【作者】 张玲；

【导师】 方禹之； 何品刚；

【作者基本信息】 华东师范大学 ， 分析化学， 2005， 硕士

【摘要】 化学发光是在一些特殊的化学反应中吸收了反应释放的化学能,而处于电子激发态的反应中间体或反应产物由激发态回到基态时所产生的一种光辐射,化学发光分析是根据化学反应产物的光辐射(化学发光)确定物质含量的一种痕量分析方法。它的特点是灵敏度高和线性范围宽,不需要任何光源,只需要高灵敏度的光电转换元件和电子放大装置,因而仪器设备简单,操作简便,分析快速,易于实现自动化和连续分析,而且可与其它分析方法联合使用,进一步拓宽其应用范围。电致化学发光是将电化学方法和光化学方法结合起来的一种分析技术,它是通过对电极施加一定的电压进行电化学反应,电极反应产物之间再进行化学反应而发光。这种分析技术由于是利用电解技术在电极表面产生某些氧化还原物质而导致的化学发光,所以它保留了化学发光所具有的灵敏度高、线性范围宽、观察方便和仪器简单等优点;同时还具有化学发光无可比拟的优点,例如装置简单、重现性好、控制容易、可进行原位(in situ)发光,一些试剂可以重复使用,当多种组分同时存在时,可以施加不同波形、不同电压信号进行选择性测定等优点,特别是对于使用不稳定氧化物及产生短寿命激发态的化学发光,更具有灵敏度高的优点。流动注射(FI)作为一种强有力的样品处理技术,只有同特定的检测技术相结合才能形成一个完整的分析体系,但也正因此它才有极为广泛的适用性。对于化学发光分析法(chemiluminescence,CL),由于通常所使用的发光反应速度很快,所以必须保证样品与发光试剂能够快速、有效、高度重现的混合,流动注射技术满足了这一要求。化学发光分析法具有高灵敏度和宽的动态范围、仪器简单和不存在空白等优点,将其与流动注射的快速分析和高精度相结合使之成为一种有效的痕量分析技术,更兼有分析速度快、精度高、易实现自动化的特点。而随着药物分析的不断发展,它不但要求分析结果准确可靠,且要求分析方法简单快速,尤其是对痕量和微量药物分析,流动注射-化学发光法显得更为重要。更多还原

【Abstract】 Chemiluminescence （CL） can be defined as the characteristic emission of radiation from a molecule, atom or effective fiuorophore, in an excited electronic state, produced in an exothermic chemical reaction. It can take place in the gas, liquid and solid phase. In recent years, CL has become a powerful analytical tool for selective and sensitive detection of chemical species. CL applications in analytical chemistry have numerous advantages such as high sensitivity, a wide linear range, simple and inexpensive instrumentation, and considerable reduction of the background noise. There are numerous reports supporting the importance of chemiluminescent methods in analytical chemistry, including a great variety of fields such as food, biomedical, anyway as detection system.Electrogenerated chemiluminescence （ECL）, know as electrochemilumicescence, which combines chemiluminescence （CL） and electrochemistry. The CL reaction was initiated by an electrochemical reaction at electrode surface. Such an electro-initiation reaction introduces a large number of additional advantages, such as high sensitivity and selectivity, rapid and convenient operation and relatively simple instrumentation system. So ECL is becoming more and more important in many fields.Flow-injection chemiluminescence （FI-CL）, which combines chemiluminescence （CL） and flow-injection, has high efficiency and accuracy. It becomes more and more important in pharmaceutic analysis. The dissertation is composed of three chapters as followings:Chapter 1: Introduced the ECL and its application in analytical chemistry field, paid more attention to the types of ECL reaction and ECL sensors. Introduced the FI-CL and its application in pharmaceutic analysis. At last pointed out the purpose of the dissertation.Chapter 2: Determination of Co²⁺ based on the cobalt（ It ）-catalyzed electrochemiluminescence of luminol in acidic solutionThe catalytic reaction of cobalt（II） to Luminol and hydrogen peroxide was investigated, the electrochemical behavior of luminol in weakly acidic solution was studied. It is found that Co + remarkably enhances the electrochemiluminescence （ECL） of luminol in citric acid-sodium citrate buffer solution （pH=4.0） when a pulse potential （-1.8-+1.0 V, vs. Ag/AgCl） is applied to the Pt electrode. The selectivity for Co2+ is very good because most of the other water soluble metal ions do not interfere. A sensitive and selective ECL method for determination of Co2+ is proposed. After optimization of the reaction conditions and electrochemical parameters influencing the relative ECL intensity, the linear range responding to Co2+ is 5.0xl0-12-1.0xl0’7 mol/L, and the detection limit is 2.0><l 0’12 mol/L.Chapter 3: Flow injection chemiluminescence determination of injection dobutamine hydrochloride using luminol-ferricyanide/ferrocyanide systemIt was found that the weak chemiluminescence produced from the reaction of dobutamine hydrochloride with luminol in alkaline solution could be strongly enhanced by potassium ferricyanide and potassium ferrocyanide. Based on this found, a new flow injection chemiluminescence method is proposed for the determination of dobutamine hydrochloride. Under the optimum conditions, the proposed procedure has a linear range between 7 x 10-10g/ml and 5 x 10-7 g/ml, with a detection limit of 5.6 x 10-10g/ml for dobutamine hydrochloride（3o）. The proposed method has been applied for the determination of dobutamine in its pharmaceutical formulations. The results obtained compared well with those by an official method. The possible mechanism of this chemiluminescence reaction was also proposed.Chapter 4: Flow injection chemiluminescence determination of meloxicam by oxidation with N-bromosuccinimideA rapid and sensitive flow injection chemiluminescence （CL） method is described for the determination of meloxicam （MLX） based on its reaction with N-bromosuccinimide in alkaline medium. The CL intensity is greatly enhanced if fluorescein is presented in the reaction solutions. Under the optimum conditions, the logarithm of rela更多还原