余甘子回流过程中鞣质转化及药典含量测定方法合理性探讨

Tannin Transformation During the Reflux Process of Phyllanthus emblica L. and Discussion of the Content Determination Method in Chinese Pharmacopoeia

目的揭示2015年版《中国药典》中余甘子加热回流提取供试品制备过程中成分转化现象,研究其转化机制,提出新的供试品制备方法并进行提取工艺参数优化。方法采用高效液相指纹图谱对回流过程中余甘子中多种鞣质成分变化进行跟踪,并制备模型溶液揭示其转化机制,使用2015年版《中国药典》一部余甘子项下方法跟踪余甘子提取过程没食子酸含量变化,采用超声提取作为新的提取方法并进行方法学优化。结果指纹图谱结果显示,回流过程中诃黎勒酸、柯里拉京、没食子儿茶素等呈明显下降趋势,没食子酸、诃子次酸与鞣花酸则有明显上升趋势;模型溶液结果显示,在水解过程中,柯里拉京水解生成没食子酸和鞣花酸,而诃黎勒酸首先产生1分子柯里拉京和1分子的诃子次酸,柯里拉京则继续水解生成鞣花酸和没食子酸;药典回流提取法跟踪调查显示,随回流时间增加,没食子含量不断增加。超声提取的最佳优化结果为提取时间20min,提取功率300 W,溶媒用量30 m L,提取次数1次。结论余甘子加热回流过程中所含的水解鞣质如诃黎勒酸、柯里拉京等受热水解会导致所检测的没食子酸含量偏高,影响检测结果准确性,采用超声提取可抑制鞣质的水解,保证测定结果的准确性。

OBJECTIVE To reveal the phenomenon of component transformation during the heating reflux extraction of Phyllanthus emblica L.as described in the Chinese Pharmacopoeia,study its transformation mechanism,and propose a new Phyllanthus emblica extraction method.METHODS HPLC fingerprints were used to track the changes of various tannins in Phyllanthus emblica L.during the process of heating reflux extraction,and model solution was used to reveal the transformation mechanism.The pharmacopoeia method was used to track the changes of gallic acid content in the heating reflux extraction process of Phyllanthus emblica L..Finally,ultrasonic extraction was used as a new extraction method and the process was optimized.RESULTS The fingerprints showed that the contents of chebulagic acid,corilagin and gallocatechin decreased significantly during the heating reflux extraction process,while gallic acid,chebulic acid and ellagic acid increased significantly.The results of model solution showed that during the hydrolysis process,corilagin hydrolyzed to produce gallic acid and ellagic acid.While chebulagic acid hydrolyzed to produce one molecule of corilagin and one molecule of chebulic acid.And then the corilagin continued to hydrolyze.The tracking survey using pharmacopoeia reflux extraction method showed that with the increase of reflux time,the content of gallic acid was increasing.The best optimization result of ultrasonic extraction was as follows:extraction time 20 min,extraction power 300 W,solvent volume 30 m L,extraction 1 time.CONCLUSION The hydrolysis of hydrolyzable tannins contained in the Phyllanthus emblica L.during the heating reflux extraction process,such as chebulagic acid and corilagin,may cause the increase of detected gallic acid content,which may affect the accuracy of the detection results.Ultrasonic extraction can inhibit the hydrolysis of tannins,which can ensure the accuracy of the determination results of gallic acid.