【作者】 何德勇；

【导师】 章竹君；

【作者基本信息】 西南师范大学 ， 分析化学， 2003， 硕士

【摘要】 化学发光(chemiluminescence，简称CL)是化学反应的反应物或生成物吸收了反应过程中释放的化学能，电子由基态跃迁至激发态，在由激发态返回到基态时所产生的光辐射。根据化学发光反应在某一时刻的发光强度或发光总量来确定反应中响应组分含量的分析方法叫做化学发光分析法。此法具有灵敏度高、线性范围宽、仪器简单、分析快速等优点。化学发光分析法作为一种有效的痕量分析方法在药物分析、环境科学及生命科学等领域中具有广泛的应用前景。 本文的主要内容是铁氰化钾化学发光体系在儿茶酚胺类药物中的分析应用。全文由两部分组成。 第一部分综述介绍了自1995年以来化学发光药物分析的理论研究与应用进展情况。 第二部分研究报告介绍了铁氰化钾化学发光体系在儿茶酚胺类药物中的分析应用。它分为三章，第一章介绍了儿茶酚胺类药物的药理作用，并对分析方法做了较为详细的综述。第二章扩大了铁氰化钾直接氧化化学发光体系的应用范围，详细研究了在碱性条件下铁氰化钾作为氧化剂直接氧化儿茶酚胺类药物产生化学发光，从而建立起了简单、灵敏、快速测定肾上腺素、异丙肾上腺素、多巴酚丁胺的流动注射化学发光新方法，并对其反应机理进行了初步探讨。第二章是在鲁米诺-铁氰化钾化学发光体系的基础上，基于儿茶酚胺类药物对此体系发光的增强作用，建立测定肾上腺素、多巴胺、去甲肾上腺素、异丙肾上腺素和多巴酚丁胺的高灵敏度、快速的流动注射化学发光新方法，并对其反应机理进行了初步探讨。虽然该体系选择性较铁氰化钾直接氧化化学发光体系差，但灵敏度提高了2-3个数量级。 1．铁氰化钾直接氧化化学发光体系在儿茶酚胺类药物中的分析应用 1)．铁氰化钾-肾上腺素体系 基于铁氰化钾可以在碱性条件下直接氧化盐酸肾上腺素产生化学发光这一现象，并结合流动注射技术建立了一种直接测定盐酸肾上腺素的流动注射化学发光新 摘 要方法。该方法的线性范围是5刀xlo叉5刀xlo‘旮mL，检出限为2．8x10一为mL门a人对 5刀xl ohemL的盐酸肾上腺素连续门次测定的标准偏差为 3．2％。该法己成功测定了注射液中的盐酸肾上腺素的含量，结果令人满意c2）．铁氰化钾一异丙肾上腺素体系 在NaOH碱性介质中，铁氰化钾可以直接氧化盐酸异丙肾上腺素产生化学发光，由此建立了一种快速、简单、灵敏测定盐酸异丙肾上腺素的流动注射化学发光法。盐酸异丙肾上腺素浓度在 5刀xlo久巧．oxlo”毛／mL范围内与发光强度呈良好的线性关系。该方法的检测限为 1．Zxlo’毛／mL（3a人对 5刀xlo－’g／mL的盐酸异丙肾上腺素连续测定 11次，其 RSD—2．8％。该法应用于注射液中盐酸异丙肾上腺素含量的测定，结果令人满意。3）．铁氰化钾一多巴酚丁胺体系 根据在碱性介质中铁氰化钾可以氧化盐酸多巴酚丁胶产生较强的化学发光，并结合流动注射技术，建立了测定盐酸多巳酚丁胺的新方法。盐酸多巴酚丁胺浓度在2刀xlo“叉 l刀xlo“‘g／mL范围内与化学发光强度呈良好的线性关系，检出限达6刀xlo一、／mL（3X对 5刀xlo”’g／hL的盐酸多巴酚丁胺连续平行测定 11次，相对偏差（RSD）为1．8％。将本法用于注射液中盐酸多巳酚丁胺含量的测定，结果另人满意。2．鲁米诺一铁氰化钾化学发光体系在儿茶酚胺类药物中的分析应用1）．鲁米诺一铁氰化钾一肾上腺素体系 在NaHCO上NaOH介质中，铁氰化钾和鲁米诺混合可以产生化学发光，盐酸肾上腺素的存在可以大大增强此发光。在此基础上结合流动注射技术建立了一种高灵敏度测定盐酸肾上腺素的流动注射化学发光新方法。该方法的线性范围在10x 10J’－50xl0－’g／mL，检出限为4．sxloJ’g／mL（3a）。对l．oxlo”’g／mL的盐酸肾卜腺素连续 11次测定的标准偏差为 4二％。该法己成功测定了注射液中的盐酸肾上腺素含量，结果令人满意。2）．鲁米诺一铁氰化钾一多巴胺 铁氰化钾与碱性鲁米诺溶液混合产生化学发光，盐酸多巴胺的存在可以大大增强其化学发光强度。在此基础上结合流动注射技术建立了一种高灵敏度测定盐酸多巴sy的流动注射化学发光新方法。该方法的线性范围在 1刀X10’0l刀xl08g／mL，检 2 摘 要出限为 4．oxlo””g／mL门a人对 1．oxlo“’g／mL的盐酸多巳胺连续 11次测定的标准偏差为2．4％。该法己成功测定了注射液中盐酸多巴胺的含量，结果令人满意。3）．鲁米诺一铁氰化钾一去甲肾上腺素 在NaHCO3－NaOH介质中，重酒石酸去甲肾上腺素的存在对LuminolK。Fe（CN）0化学发光体系有很强的增敏作用。在此基础上建立了流动注射化学发光法测定重酒石酸去甲肾上腺素的新方法。该法的线性范围是 5刀X10’、／mL巧．OX10”、／mL。检测限为 1．sxlo“’、／mL。对 5刀xl09g／mL的重酒石酸去甲肾上腺素连续平行测定＊次，相对标准偏差为2石％。更多还原

【Abstract】 Chemiluminescence (CL) is defined as the emission of light from an electronically excited state species which is produced during the course of a chemical reaction, and is observed when the electronically excited product or intermediate formed decays to the ground state with a photon emitted. Due to its high sensitivity, wide linear range and simple instrumentation, the Chemiluminescence method has been successfully applied in pharmaceutical science, environmental science and life science, and has become one of the most powerful techniques in analytical chemistry.Studies on the application of potassium ferricyanide Chemiluminescence system in catecholamine measurements were carried out in this work. The dissertation is divided into two parts.Part 1 describes the development of the Chemiluminescence theory and its application in pharmaceutical analysis since 1995.Part 2 describes the application of potassium ferricyanide Chemiluminescence system in catecholamine measurements. It consists of three chapters. The chapter 1 presents the function of catecholamine and the analytical methods for catecholamine measurement in open literatures. The chapter 2 describes a novel Chemiluminescence system for the determination of adrenaline, isoprenaline and dobutamine based on the potassium ferricyanide oxidating the catecholamine directly in alkaline medium. The mechanism of the method was discussed briefly too. Chapter 3 describes the Chemiluminescence system for the determination of catecholamine including adreanline, dopamine, noradrenaline, isoprenaline, dobutamine, which based on the reaction of potassium ferricyanide with luminol in the NaHCO3-NaOH buffer solution sensitized by the analytes. The proposed method is sensitive, simple, rapid. The possible Chemiluminescence reaction mechanism was also discussed briefly.1. The application of Ferricyanide Chemiluminescence system in catecholamine.1). Ferricyanide-adrenaline chemiluminescence systemA flow injection chemiluminescence method for the determination of adrenaline hydrochloride which based on the reaction of ferricyanide with adrenaline hydrochloride in sodium hydroxide medium. The chemiluminescence intensity is proportional toadrenaline hydrochloride concentration over the rage 5.0x10-8-5.0x10-6g/mL with a detection limit 2.8x10-8g/mL (3d). The relative standard deviation (R.S.D) is 3.2% for 5x10-7g/mL adrenalin hydrochloride (n=11). The proposed method was applied to determination of adrenaline hydrochloride in pharmaceutical preparations successfully. 2). Ferricyanide - isoprenaline chemiluminescence systemA novel flow injection chemiluminescence method for the determination of isoprenaline hydrochloride was proposed. It was based on the reaction of ferricyanide with isoprenaline hydrochloride in sodium hydroxide medium. The linear range is 5.0x10-8-5.0x10-6 g/mL with a detection limit of 1.2x10-8g/mL (3a). The relative standard deviation is 3.2% for 5.0x 10-7 g/mL isoprenaline hydrochloride (n=11). The proposed method was simple, quick, sensitive and applied to determination of isoprenaline hydrochloride in pharmaceutical preparations successfully. 3). Ferricyanide-dobutamine chemiluminescence systemA novel flow injection chemiluminescence (FI-CL) system for the determination of dobutamine hydrochloride was described. It was based on the chemiluminescence reaction of ferricyanide oxidating dobutamine directly. The chemiluminescence intensity is proportional to dobutamine hydrochloride concentration over the range 2.0x10-8g/mL-1.0x10-6g/mL. The detection limit is 6.0x10-9g/mL with the relative standard deviation of 1.8%(n=11). This method has been successfully applied to determination of dobutamine hydrochloride in injection.2. The application of ferricyanide-luminol chemiluminescence system incatecholamine measurement1). Ferricyanide-luminol-adrenaline chemiluminescence systemA novel flow injection chemiluminescence (FI-CL) system for the determination of adrenaline hydrochloride was described. It was base更多还原