【作者】 王颖莉；

【导师】 常丽萍；

【作者基本信息】 太原理工大学 ， 化学工程与技术， 2012， 博士

【摘要】 远志是传统的常用中药材之一,药用历史悠久,大规模的种植加工是远志中药材今后发展的方向。本课题主要针对远志有效成分现代提取技术,干燥炮制温度对远志化学成分的影响进行研究。研究结论对于提高远志有效成分提取率,降低干燥炮制过程对远志有效成分的影响具有重要理论意义和应用价值。选取山西、陕西、河北、内蒙、四川、甘肃六个产地的远志为研究对象,以山西远志为重点,系统研究了挥发油和远志总皂苷的现代提取工艺并对这些提取工艺的特点进行了分析总结；研究了远志多糖的结构特点及其抗氧化活性；在此基础上,考查了远志干燥过程对脂溶性和醇溶性成分的影响；基于中药炮制反应的特点,在模拟空气气氛条件下,采用热重方法研究了远志及其脂溶性和醇溶性成分的热解特性。得到以下主要结论：①CO2超临界法萃取远志挥发油收率高,可有效避免水蒸气蒸馏法所造成的对有效成分的影响。GC／MS分析表明,远志挥发油中含有多种活性成分,如alpha-细辛醚、甲基丁香酚、棕榈酸等。通过CO2超临界萃取得到alpha-细辛醚这一抗抑郁活性成分,有力地证明了远志抗抑郁作用的化学物质基础。山西远志中脂溶性成分含量达24%,其中,Octadec-9-enoic acid含量为81.40%,活性成分棕榈酸含量为7.34%。这一研究结论,为拓展远志的新用途提供了物质基础。②65%乙醇为溶媒,传统乙醇回流法提取远志总皂苷,连续索氏提取1h,提取率为1.11%；微波-酶法提取远志总皂苷,固液比为1：25,微波功率为255W,辐射时间为8min,远志总皂苷提取率达1.98%；而超声提取远志总皂苷,固液比1：25,超声时间20min时,远志总皂苷提取率为2.17%；超声波、微波-酶法现代提取方法可减少有机溶剂的使用量,两种方法的提取效率接近,为远志流浸膏的生产提供了新思路。③远志多糖可以显著提高衰老小鼠的脏器系数、延缓衰老,具有抗氧化作用。山西远志总多糖含有50%以上以葡萄糖计的多糖。红外图谱分析表明,远志多糖在500-4000cm-1范围具有多糖的特征吸收峰；紫外图谱分析中260nm及280nm处无特征吸收峰,表明远志多糖不含蛋白质和核酸类物质；远志多糖在快速热解阶段由多个峰组成是逐级热解。④6个不同产地远志超临界挥发油成分相似度在0.90以上。不同产地远志红外光谱分析表明,共有峰为2926.1cm-1,2856.7cm-1,1710.8cm-1,1647.8cm-1,1517.7cm-1,1458.7Cm-1；双指标系列分析表明,不同产地远志有明显差异。山西远志经50℃,70℃,90℃干燥后,超临界萃取物中挥发油成分发生了变化；红外光谱分析表明,共有峰相对强度受温度的影响较大,2926cm-1和2857cm-1处的甲基、、亚甲基的伸缩振动峰相对强度值始终大于1742cm-1处的羰基吸收峰的相对强度值；干燥温度对化学成分影响较大。远志干燥过程不仅有水分的挥发,同时存在脂溶性、醇溶性挥发分的析出。恒温干燥动力研究表明,不同产地远志药材在50℃、70℃和90℃恒温干燥过程符合Page模型。⑤模拟空气气氛条件下,6个不同产地远志、脂溶性和醇溶性成分的热重分析显示,远志的脂溶性成分中主要含有不饱和脂肪酸,其起始分解温度在170℃,热解过程可分成四个阶段,其中第二、三阶段主要是脂溶性挥发分的析出与燃烧；远志醇溶性成分起始失重温度在90℃,当温度超过90℃即有醇溶性挥发分的析出,235℃即会造成远志皂苷元的分解。远志药材挥发分的最大析出速率温度在200℃附近。远志挥发分特性指数：r可用于判断远志在空气气氛下热解过程对化学成分的影响,为分析中药炮制这一加热过程提供了一个可以定量分析的指标升温速率是影响远志热解过程的重要因素之一,在不同的升温速度下,远志热解反应的机理和过程会有所改变。动力学分析表明中药远志的炮制温度在120-270℃范围符合一级反应模型,活化能均值为22.78kJ/mol。更多还原

【Abstract】 Polygala, a traditional Chinese medicinal herd, has been commonly used for a long medicinal history. The large-scale cultivation and processing of Polygala should be the development direction of Chinese herbal medicines in the future. This study focuses on the extraction technology for the active ingredient of Polygala, the effect of temperature in drying and concocting process on the chemical ingredients of Polygala. The research conclusions have the important theoretical significance and application value to improving the utilization of traditional Chinese medicine active ingredients and reducing the effects of drying and concocting process of Polygala on active ingredients.The experimental samples are collected from Shan Xi, Shann Xi, He Bei, Inner Mongolia, Si Chuan and Gan Su regions in China, especially for the sample from Shan Xi province. The modern extraction technology of volatile oil and Polygala tenuifolia total saponins has been systematically researched and the features of these extraction technology were summarized. The structure features and anti-oxidation activity of Polygala tenuifolia polysaccharide and the effect of Polygala tenuifolia drying process on the lipid dissolved and alcohol dissolved components were also researched. Based on Chinese medicine processing reaction’s features, the pyrolysis properties of crude radix polygalae, its lipid solubility and alcohol-soluble constituents by thermogravimetric method in simulation air atmosphere conditions. The following main conclusions have been drawn:①CO2supercritical method has high extraction yield of volatile oil from radix polygalae, which can primely avoid the impact of distillation by steam on effective compositions. The results from GC/MS analysis show that the volatile oil from radix Polygalae has multiple active constituents, such as Alpha-ether, methyl eugenol, Palmitic acid of asarum. Alpha-ether, the antidepressant activity composition of as arum, from CO2supercritical extraction strongly proves the antidepressant components of Polygala.The content of lipid-soluble components in Polygala can reach to24%, in which the content of Octadec-9-enoic acid is81.4%and the content of active component of Palmitic acid is7.34%. This conclusion provides a material basis for expanding new uses of Polygala tenuifolia Willd..②The extraction rate of Saponins from Polygala using traditional ethanol reflux by Soxhlet extraction1h in the65%ethanol solvent is1.11%. In the same ethanol solvent, extraction rate of total saponins of Polygala by microwave-enzyme under the conditions of the solid-liquid ratio of1:25, microwave power of255W and radiation time of8min is1.98%. The use of ultrasonic technique can make the extraction rate of total saponins of Polygala enhance to2.17%under the ultrasonic time of20min. Ultrasonic microwave-emzyme modern extraction can decrease the use level of organic solvents, which provides a new thought for the production of Polygala’s extracts.③Polysaccharides from Polygala can significantly improve the organ coefficients and present a remarkable anti-aging and antioxidant effects in aging mice. The content of polysaccharides calculated according to glucose from Shanxi Polygala is above50%. The polysaccharides from Polygala presents the features of carbohydrate infrared absorption peak in the range of500-4000cm-1. The lack of ultraviolet absorption peak feature at260and280nm shows that the protein and nucleic acid-containing substances is not included in the polysaccharides from Polygala. During the rapid pyrolysis, the presence of multiple peaks show that the polysaccharide from Polygala is decomposed step by step.④The similarity of the composition of Polygala’s volatile oil from different habitats is more than0.90. The infrared characterization results of Polygala from different habitats shows that there are six common peaks in the position of2926.1cm-1,2856.7cm-1,1710.8cm-1,1647.8cm-1,1517.7cm-1and1458.7cm-1. The dual-index sequence analysis suggests that there are a significant differences for the different origins’Polygala.Shanxi Polygala after drying at50℃,70℃,90℃, the volatile oil components from supercritical fluid extraction occur some changes. Their infrared spectrum indicates that the relative strength of common peak is greatly affected by temperature. The strength value of methyl, and methylene vibration peak (2926cm-1and2857cm-1) is always greater than carbonyl absorption peak (1742cm-1), which shows that the drying temperature has a evident effect on chemical components. Polygala’s drying is not only the loss of water, but also the evolution of volatile’s grease. The maximum loss temperature and the weight loss rate during the drying of six Polygala samples are different, the peak temperature in drying phase ranges from119℃to135℃and the maximum decomposition temperature of alcohol-soluble extract is90℃.Dynamic study of constant temperature drying of Polygala from different origins at50℃,70℃and90℃shows that this drying process is suited to the Page model.⑤In the simulative air atmosphere, the liposoluble constituents and alcohol-soluble extract of six Polygala from different habitats have been analyzed by the thermogravimetric technique. Liposoluble constituent of Polygala mainly is fatty acid and its initial decomposition temperature is200℃. The pyrolysis process can be divided into four stages and its lipid-soluble volatiles are released and combusted in the second and third stages. The initial evoluted temperature of alcohol-soluble extracts of Polygala is90℃and the sapogenin start to decompose at235℃.Maximum emission temperature of volatiles from Polygala is near the temperature of200℃. The volatility characteristic index (r) of Polygala is: r can be used to determine the impact of the processing process on chemical constituents of Polygala, which provides a quantitative indicators to analyze the heating process of processing Chinese medicine.Heating rate is one of the important factors influencing the pyrolysis process of Polygala and it has a relation to the pyrolysis reaction mechanisms and processes. Based on the process of preparing Chinese medicine in the temperature range of120℃-270℃, the dynamics analysis shows that it meets the level model and its activation energy is22.78kJ/mol.更多还原