Tianjin State Key Laboratory of Modern Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 300193, China.
Tianjin Key Laboratory of TCM Chemistry and Analysis, Tianjin University of Traditional Chinese Medicine, Tianjin 300193, China.
Molecules. 2019 Jul 25;24(15):2708. doi: 10.3390/molecules24152708.
The complexity of herbal matrix necessitates the development of powerful analytical strategies to enable comprehensive multicomponent characterization. In this work, targeting the multicomponents from C.A. Meyer, both data dependent acquisition (DDA) and data-independent high-definition MS (HDMS) in the negative electrospray ionization mode were used to extend the coverage of untargeted metabolites characterization by ultra-high-performance liquid chromatography (UHPLC) coupled to a Vion IM-QTOF (ion-mobility/quadrupole time-of-flight) high-resolution mass spectrometer. Efficient chromatographic separation was achieved by using a BEH Shield RP18 column. Optimized mass-dependent ramp collision energy of DDA enabled more balanced MS/MS fragmentation for mono- to penta-glycosidic ginsenosides. An in-house ginsenoside database containing 504 known ginsenosides and 60 reference compounds was established and incorporated into UNIFI, by which efficient and automated peak annotation was accomplished. By streamlined data processing workflows, we could identify or tentatively characterize 178 saponins from , of which 75 may have not been isolated from the genus. Amongst them, 168 ginsenosides were characterized based on the DDA data, while 10 ones were newly identified from the HDMS data, which indicated their complementary role. Conclusively, the in-depth deconvolution and characterization of multicomponents from were achieved, and the approaches we developed can be an example for comprehensive chemical basis elucidation of traditional Chinese medicine (TCM).
草药基质的复杂性要求开发强大的分析策略，以实现全面的多组分表征。在这项工作中，针对 C.A. Meyer 的多组分，我们在负离子电喷雾电离模式下同时使用了数据依赖采集（DDA）和数据非依赖高分辨 MS（HDMS），以扩展超高效液相色谱（UHPLC）与 Vion IM-QTOF（离子淌度/四极杆飞行时间）高分辨质谱联用对非靶向代谢物特征的覆盖范围。通过使用 BEH Shield RP18 柱实现了有效的色谱分离。DDA 的优化质量相关 ramp 碰撞能量使单糖至五糖糖苷型人参皂苷的 MS/MS 碎片化更平衡。建立了一个包含 504 种已知人参皂苷和 60 种对照化合物的内部人参皂苷数据库，并将其整合到 UNIFI 中，通过该数据库可以实现高效自动化的峰注释。通过简化的数据处理工作流程，我们可以从 中鉴定或暂定鉴定 178 种皂苷，其中 75 种可能尚未从 属中分离出来。其中，根据 DDA 数据鉴定了 168 个人参皂苷，而从 HDMS 数据中鉴定了 10 个人参皂苷，表明它们具有互补作用。总之，从 中深入解析和表征了多组分，并开发了可以为中药（TCM）全面化学基础阐明提供范例的方法。
