【作者】 黄端华；

【导师】 张兰；

【作者基本信息】 福州大学 ， 分析化学， 2006， 硕士

【摘要】 本文以当今分析化学研究领域的热点问题-天然药物为研究对象,运用毛细管区带电泳和毛细管胶束电动色谱新技术、新方法,对三类天然药物的药效成分、物理常数和药代动力学等进行了全面的、系统的研究。无论对于拓展高效毛细管电泳方法学的应用范围,还是丰富药物分析新方法等方面都有重要意义。全文共分四章,主要包括一下几个方面:一、建立了祖师麻主要成分的毛细管电泳分析和研究的新方法。采用胶束毛细管电动色谱法对祖师麻五种主要成份进行了分析。优化了分离检测条件,发现:当分离电压为20 kV,运行缓冲液为硼砂硼酸（20 mmol/L,pH 9.0）,SDS为10 mmol /L,压力进样30 mbar×10 s,在波长214 nm处,紫丁香苷,7-甲氧基香豆素,瑞香苷,瑞香素和7-羟基香豆素的线性响应范围分别为:1.0-100μg/mL ,1.5-100μg/mL ,5.0-75μg/mL,5.0-75μg/mL,1.0-75μg/mL;检测限达到0.3μg/mL、0.5μg/mL,1.7μg/mL,1.7μg/mL和0.3μg/mL。方法成功的用于实际样品祖师麻片的提取液和祖师麻注射液的检测。在成分分析的基础上尝试了瑞香苷、瑞香素和7-羟基香豆素三种香豆素的离解常数的测定,利用毛细管区带电泳在不同pH条件下有效淌度的倒数（1/μe）与缓冲液中氢氧根离子浓度（[OH-]）的线性关系,推导了CE-UV法测定三种香豆素（瑞香苷,瑞香素和7-羟基香豆素）的电离常数的线性模型并建立了三种香豆素的pKa测定方法;同时也采用经典方法-紫外分光光度法对这些物质的pKa进行测定以验证CZE法的可靠性,实验结果说明CE-UV法用于三种香豆素的电离常数的测定,快速、简便、结果可靠。进一步以瑞香苷为例,进行了另一种物理常数――水解速率常数测定的方法研究,建立了瑞香苷水解速率常数测定的最佳电泳分析方法,实现瑞香苷和瑞香素实时浓度检测,进而计算得水解的速率常数,并总结了温度及催化剂浓度对速率常数影响的规律。在所加入的盐酸浓度为1M的条件下,温度为337,347,351,363,371 K时的水解常数分别是1.1×10^-3,4.6×10^-3,6.6×10^-3,17.3×10^-3,33.5×10^-3 min^-1。同时,根据阿仑尼乌斯公式计算该反应的活化能为91.62 kJ mol^-1。实验结果表明,水解速率常数将随着温度的升高而逐渐变大,同时反应速率常数也随催化剂盐酸的浓度增加而增大。更多还原

【Abstract】 The high Performance capillary electrophoresis (CZE) and micellar electrokinetic capillary chromatography (MECC) are applied to three herbal medicines study and analysis in this thesis. This investigation was very useful for expanding the application of CE,MECC and developing analytic method for Chinese traditional medicine. The thesis consist four chapters and main content as follows:1. The research and analysis of the major ingredients in Cortex DaphnesThe MECC is applied to the separation and determination of five major components in the tablets and the injection of Cortex Daphnes according to experimental condition as follows: 20 mM borate (pH=9.0), 10 mM SDS, and applied voltage of 20 kV, detection UV 214 nm, 30mbar pressure injection for 10s. The experimental results show that the calibration graph is linear from 1.0 to100μg/mL for syringin, from 1.0 to 75μg/mL for herniarin, from 5.0 to 75μg/mL for daphnin, from 5.0 to 75μg/mL for daphnetin, from 1.0 to 75μg/mL for umbelliferone, and the detection limits of syringin, herniarin, daphnin, daphnetin and umbelliferone was 0.3μg/mL、0.5μg/mL,1.7μg/mL,1.7μg/mL和0.3μg/mL, respectively. The proposed method successfully analyzed the components in the tablets and the injection of Cortex Daphnes.pKa values of investigated cumarin derivatives in Cortex Daphnes were determined by capillary zone electrophoresis (CZE) in the borax and Potassium dihydrogen phosphate (KDP) buffers,which method relies on measuring the ionic mobility of the solute as a function of pH. The pKa values obtained through the method were in agreement with the values by typical spectrophotometric method.Daphnetin is the product of the hydrolysis reaction of daphnin. A high sensitivity and good repeatability method base on the proposed MECC method for the determination of five ingredients above and being made little adjustment was applied to the determination of the hydrolysis rate constants of daphnin. Under the optimum condition, at the separation voltage of 24 kV and UVλ= 320 nm, the rate constants of更多还原