绿色化学----浊点萃取和悬浮液滴分散液液微萃取技术在中药及制剂检测中的应用

密级：学校代码：10075分类号：学号：20090955理学硕士学位论文浊点萃取和悬浮液滴分散液液微萃取技术在中药及制剂检测中的应用学位申请人： 颜骏景指导教师： 石志红 教授学位类别： 理学硕士学科专业： 分析化学授予单位： 河北大学答辩日期： 二〇一二年六月Classified Index: CODE:10075 U.D.C: NO:20090955A Dissertation for the Degree of M. S.The Application of the Cloud-point Extraction Method and DLLME-SFO Technique in the Determination ofTraditional Chinese Herb andPreparationCandidate: Yan JunjingSupervisor: Prof. Shi ZhihongAcademic Degree Applied for: Master of ScienceSpecialty: Analytical ChemistryUniversity: Hebei UniversityDate of Oral Examination: June，2012摘 要中药材历史悠久，资源丰富，具有很高的实用价值和丰富的科学内容，是我国医药宝典中的重要组成部分。

但近些年因中药材中有害成分的残留影响了中药材的品质，同时阻碍了中药材走进国际市场的脚步，成为中药材发展的瓶颈。

为了尽早达到国际贸易的检测和限量标准，建立一套简便、快速、有效的检测技术具有十分重要的意义。

中药制剂的质量控制标准是决定中药制剂能否在国内外顺利发展的重中之重，解决质量控制技术问题迫在眉睫。

对中药制剂中多个有效成分的定性、定量检测是使中药制剂的质量控制得到提高的有效方法之一。

本文中详细介绍了一种新型的萃取方法，对中药制剂的质量控制标准制定和关键技术问题均能起到指导的作用。

全文共分为三章：第一章：在参考大量文献的基础上，对中药材中有害物质的前处理方法进行归纳总结，同时对中药制剂质量控制方法进行综述。

第二章：建立了超声辅助-浊点萃取法萃取中药材中多环芳烃并采用高效液相色谱-荧光检测器进行检测。

对表面活性剂浓度、超声波辅助提取时间、液固比、盐浓度以及平衡时间和温度等诸因素进行了优化。

五种多环芳烃在0.05-20 ng/mL的浓度范围内，峰面积对浓度的线性关系良好，相关系数在0.9989-0.9999之间，此方法已成功应用于地黄、板蓝根、黄莲、白芪、黄芩等五种中药材中多环芳烃残留的检测。

相对标准偏差为4.6 %-6.6 %。

在最佳条件下对地黄、板蓝根、黄莲、白芪、黄芩五种中药材中多环芳烃的含量进行测定。

第三章：建立了一种新型的悬浮凝固液滴-分散液液微萃取测定复方丹参注射液中丹参酮的新方法。

对分散剂和萃取剂的种类和用量以及离心速率和盐效应进行了优化。

在最佳条件下对四种品牌的复方丹参注射液中的丹参酮进行了检测。

本方法具有检出限低、耗用有机溶剂少、萃取时间短、灵敏度高、重现性好、操作简便等优点。

关键词 HPLC 浊点萃取法 悬浮凝固液滴-分散液液微萃取法 多环芳烃 丹参酮AbstractChinese herbal medicine is an ancient but still dynamic academic subject with high practical value. Chinese herbal medicines have been an important part of Chinese Pharmacopoeia. Recently, the residues of harmful ingredients in the herbal medicines affect the quality of the medicines, and hinder the pace of Chinese herbal medicines into the international market. So it has become the bottle-neck of the development of Chinese herbal medicines. In order to achieve the detection limits for international trade as soon as possible, establishing a simple, rapid and effective detection technology has a great significance.The undefined quality control standard has limited the development of Chinese herbal medicine internationally for a long time. Therefore, it has been a big issue to define the standard. One of the solutions is qualitative and quantitative determination of multiple effective test components in Chinese herbal medicine. This paper describes a new extraction method which plays a guiding role both in the definition of Chinese herbal medicine quality control standard and the solving of key technical problems in it.The paper has 3 chapters:Chapter 1: The pre-treatment methods of harmful substances in herbal medicines are summarized on the basis of large number of papers. At the same time, the quality control of traditional Chinese medicine preparation is reviewed.Chapter 2: A technique named Cloud Point Extraction adopted to extract and determine polycyclic aromatic hydrocarbons (PAHs) residues in Chinese Medicinal Materials is validated. HPLC coupled with a fluorescence detector is used for qualitative analysis.The effect of some parameters, for example, ultrasonic time and the cloud extraction, are optimized. On the optimized conditions, the PAHs of rehmannia, radix isatidis, goldthread root, Baiqi and scutellaria are measured. The experimental results show that it is a simple and fast pre-treatment method.Chapter 3: Dispersive Liquid-Liquid micro-extraction based on the solidification of a floating organic droplet (DLLME-SFO) followed by high-performance liquid chromatography-UV (HPLC-UV) is applied for enrichment and detection of Cryptotanshinone, Tanshinone I and Tanshinone IIA in Traditional Chinese Medicinal Injections Containing Salvia Miltiorrhiza Bunge. The important variable parameters, forexample, the type of disperser and extraction solvent and the volume of disperser and extraction solvent, are optimized. On the optimized conditions, different brands of tanshinone injectors are determined. This method with less organic solvent consumption is not only more accurate, but also fast and easy.Keywords HPLC Cloud-point extraction DLLME-SFO PAHs Tanshinone目 录第1章综述 (1)1.1 中药材有害残留物前处理技术 (1)1.2 中药材制剂前处理方法概述 (6)1.3 选题思想 (9)第2章浊点萃取-高效液相色谱法测定中药材中多环芳烃的残留 (11)2.1 引言 (11)2.2 实验部分 (12)2.2.1 仪器装置 (12)2.2.2 化学品和试剂 (12)2.2.3 萃取过程 (12)2.2.4 色谱条件 (13)2.3 结果和讨论 (13)2.3.1 浊点萃取条件的优化 (13)2.3.2 方法的线性范围和检出限 (17)2.3.3 样品测定 (18)2.4 结论 (18)第3章悬浮凝固液滴-分散液液微萃取测定复方丹参注射液中丹参酮 (20)3.1 引言 (20)3.2 实验部分 (21)3.2.1 仪器与试剂 (21)3.2.2 色谱条件 (22)3.2.3 实验方法 (22)3.3 结果与讨论 (23)3.3.1 DLLME-SFO萃取条件的优化 (23)3.3.2 方法的线性范围、精密度、重现性和检出限 (27)3.3.3 样品分析 (28)3.4 结论 (28)参考文献 (29)致谢 (35)攻读学位期间取得的科研成果 (36)第1章综述近些年，随着对食品安全、环境等问题的重视，中药材及制剂的监控也逐渐引起国家的关注。