超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法对三七果中皂苷类成分的快速鉴定  

Rapid Identification of Saponins in Panax Notoginseng Fruits by Ultra High Performance Liquid Chromatography-Orbitrap High Resolution Mass Spectrometry

作　　者：曲正义[1] 郑培和[1] 李亚丽[1] 侯微[1] 王英平[2] QU Zheng-Yi;ZHENG Pei-He;LI Ya-Li;HOU Wei;WANG Ying-Ping(Institute of Special Wild Economic Animals and Plants,Chinese Academy of Agricultural Sciences,Changchun 130112,China;College of Traditional Chinese Herbal Medicines,Jilin Agricultural University,Changchun 130118,China)

机构地区：[1]中国农业科学院特产研究所,长春130112 [2]吉林农业大学中药材学院,长春130118

出　　处：《分析化学》2022年第2期225-234,共10页Chinese Journal of Analytical Chemistry

基　　金：吉林省自然科学基金项目(No.20190201160JC);吉林省发展和改革委项目(Nos.2021C040-2,2019C052-10);中央级公益性科研院所基本科研业务费专项基金项目(Nos.125161034-2021-005,125161034-2021-014,125161034-2021-038);吉林省中药材及饮片加工转化科技创新中心和吉林省中药材种植(养殖)重点实验室资助。

摘　　要：采用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法(UPLC-Orbitrap HRMS),通过对照品的保留时间、相对分子质量、二级质谱碎片和相关文献等信息对三七果中的皂苷类化合物进行了解析,以探明三七果中的皂苷类成分及其结合态糖苷类化合物构成。从三七果中共鉴定出60种三萜皂苷,包括43种原人参二醇型皂苷、3种原人参三醇型皂苷、12种C-17支链发生变化的三萜皂苷和2种齐墩果酸型皂苷,其中双丙二酰基人参皂苷Rc(Double malonyginsenoside Rc)、双丙二酰基人参皂苷Rb_(2)(Double malonyginsenoside Rb_(2))和双丙二酰基人参皂苷Rb_(3)(Double malonyginsenoside Rb_(3))为首次从三七果中鉴定出的3种双丙二酰基人参皂苷。同时,根据离子碎片信息推测了皂苷的裂解途径,揭示了不同类型皂苷的质谱裂解规律。本研究较为全面地阐明了三七果中的皂苷类成分,为三七果中皂苷类成分的鉴定以及三七非药用部位果实的后续开发利用提供了理论依据。Panax notoginseng(Burk.)F.H.Chen is a species of genus Panax,family Araliaceae,and has been widely used as a traditional Chinese medicine for treatment of cardiovascular diseases.Previous studies on the chemical constituents of Panax notoginseng are mainly focused on the roots and leaves parts,but there are few research on the fruits part.Panax notoginseng fruits(PNF)is a mature berry drupe of Panax notoginseng.In the interest of further exploitation and utilization of this precious medicinal plant,developing new medicinal parts of Panax notoginseng and finding new trace active components,the main chemical ingredients of saponins in PNF were rapidly analyzed and identified by ultra high performance liquid chromatography-orbitrap high resolution mass spectrometry(UPLC-Orbitrap HRMS)in this work,based on the accuracy of the relative molecular mass,fragment ions,and retention behavior compared to those of reference substances.A total of 60 kinds of triterpenoid saponins were identified from ethanol extraction of PNF,including 43 kinds of protopanaxadiol saponins,3 kinds of protopanaxatriol saponins,12 kinds of C-17 side chain varied saponins,and 2 kinds of oleanolic acid saponins,respectively.Among them,3 kinds of double malonylginsenosides were first identified from PNF,namely double malonyginsenoside Rc,double malonyginsenoside Rb_(2)and double malonyginsenoside Rb_(3).Meanwhile,the fragmentation patterns of different saponin types were analyzed and summarized.The saponins of PNF were comprehensively clarified in this study,which could provide a theoretical basis for the identification of saponins and utilization of non-medicinal parts of PNF.

关 键 词：三七果 超高效液相色谱-四极杆/静电场轨道阱高分辨质谱 皂苷 裂解规律 

分 类 号：O657.63[理学—分析化学] R284.1[理学—化学]