中文摘要准确控制元素在特定样品中的存在形态，才能可靠地评价重金属元素对机体健康的真实影响，因此，深入开展重金属在中药材中存在状态及其毒理学方面的研究，弄清重金属在药材中存在的形态及其生物毒性，具有重要的社会效益与经济效益。中药材重金属检查由总量控制向总量与形态并重方向转变，但是中药材涉及的重金属及其形态检测痕量甚至超量，且样品基质复杂，目前尚缺乏理想的集分离与分析于一体的快速、简单、重现性好的理想分析方法。毛细管电泳分离效率高、样品处理相对简单，在重金属形态分析领域具有独特的优势。本课题将毛细管电泳应用于中药材中重金属及其形态分析，并在此基础上，结合中药材用药安全评价及中药材质量量化分级探讨中药材质量控制新方法体系。主要工作及成果如下： 建立了中药材CE检测重金属总量方法体系。1）建立了同时测定中药材黄连中Cu、Pb的CE检测方法。以熔融石英毛细管( 57 cm×75 μm)为分离通道，运行缓冲液为pH 5.5的含0.05 M 乙酸钠的0.5 mM CTAB的缓冲液，分离电压-11 kV，检测波长254 nm，Cu2+加标回收率为90.1%，Pb2+加标回收率为86.2%，相对标准偏差(RSD)分别为5.1%与3.6%. 2）建立了一种分散液液微萃取-毛细管电泳检测细辛药材中Cd2+、Cu2+的新方法。药材样品消解、分散液液微萃取处理后，以AB-EDTA柱前络合CE检测。以熔融石英毛细管( 57 cm×75 μm)为分离通道，运行缓冲液为经NaOH溶液调pH至9.5的硼酸-乙腈溶液，分离电压25kV，检测波长254 nm，Cd2+在0.1~5mg/L范围内进行添加回收实验，加标回收率为98.06 %~103.55 %，相对标准偏差(RSD)为2.17 %；Cu2+在0.2~20 mg/L范围内进行添加回收实验，加标回收率为97.25 %~102.22 %，相对标准偏差(RSD)为2.02 %，并应用于不同产地细辛中多种重金属的CE同时检测、不同药材中多种重金属的CE同时检测。并在此基础上，中药材质量量化分级方法研究。结合中药材中重金属形态分析，进行了中药材质量量化分级。采用单因子指数（Pij=Cij/S）评价分级标准成功对不同产地中药材黄芪重金属污染程度进行了质量评价分级。按照单因子指数分为优质、合格、轻度污染、重度污染及极重污染五个等级，采用相应等级符号。 在CE检测重金属总量基础上，结合中药材用药特点，对其水提部位进行重金属初级形态分析。根据中药用药常用形式，分别考察了以药材原粉、去离子为溶剂进行提取，采用建立的方法进行了不同提取方式重金属的提取量，探讨了重金属初级形态分布特点。采用cDLLME-CE分析了黄连中Cu形态、黄芪中Cu、Pb、Cd的形态，川芎中Hg总量及不同Hg形态的分析。本文在建立了中药材CE检测重金属总量方法体系基础上，结合中药材中重金属形态分析，进行了中药材质量量化分级。并结合中药材原粉入药和汤剂给药的用药特点，拟定中药材中重金属限度标准。

AbstractThe species of heavy metals and their biological toxicology in Chinese medicinal materials is the basic premise to understand their biological toxicology and the real potential impact on human health. So the total amount test of heavy metals would be replaced with combination of the total amount and speciation test. However most of these analytical techniques to be interfered are limited for the complexity of the sample matrix. Capillary electrophoresis is an excellent system which combines the unique possibility to separate and detect the analytes with high resolution. So far as we know, few reports were done about herbal medicine due to the low heavy metal content and the serious interference from the sample matrix. In this paper capillary electrophoresis was used to analyze the total amount and speciation of heavy metals, and the results of thess works was applied for safety evaluation of traditional Chinese medicine and the quantized quality classification of Chinese medicinal materials. Main works are as follows: Firstly, the CE determination method of heavy metals in Chinese Medicinal Materials was established. Separations were performed on a fused silica capillary(57cm×75μm ID，an effective length of 50 cm)．The running buffer was composed of 0.05 M acetate and 0.5 mM CTAB solution (pH 5.5). The applied voltage was -11 kV and the capillary temperature was 25℃. The detection wavelength was 254 nm．The average recoveries were 86.2 for Pb and 90.1% for Cu, while the relative standard deviations were 5.1% and 3.6% respectively. 2）A novel method of dispersive liquid-liquid microextraction (DLLME) coupled with capillary zone electrophoresis was developed for determination of heavy metals in Radix et Rhizoma Asari. Test samples were digested and pretreated by DLLME, and then was coordinated with ABEDTA for CE detection. A fused silica capillary (57 cm × 75 μm ID) was used. The running buffer was composed of boric acid and acetonitrile with pH adjusted to 9.5. The applied voltage was 25 kV and the detection wavelength was at 254 nm. The average recoveries of Cd2+ was 98.06 % to 103.55% with the spiked concentration of 0.1-5.0 mg/L, Relative standard deviation (RSD) was 2.17 %. The average recoveries of Cu2+ was 97.25% to 102.22% with the spiked concentration of 0.2-20 mg/L, Relative standard deviation (RSD) was 2.02 % respectively. In addition, according to the content of heavy metals, Chinese medicinal materials are graded and divided into excellent, qualified, mild pollution, heavy pollution and heavy pollution category, using quantitative classification model for the quality of Chinese herbal medicine established in this paper.Oral administration is the common form of Chinese medicine，the primary speciation of trace elements in ligusticum wallichii franch was studied by CE determination. Deionized water and ethanol was used as extracting solvent to prepare water and ethanol fraction respectively, then the heavy metals were determined. In addition, a new sensitive and selective method based on chelatometric dispersive liquid-liquid microextraction (cDLLME) coupled with spectrophotometric determination for analysis of mercury in Rhizoma Chuanxiong digestion was proposed. Furthermore a new method using CE coupled with DLLME procedure for determination of mercury species in Chinese Medicinal Materials was developed. On the basis of these works, the limit standard of heavy metals in herbal medicine was drawn up considering the influence of its species.In this paper, the content and species of heavy metals in herbal drugs were determined by CE coupled with appropriate sample pretreatment methods. In addition, quantitative classification model for the quality of Chinese herbal medicine was established to evaluate its quality using single factor index method and the limit standard of heavy metals in herbal medicine was drawn up considering the influence of its species.