In-source fragmentation of ginsenosides in the positive ESI mode (pISF-G) frequently occurs, which results in little fragment information useful for the structural elucidation. We are aimed to unveil the genesic mechanism and explore its potential significance in quality control of Ginseng and the related compound formulae. By applying six high-resolution mass spectrometers from Agilent, Waters, and Thermo Fisher, we could primarily demonstrate the susceptibility of pISF-G. The ion clusters in the positive full-scan MS1 spectra were generated from the protonated sapogenins by successive elimination of H2O, and showed specificity for ginsenoside classification. Selective ion monitoring (SIM) of the sapogenin product ions could delineate group-target ginsenoside profiles from Ginseng. A high-selectivity characteristic chromatogram (CC) was elaborated for Ginseng, on the Vion™ IMS-QTOF mass spectrometer by IM (ion mobility) separation and quadrupole filtering of four sapogenin fragments (m/z 407.37/CCS 206.24 Å2; m/z 423.36/CCS 211.26 Å2; m/z 439.36/CCS 209.60 Å2; m/z 457.37/CCS 217.81 Å2). Chemometric analysis, based on the CC data of seven Ginseng drugs (P. ginseng, P. quinquefolius, P. notoginseng, Red ginseng, leaf of P. ginseng, P. japonicus, and P. japonicus var. major), disclosed 35 marker compounds. We could readily discriminate among P. ginseng, P. quinquefolius, and P. notoginseng, in 15 different compound formulae by identifying these marker compounds on both the Vion IMS-QTOF and QTrap 4500 mass spectrometers. Conclusively, SIM of the pISF-G sapogenin product ions renders a new concept of CC enabling the group-target profiling of ginsenosides and authentication of Ginseng and the related compound formulae.

中文翻译：

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以正向模式高度选择性地监测源中分裂型皂甙元产物离子，可对靶标人参皂苷进行谱分析并同时鉴定七种人参草药。

人参皂苷以正ESI模式（pISF-G）经常发生源内碎裂，导致几乎没有碎片信息可用于结构阐明。我们旨在揭示其发生机理，并探讨其在人参及相关化合物配方质量控制中的潜在意义。通过使用安捷伦，沃特世和赛默飞世尔的六台高分辨率质谱仪，我们可以主要证明pISF-G的敏感性。通过连续消除H2O，从质子化的皂甙元生成正全扫描MS1光谱中的离子簇，并显示出对人参皂苷分类的特异性。皂苷元产物离子的选择性离子监测（SIM）可以描绘出人参的组靶标人参皂苷谱。通过IM（离子迁移率）分离和四个皂甙元片段的四极杆过滤（m / z 407.37 / CCS 206.24Å2; m / z 423.36 / CCS 211.26Å2； m / z 439.36 / CCS 209.60Å2； m / z 457.37 / CCS 217.81Å2）。根据七种人参药物（人参，西洋参，三七，红参，人参叶，日本对虾和日本对虾）的CC数据进行化学计量分析，揭示了35种标记化合物。通过在Vion IMS-QTOF和QTrap 4500质谱仪上鉴定这些标记化合物，我们可以很容易地在15种不同的化合物配方中区分人参，西洋参和三七。最后，