毛细管电泳—电化学发光检测技术及其在生物碱分析中的应用
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摘要
生物碱是许多药用植物的有效成分,但传统的分离方法能耗大、杂质多、效率低、分离后样品的测定困难。毛细管电泳(CE)具有高效的分离能力,将它与高灵敏的电化学发光(ECL)方法相结合并用于包括生物碱在内的复杂样品的分离分析已引起人们极大的兴趣。目前,CE-ECL分离及检测技术的研究在国内外都刚刚起步,尤其是将该技术直接用于尿样及植物提取液中活性成分的分离测定具有一定的发展空间和实际应用价值。此外,利用化学修饰电极改善分离与分析,在CE-ECL领域鲜有报道。因此本工作的主要内容是利用电化学聚合法制备了稀土铕离子(Ⅲ)掺杂的类普鲁士蓝膜(Eu-PB)修饰的铂工作电极,并在此基础上建立了一系列基于Ru(bpy)_3~(2+)体系的CE-ECL联用的分析方法,实现了植物提取液及人体尿样中青藤碱、阿托品、樟柳碱和山莨菪碱等几种生物碱的分离与检测,有助于进一步拓展生物碱类物质的分离和检测方法以及扩大CE-ECL分析方法的应用范围。
     论文包括三个部分:
     第一部分文献综述
     第一章电化学发光分析概述
     介绍了电化学发光分析的基本原理和定量基础,对常见的电化学发光体系进行了归纳和总结,评述了化学修饰电极在电化学发光分析中的应用,展望了电化学发光分析的发展趋势和应用前景。
     第二章毛细管电泳技术概述
     介绍了毛细管电泳技术的基本原理、分离模式和检测方式,对近年来毛细管电泳与化学发光及电化学发光分析联用技术的研究现状和存在的问题进行了总结和评述。
     第三章生物碱及其分析方法
     对近年来生物碱分析的常用方法如电化学法、薄层扫描法、气相色谱法、高效液相色谱法及毛细管电泳法等进行了总结和评述,共引用文献55篇。
     第二部分Eu-PB修饰铂电极的制备及其性能研究
     第四章Eu-PB修饰铂电极的制备及其性能研究
     利用电化学聚合法制备了稀土铕离子(Ⅲ)掺杂的类普鲁士蓝膜(Eu-PB)修饰的铂电极,采用循环伏安法(CV)和示差脉冲伏安法(DPV)考察了该修饰电极在实验条件下的稳定性、电化学性质以及它对Ru(bpy)_3~(2+)体系CE-ECL信号的影响,并初步探讨了该修饰电极上Ru(bpy)_3~(2+)ECL反应的机理。
     第三部分毛细管电泳-电化学发光方法在生物碱分析中的应用研究
     工作基于Eu-PB修饰铂电极上Ru(bpy)_3~(2+)体系的CE-ECL,对青藤碱、阿托品、樟柳碱和山莨菪碱等生物碱进行了分离检测。主要内容如下:
     第五章青藤碱的CE-ECL检测研究
     本章首次建立了一种CE-ECL测定青藤碱的新方法。在最优条件下,ECL强度与青藤碱的浓度在0.01-1.0μg/mL范围内呈良好的线性关系(r=0.9993),检出限为2.0 ng/mL(3s),迁移时间和发光强度的相对标准偏差分别为0.93%和1.11%。将该法用于正清风痛宁片和中草药青风藤中青藤碱含量的测定,回收率在98.6-102.7%之间。
     第六章硫酸阿托品的CE-ECL检测研究
     本章建立了Eu-PB修饰电极上硫酸阿托品的CE-ECL分析方法。在最优条件下,ECL峰面积与硫酸阿托品的浓度在0.08-20μg/mL范围内呈良好的线性关系(r=0.9994),检出限为0.05μg/mL,迁移时间和发光峰面积的相对标准偏差分别为0.81%和3.19%。将该法用于注射液和人体尿液中硫酸阿托品的分离检测,回收率在90.9-99.6%之间。
     第七章唐古特山莨菪中托烷类生物碱的CE-ECL分离及检测研究
     本章首次建立了分离和检测唐古特山莨菪中樟柳碱和山莨菪碱的新方法。在最优条件下,ECL强度与樟柳碱的浓度和山莨菪碱的浓度分别在5.0×10~(-6)-1.0×10~(-3)mol/L(r=0.9993)和1.0×10~(-6)-1.0×10~(-3)mol/L(r=0.9991)范围内呈良好的线性关系,检出限分别为1.2×10~(-7)mol/L和4.3×10~(-8)mol/L(3s)。该法可用于植物唐古特山莨菪不同部位中两种生物碱的检测,并可对种子和根茎中樟柳碱的含量进行定量检测,平均回收率分别为102.9%和97.4%。
Alkaloids are usually the biologically active compounds in many Chinese medicinal plants.However,it is very difficult to detect the alkaloids extracted from the plants due to the large energy consumption,complicated sample matrices and low extraction yield in traditional separation methods.In recent years,there are increasing interests in coupling high-efficient capillary electrophoresis separation(CE)with high-sensitive electrochemiluminescence detection(ECL)for alkaloids analysis and other complicated samples.At present,the developments of CE-ECL are still in its preliminary state,and especially the related methods for the separation and determination of active components in urines and plant extracts are popular and welcome.However,there are few reports on the ulitization of chemically modified electrodes(CMEs)in the field of CE-ECL detection although the resolution and sensitivity can be improved by use of CMEs.Therefore,in this paper,a microdisk platinum electrode modified with Europinum(Ⅲ)-doped Prussian Blue analogue (Eu-PB)film was prepared by means of electrodepositing and used as a working electrode.Given this,a series of Ru(bpy)_3~(2+)-based ECL detection coupled with CE have been established for the determination of sinomenine,atropine sulfate,anisodine and/or anisodamine in plant extracts or in human urines,respectively.The present work would be helpful to the further developments of detection methods for some alkaloids and to the spreads of applications of CE-ECL technique.
     This paper consists of three parts.
     Part One Areview
     Chapter One Areview on ECL analysis
     This chapter introduces the basic principles and the quantification foundation of ECL analysis.The common ECL systems and their analytical applications,as well as the applications of CMEs in ECL are also summarized.In addition,the vista of the newly developing techniques and further trends of ECL methods are reviewed,too.
     Chapter Two A review on CE technique
     The basic principles,separation modes and detectors of CE are introduced in the chapter.The development of CE technique coupled with CL or ECL is reviewed as well.
     Chapter Three The development of analysis of alkaloids
     All kinds of methods including electrochemical methods,thin-layer chromatography(TLC),gas chromatography(GC),high-performance liquid chromatography(HPLC),and CE methods for the analysis of alkaloids in recent years are reviewed,and 55 references are cited.
     Part Two Preparation and performance of the Eu-PB modified platinum electrode
     Chapter Four Preparation and performance of the Eu-PB modified platinum electrode
     A platinum electrode modified with Europinum(Ⅲ)-doped Prussian Blue analogue (Eu-PB)film was prepared successfully by means of electrodepositing.The stability, electrochemical characteristics of the prepared.electrode,and its effect on Ru(bpy)_3~(2+)-based CE-ECL signal was studied by cyclic voltammograms and differential pulse voltammetries.The Ru(bpy)_3~(2+)-based ECL mechanism at the modified electrode was preliminarily discussed as well.
     Part Three Applications of CE-ECL methods in the analysis of alkaloids
     In this part,some research reports were given.Based on the Ru(bpy)_3~(2+)-based CE-ECL in the Eu-PB modified platinum electrode,a series of alkaloids including sinomenine,atropine,anisodine and anisodamine were separated and detected.The detailed works are as follows:
     Chapter Five Detection of sinomenine by CE-ECL
     A Ru(bpy)_3~(2+)-based ECL coupled with CE has been established for the determination of sinomenine for the first time.Under the optimized conditions,the ECL intensity was in proportion to sinomenine concentration in the range from 0.01 to 1.0μg mL~(-1)with a detection limit of 2.0 ng mL~(-1)(3s).The relative standard derivations of migration time and ECL intensity were 0.93 and 1.11%,respectively. The levels of sinomenine in Sinomenium tablet and Sinomenium acutum were easily determined with recoveries between 98.6%and 102.7%.
     Chapter Six Detection of atropine sulfate by CE-ECL
     A Ru(bpy)_3~(2+)-based ECL coupled with CE was developed for the determination of atropine sulfate at the Eu-PB modified platinum electrode.Under the optimized conditions,the ECL response peak area was in proportion to atropine sulfate concentration in the range 0.08-20μg·mL~(-1)(r=0.9994)with a detection limit of 0.05μg mL~(-1).The relative standard derivations of migration time and peak area were 0.81 and 3.19%,respectively.The proposed method has been successfully applied to direct determination of atropine sulfate in injection and especially in human urines with the recoveries of 90.9-99.6%.
     Chapter Seven Separation and detection of tropane alkaloids in Anisodus tanguticus by CE-ECL
     A Ru(bpy)_3~(2+)-based ECL coupled with CE has been established for the separation and detection of anisodine and anisodamine in Anisodus tanguticus for the first time. Under the optimized conditions,the ECL intensity was in proportion to anisodine and anisodamine concentrations in the range 5.0×10~(-6)-1.0×10~(-3)mol/L(r=0.9993)for anisodine and 1.0×10~(-6)-1.0×10~(-3)mol/L(r=0.9991)for anisodamine,with the detection limits of 1.2×10~(-7)mol/L and 4.3×10~(-8)mol/L,respectively.The proposed method has been successfully applied for the detection of two alkaloids in different parts of Anisodus tanguticus,and especially for the quantitative determination of anisodine in the plant seeds and roots with an average recovery of 102.9%and 97.4%, respectively.
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