毛细管电泳—电化学检测技术在药物分析中的应用研究
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摘要
毛细管电泳(Capillary Electrophoresis,CE)是20世纪80年代初建立并迅速发展起来的一种新型分离技术,是分析科学中继高效液相色谱之后的又一重大进展,具有分离效率高、分析速度快、样品和试剂消耗少、操作简便等特点,已广泛应用于化学、生命科学、药物和环境分析等领域。毛细管电泳具有多种检测技术,如紫外检测、激光诱导荧光检测、电化学检测和质谱等。其中,电化学检测技术,相对而言具有较高的灵敏度,且仪器简单、成本低廉、线性范围宽、操作简便,因而毛细管电泳-电化学检测法在分析化学领域得到了广泛的研究、应用和发展。由于许多药物的有效成分具有电化学活性,因此采用毛细管电泳-电化学检测方法分析药物有效成分是可行的。本论文在前人工作的基础上,开展了一些创新性的研究工作。本论文一共分为四个部分。
第一章绪论。首先简单回顾了毛细管电泳(CE)的历史、现状和发展趋势,对CE的基本原理和特点进行了简单介绍。其次对毛细管电泳分析中的检测联用技术进行了较为全面的综述,介绍了毛细管电泳技术在药物分析领域的应用,并简单阐述了本论文的研究目的和意义。
第二章探讨了利用毛细管电泳-电化学检测法测定中药黄芪及其制剂中的活性成分。研究了各种实验条件对分离效果的影响,得到了优化的实验条件。在优化的实验条件下,以直径300μm的碳圆盘电极为工作电极,检测电位为+0.95V(vs.SCE),在10mmol/L硼酸盐(pH8.2)的运行缓冲溶液中,六个分析物能够在17min内实现很好的基线分离,被测物浓度与峰电流在3个数量级呈良好的线性,检测限(S/N=3)范围从7.8×10~(-8)g/mL到1.1×10~(-7)g/mL。该方法具有良好的重现性,被测组分的迁移时间和峰高的相对标准偏差(RSDs)小于4%(n=7)。该方法已应用于实际样品的分析,样品处理简单,无需预富集,获得了令人满意的结果。
第三章对中草药杠板归中的五种活性成分阿魏酸、香草酸、槲皮素、咖啡酸、原儿茶酸进行了研究。首次采用毛细管电泳-电化学检测法成功的分离了杠板归中的阿魏酸、香草酸、槲皮素、咖啡酸、原儿茶酸,并优化了分离和检测条件。在优化的实验条件下,以直径300μm的碳圆盘电极为工作电极,检测电位为+0.95V(vs.SCE),在10mmol/L磷酸盐(pH9.2)的运行缓冲溶液中,五个分析物能够在17min内实现很好的基线分离,被测物浓度与峰电流在3个数量级呈良好的线性,检测限(S/N=3)范围从7.1×10~(-8)g/mL到9.3×10~(-8)g/mL。该方法已应用于实际样品的分析,样品处理简单,获得了令人满意的结果。
第四章利用毛细管电泳-电化学检测技术对饲料中的六种磺胺类药物磺胺脒、磺胺二甲嘧啶、磺胺甲嘧啶、磺胺二甲氧嘧啶、磺胺嘧啶、磺胺甲恶唑进行了直接分离与检测。研究了各种实验条件对分离效果的影响,得到了优化的实验条件,有很高的灵敏度和选择性。
Capillary electrophoresis (CE) is a new-style separation technique which was established and quickly developed in the early 1980s. Nowadays, CE has been widely used in the fields of chemistry, life science, pharmaceutics, environment analysis and so on, due to the advantages of higher separation power, short analysis time, small sample and reagent consumption and simplicity. There are many detection methodologies coupled with CE, such as UV-Visible detection (UV-Vis), Laser Induced Fluorescence detection (LIF), Electrochemical detection (ED) and Mass Spectrum (MS). Since ED has much advantage over other widely used techniques in that it is much more economical, without complicated pretreatment procedure, and it provides good selectivity as well as high sensitivity, it has flourished to various areas. Many medicaments and its effective components are electrochemical active, therefore, electrophoresis-electrochemical detection (CE-ED) method can be used to the separation and analysis of medicaments and its effective component. In this dissertation, we have carried out major innvative work on the base of previous work. The contents of this dissertation include four chapters:
Chapter 1 In the first chapter, the preface has reviewed the history, the current situation and the future trend of capillary electrophoresis (CE). The fundamental theory of CE and the characteristics of CE, the separation modes, the detections coupled with CE are introduced. It also contains the applications of CE in drug analysis. The goal and significance of this dissertation are introduced, too.
Chapter 2 In this section, a method based on capillary electrophoresis with electrochemical detection (CE-ED) had been developed for the determination of six kinds of active ingredients in Radix Astragali and its medicinal preprations. The analytes could be separated within 17 min in a 75cm length capillary at a separation voltage of 18 kV in a 10 mmol/L borate buffer (pH 8.2). A 300μm diameter carbon disk electrode generated good response at + 0.95V (vs. SCE) for all analytes. The relationship between peak currents and analyte concentrations was linear over about three orders of magnitude with detection limits (S/N = 3) ranging from 7.8×10~(-8) g/mL to 1.1×10~(-7) g/mL for all analytes. With relative standard deviations of less than 4% for both migration time and peak current (n=7), This proposed method has been successfully used for the determination of these analytes in real samples, and the assay result was satisfactory.
Chapter 3 In this chapter, the determination of active ingredients (ferulic acid, vanillic acid, quercetin, caffeic acid and protocatechuic acid) of Polygonum perfoliatum L. by capillary electrophoresis with electrochemical detection was studied. CE-ED was successfully used to separate and detect the five active ingredients for the first time, and the experiment conditions were optimized. Under the optimum conditions, the analytes could be separated within 17 min at a separation voltage of 18 kV in 10 mmol/L phosphate buffer (pH 9.2). A 300 urn diameter carbon disk electrode generated good responses at + 0.95V (vs. SCE) for the five analytes. The response was linear over three orders of magnitude with detection limits (S/N = 3) ranging from 7.1×10~(-8) to 9.3×10~(-8) g/mL for the analytes. This proposed method could be successfully applied to the analysis of the real samples with relatively simple extraction procedures, and the assay results were satisfactory.
Chapter 4 In this section, a method based on capillary electrophoresis with electrochemical detection (CE-ED) has been developed for the separation and determination of six sulfonamides (sulfaguanidine, sulfamethazine, sulfamerazine, sulfadimethoxine, sulfadiazine, and sulfamethoxazole) in feed. The effects of working electrode potential, pH and concentration of running buffer, separation voltage and injection time on CE-ED were investigated, and then the optimum experimental conditions were obtained.
第一章绪论。首先简单回顾了毛细管电泳(CE)的历史、现状和发展趋势,对CE的基本原理和特点进行了简单介绍。其次对毛细管电泳分析中的检测联用技术进行了较为全面的综述,介绍了毛细管电泳技术在药物分析领域的应用,并简单阐述了本论文的研究目的和意义。
第二章探讨了利用毛细管电泳-电化学检测法测定中药黄芪及其制剂中的活性成分。研究了各种实验条件对分离效果的影响,得到了优化的实验条件。在优化的实验条件下,以直径300μm的碳圆盘电极为工作电极,检测电位为+0.95V(vs.SCE),在10mmol/L硼酸盐(pH8.2)的运行缓冲溶液中,六个分析物能够在17min内实现很好的基线分离,被测物浓度与峰电流在3个数量级呈良好的线性,检测限(S/N=3)范围从7.8×10~(-8)g/mL到1.1×10~(-7)g/mL。该方法具有良好的重现性,被测组分的迁移时间和峰高的相对标准偏差(RSDs)小于4%(n=7)。该方法已应用于实际样品的分析,样品处理简单,无需预富集,获得了令人满意的结果。
第三章对中草药杠板归中的五种活性成分阿魏酸、香草酸、槲皮素、咖啡酸、原儿茶酸进行了研究。首次采用毛细管电泳-电化学检测法成功的分离了杠板归中的阿魏酸、香草酸、槲皮素、咖啡酸、原儿茶酸,并优化了分离和检测条件。在优化的实验条件下,以直径300μm的碳圆盘电极为工作电极,检测电位为+0.95V(vs.SCE),在10mmol/L磷酸盐(pH9.2)的运行缓冲溶液中,五个分析物能够在17min内实现很好的基线分离,被测物浓度与峰电流在3个数量级呈良好的线性,检测限(S/N=3)范围从7.1×10~(-8)g/mL到9.3×10~(-8)g/mL。该方法已应用于实际样品的分析,样品处理简单,获得了令人满意的结果。
第四章利用毛细管电泳-电化学检测技术对饲料中的六种磺胺类药物磺胺脒、磺胺二甲嘧啶、磺胺甲嘧啶、磺胺二甲氧嘧啶、磺胺嘧啶、磺胺甲恶唑进行了直接分离与检测。研究了各种实验条件对分离效果的影响,得到了优化的实验条件,有很高的灵敏度和选择性。
Capillary electrophoresis (CE) is a new-style separation technique which was established and quickly developed in the early 1980s. Nowadays, CE has been widely used in the fields of chemistry, life science, pharmaceutics, environment analysis and so on, due to the advantages of higher separation power, short analysis time, small sample and reagent consumption and simplicity. There are many detection methodologies coupled with CE, such as UV-Visible detection (UV-Vis), Laser Induced Fluorescence detection (LIF), Electrochemical detection (ED) and Mass Spectrum (MS). Since ED has much advantage over other widely used techniques in that it is much more economical, without complicated pretreatment procedure, and it provides good selectivity as well as high sensitivity, it has flourished to various areas. Many medicaments and its effective components are electrochemical active, therefore, electrophoresis-electrochemical detection (CE-ED) method can be used to the separation and analysis of medicaments and its effective component. In this dissertation, we have carried out major innvative work on the base of previous work. The contents of this dissertation include four chapters:
Chapter 1 In the first chapter, the preface has reviewed the history, the current situation and the future trend of capillary electrophoresis (CE). The fundamental theory of CE and the characteristics of CE, the separation modes, the detections coupled with CE are introduced. It also contains the applications of CE in drug analysis. The goal and significance of this dissertation are introduced, too.
Chapter 2 In this section, a method based on capillary electrophoresis with electrochemical detection (CE-ED) had been developed for the determination of six kinds of active ingredients in Radix Astragali and its medicinal preprations. The analytes could be separated within 17 min in a 75cm length capillary at a separation voltage of 18 kV in a 10 mmol/L borate buffer (pH 8.2). A 300μm diameter carbon disk electrode generated good response at + 0.95V (vs. SCE) for all analytes. The relationship between peak currents and analyte concentrations was linear over about three orders of magnitude with detection limits (S/N = 3) ranging from 7.8×10~(-8) g/mL to 1.1×10~(-7) g/mL for all analytes. With relative standard deviations of less than 4% for both migration time and peak current (n=7), This proposed method has been successfully used for the determination of these analytes in real samples, and the assay result was satisfactory.
Chapter 3 In this chapter, the determination of active ingredients (ferulic acid, vanillic acid, quercetin, caffeic acid and protocatechuic acid) of Polygonum perfoliatum L. by capillary electrophoresis with electrochemical detection was studied. CE-ED was successfully used to separate and detect the five active ingredients for the first time, and the experiment conditions were optimized. Under the optimum conditions, the analytes could be separated within 17 min at a separation voltage of 18 kV in 10 mmol/L phosphate buffer (pH 9.2). A 300 urn diameter carbon disk electrode generated good responses at + 0.95V (vs. SCE) for the five analytes. The response was linear over three orders of magnitude with detection limits (S/N = 3) ranging from 7.1×10~(-8) to 9.3×10~(-8) g/mL for the analytes. This proposed method could be successfully applied to the analysis of the real samples with relatively simple extraction procedures, and the assay results were satisfactory.
Chapter 4 In this section, a method based on capillary electrophoresis with electrochemical detection (CE-ED) has been developed for the separation and determination of six sulfonamides (sulfaguanidine, sulfamethazine, sulfamerazine, sulfadimethoxine, sulfadiazine, and sulfamethoxazole) in feed. The effects of working electrode potential, pH and concentration of running buffer, separation voltage and injection time on CE-ED were investigated, and then the optimum experimental conditions were obtained.
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