黄连等6味中药中生物碱苷类成分的发现、分离和结构鉴定  

Discovery,isolation and structural identification of alkaloid glycosides in six traditional Chinese medicine such as Coptis chinensis

作　　者：王茹 关亮俊 陈两绵[2] 彭锐 朱晶晶[2] 刘晓谦[2] 高慧敏[2] 王智民[2,3] WANG Ru;CUAN Liang-jun;CHEN Liang-mian;PENG Rui;ZHU Jing-jing;LIU Xiao-qian;GAO Hui-min;WANG Zhi-min(Tianjin University of Traditional Chinese Medicine,Tianjin 301617,China;National Engineering Laboratory of Quality Control Technology of Chinese Materia Medica,Institute of Chinese Materia Medica,China Academy of Chinese Medical Sciences,Beijing 100700,China;School of Pharmacy,Henan University of Chinese Medicine,Zhengzhou 450046,China)

机构地区：[1]天津中医药大学,天津301617 [2]中国中医科学院中药研究所中药质量控制技术国家工程实验室,北京100700 [3]河南中医药大学药学院,河南郑州450046

出　　处：《中国中药杂志》2023年第17期4598-4609,共12页China Journal of Chinese Materia Medica

基　　金：中国中医科学院科技创新工程项目(CI2021A04401);国家重点研发计划“中医药现代化研究”专项(2017YFC1701900)。

摘　　要：生物碱是许多中药的重要活性成分,生物碱苷是其存在形式之一。因糖单元的引入改善了生物碱苷类成分的水溶性从而呈现更好的生物活性。鉴于生物碱苷在植物体内的含量较低,其研究相对较少。该研究采用超高效液相色谱串联四极杆飞行时间质谱(UPLC-QTOF-MS/MS),对含有重要生物碱的6种中药(黄连、黄柏、北豆根、青风藤、金果榄和防己)进行生物碱苷的识别和成分分析,结果表明除金果榄外,其他5种药材均含有生物碱苷,基于在线紫外吸收光谱、一级质谱准分子离子峰、二级质谱碎片离子信息以及相关文献报道,对各药材所含生物碱苷类成分进行鉴定,从中鉴定了42个生物碱苷,其中黄连和北豆根中鉴定出的生物碱苷较多,而黄连中的11个均为潜在的新化合物。进而以黄连为例,采用水煎煮,水提液经大孔吸附树脂粗分,D151阳离子交换树脂、ODS和MCI等柱色谱纯化,结合半制备高效液相色谱,进行目标生物碱苷的分离,得到2个新的生物碱苷,通过质谱、核磁等波谱数据鉴定其结构分别为(S)-7-羟基-1-(对羟基苄基)-2,2-N,N-二甲基-1,2,3,4-四氢异喹啉-6-O-β-D-吡喃葡萄糖苷和(S)-N-甲基四氢巴马汀红碱-9-O-β-D-吡喃葡萄糖苷。该研究对于丰富黄连的化学成分信息、深入开发黄连药用资源具有重要意义,同时可为从其他中药中快速鉴别和分离生物碱苷类成分提供参考。Alkaloids are important active ingredients occurring in many traditional Chinese medicines,and alkaloid glycosides are one of their existence forms.The introduction of saccharide units improves the water solubility of alkaloid glycosides thus presenting better biological activity.Because of the low content in plants,alkaloid glycosides have been not comprehensively studied.In this study,ultrahigh performance liquid chromatography-quadrupole time of flight-tandem mass spectrometry(UPLC-QTOF-MS/MS)was employed to identify and analyze the alkaloid glycosides in Coptis chinensis,Phellodendron chinense,Menispermum dauricum,Sinomenium acutum,Tinospora sagittata and Stephania tetrandra.The results showed that except Tinospora sagittata,the other five herbal medicines contained alkaloid glycosides.Furthermore,the alkaloid glycosides in each herbal medicine were identified based on UV absorption spectra,quasimolecular ion peaks in MS,fragment ions information in the MS/MS,and previous literature reports.A total of 42 alkaloid glycosides were identified.More alkaloid glycosides were identified in C.chinensis and Menispermum dauricum,and eleven in C.chinensis were potential new compounds.Furthermore,the alkaloid glycosides in the water extract of C.chinensis were coarsely se-parated by macroporous adsorption resin,purified by column chromatography with D151 cation exchange resin,ODS and MCI,combined with semi-preparative high performance liquid chromatography.Two new alkaloid glycosides were obtained,and their structures were identified by mass spectrometry and NMR data as(S)-7-hydroxy-1-(p-hydroxybenzyl)-2,2-N,N-dimethyl-1,2,3,4-tetrahydroisoquinoline-6-O-β-D-glucopyranoside and(S)-N-methyltetrahydropalmatubine-9-O-β-D-glucopyranoside,respectively.This study is of great significance for enriching the information about the chemical composition and the in-depth development of C.chinensis.Meanwhile,it can provide a reference for rapid identification and isolation of alkaloid glycosides from other Chinese herbal medicines.

关 键 词：生物碱苷 黄连 黄柏 北豆根 青风藤 金果榄 防己 

分 类 号：R284.1[医药卫生—中药学]