limit was 5×10^-9g/mL imipramine and therelative standard deviation was 1.5% for 4.0×10^-7g/mL imipramine solution in elevenrepeated measurements. The proposed method was successfully applied to thedetermination of imipramine in tablets, in human plasma and in human urine.Part three, rutin was determined by a new flow injection chemiluminescencemethod, based upon its reaction with N-bromosuccinimide and hydrogen peroxide in thepresence of cetyltrimethylammonium bromide surfactant micelles. The chemilumines-cence signal was proportional to the concentration of turin in the range of 1.0×10^-7～1.0×10^-5g/mL with a detection limit of 7×10^-8g/mL rutin. The relative standard deviationfor 1.0×10^-6g/mL rutin solution was 2.2% （n=11）. The proposed method wassuccessfully applied to the determination of rutin in four Chinese medicinal.Part four, the chemiluminescence reaction of phenol, N-bromosuccinimide andhydrogen peroxide in neutral aqueous medium in the presence of cetyltrimethy-lammonium bromide surfactant micelles was discovered. Based on this reaction, a newflow injection chemiluminescence system for the determination of phenol was proposed.The chemiluminescence signal was proportional to the concentration of phenol in therange of 1.0×10^-7～1.0×10^-5g/mL with a detection limit of 3×10^-8g/mL rutin. The relativestandard deviation for 1.0×10^-6g/mL phenol solution was 2.0% （n=11）. The proposedmethod was successfully applied to the determination of phenol in phenol ear drops更多还原