基于特征碎片离子的质谱导向策略用于中药白鲜皮中喹啉类生物碱成分的追踪分离  

Mass spectrometry guided strategy based on feature fragment ions for guided-separation on quinoline alkaloids from root barks of Dictamnus dasycarpus

作　　者：郭茜茜 毕启瑞 汪哲 谭宁华[1] GUO Xi-xi;BI Qi-rui;WANG Zhe;TAN Ning-hua(School of Traditional Chinese Pharmacy,China Pharmaceutical University,Nanjing 211198,China)

机构地区：[1]中国药科大学中药学院

出　　处：《中国中药杂志》2018年第19期3887-3892,共6页China Journal of Chinese Materia Medica

基　　金：国家自然科学基金项目(31470428);江苏省自然科学基金项目(BK20170738);江苏省博士后科研项目(1701055A);江苏省“双创团队”项目

摘　　要：白鲜皮作为一味传统中药,常应用于中药复方、临床以及实验研究中。喹啉类生物碱为其中一类主要活性成分,具有抗肿瘤、抗炎、抗菌、抗氧化、抗血小板聚集等多种活性。该研究首先对白鲜皮中生物碱成分进行化学分离,得到8个喹啉类生物碱(1~8),发现常规化学分离手段已难以再分离得到喹啉类生物碱成分,期望通过建立质谱分析策略用于指导靶向性获得白鲜皮分离剩余部分Fr. 8中更多喹啉类生物碱成分。该研究基于超高效液相色谱-电喷雾离子源串联质谱(UPLC-ESI-MS/MS),以白鲜皮中分离得到的8个喹啉类生物碱为对照品,研究该类成分的裂解规律,基于其特征离子m/z 200建立母离子扫描策略,再用于剩余部分Fr. 8中喹啉类生物碱的靶向分析与分离,最终又得到2个喹啉类生物碱8-methoxyflindersine(9)和N-metilatanina(10),其中化合物10为首次从该属植物中分离得到。结果表明,该方法不仅能快速、灵敏地对白鲜皮中喹啉类生物碱成分进行分析,还能够有效指导目标化合物的分离。The root bark of Dictamnus dasycarpus is one of common traditional Chinese medicines(TCMs). Quinoline alkaloids are one of the main active substances in this TCM and possess many biological activities including anti-titumor, anti-inflammation, anti-bacteria, anti-oxidation, and anti-platelet aggregation activities. In this study, eight quinoline alkaloids 1-8 were firstly separated from the root barks of D. dasycarpus. It was difficult to isolate more quinoline alkaloids from the remaining fraction 8 in D. dasycarpus by this conventional chemical separation, so the target analysis method combined LC-MS guided-separation of quinoline alkaloids from fraction 8 was established. MS/MS fragmentation patterns of eight quinoline alkaloids reference standard compounds 1-8 were studied by ultra-performance liquid chromatography-electrospary ionization-mass spectrometry(UPLC-ESI-MS/MS). Based on the feature fragment ion m/z 200, the parent ion scan mode was established for the target analysis of quinoline alkaloids in fraction 8. Finally, 8-methoxyflindersine(9) and N-metilatanina(10) were discovered and isolated quickly from fraction 8 guided by LC-MS, and their structures were identified by NMR and MS. Among them, compound 10 was isolated from the genus Dictamnus for the first time. These results indicated that this method is not only quick and sensitive for analyzing the quinoline alkaloids, but also to effectively guided-separate this kind of alkaloids in the root barks of D. dasycarpus.

关 键 词：白鲜皮 喹啉类生物碱 母离子扫描 靶向分离 UPLC—ESI—MS/MS 

分 类 号：R284.2[医药卫生—中药学]