## 3 Results and Discussion
### Identity Assignment and Confirmation of the Components in PJ, PM, and PZ
A total of 101 compounds were detected and tentatively identified, including 82 from PJ, 78 from PM, and 67 from PZ. Among them, 22 ginsenosides, including ginsenosides G-Rg1, G-Re, G-Rb1, G-Re, G-Rb2, G-Rb3, G-Rf, G-Rd, G-Rg2, G-Rg3, G-F3, G-Rh1, G-Rh2, G-Ro, G-F1, G-F2, NG-R1, pseudo G-F11, PPD, PPT, CS-IV, and CS-IVa, were unambiguously identified by comparing their retention times and fragment ions with the reference standards. The others were tentatively assigned by the empirical molecular formula, theoretical molecular mass, and MS/MS fragment ions as well as the retention sequence of isomeric ginsenosides. Figure 2: The base peak chromatogram of the roots and rhizes of PJ **(A)**, PM **(B)**, and PZ **(C)** in negative mode. _Panax japonicus_ **(PJ)**, _Panax japonicus_ var. major **(PM)**, _Panax zingiherensis_ **(PZ)**. In the MS spectra, most of the ginsenosides showed deprotonated ions [M \(-\) H]\({}^{-}\) and/or formic acid adduct ions [M \(+\) HCOO]\({}^{-}\) in the negative ion mode. However, it is worth noting that the malonyl-ginsenosides could not produce adduct ions [M \(+\) HCOO]\({}^{-}\) because malonyl-ginsenosides are unstable. It is easy to lose CO\({}_{2}\) from the deprotonated molecules of these compounds under demalonylation, which results in the detection of the peaks in the quasi-molecular ions of [M \(-\) H \(-\) CO2]\({}^{-}\) and [M \(-\) H \(-\) Malonyl]\({}^{-}\), which were found in compounds **19**, **22**, **31**, **40**, **45**, **46**, **50**, **51**, **56**, **57**, **59**, **65**, and **68**. Additionally, according to the negative MS, MS/MS spectra of the ginsenosides, the deprotonated ions and their product ions exhibited the common fragmentation pattern that corresponds to the successive or simultaneous loss of glycosidic units, such as the glucosyl (Glc) group (162 Da), the rhamn (Rha) group (146 Da), the xylose(Xyl)/arabinose(Ara) group (132 Da), and the glucuronyl (Glu A) group (176 Da), at the C-20, C-3, or C-6 sites until the formation of an aglycone ion. The characteristic ions at \(m/z\) 475 (C\({}_{30}\)H\({}_{51}\)O\({}_{4}\)) and \(m/z\) 459 (C\({}_{30}\)H\({}_{51}\)O\({}_{3}\)) were observed in the PPTs (such as compounds **3**, **6**, **8**, **10**, **11**, **13**, **17**, **18**, **41**, **53**, **62**, **69**, and **78** ) and PPDs (such as compounds **20**, **30**, **31**, **35**, **36**, **39**, **42**, **48**, **54**, **60**, **64**, **70**, **71**, **75**, **85**, **88**, **89**, **91**, **93**, and **98** ), respectively. As shown in Figure 3A,B, G-Rb1 produced [(205)-protopanaxadiol \(-\) H]\({}^{-}\) at \(m/z\) 459.38260 (C\({}_{30}\)H\({}_{51}\)O\({}_{3}\)) in the MS/MS spectrum by the successive loss of four Glc (162 Da), and NG-R1 gave the [(205)-protonanaxatriol \(-\) H]\({}^{-}\) at \(m/z\) 475.37848 (C\({}_{30}\)H\({}_{51}\)O\({}_{4}\)) via the successive elimination of one Xyl and two Glc. Moreover, the OAs displayed an aglycone ion at \(m/z\) 455 (C\({}_{30}\)H\({}_{47}\)O\({}_{3}\)) corresponding to [oleanadic acid \(-\) H]\({}^{-}\), which was visible for compounds **47**, **55**, **61**, **67**, **80**, **81**, **82**, **84**, and **94**. Figure 3C,D show the MS/MS spectra of G-Ro (55) and CS-IV (61). These two saponins produced [oleanadic acid \(-\) H]\({}^{-}\) at \(m/z\) 455 (C\({}_{30}\)H\({}_{47}\)O\({}_{3}\)) after the successive loss of Glc, and/or Ara, and Glu A. Notably, some Octillol-type triterpen saponins were also detected and identified in the three ginseng herbs. For example, compounds **24** (Pseudo G-F11), **34** (Vina G-R1), **95** (Vina G-R2), **100** (Pseudo G-RT4), **5**, and **21** (Vina G-R6/Yesanchinoside C) were observed at \(m/z\) 491 (C\({}_{30}\)H\({}_{51}\)O\({}_{5}\)) via the loss of a different sugar moiety, corresponding to the deprotonated ions of Octillol-type aglycone. Figure 3: The MS/MS spectrum of ginsenoside -Rb1 (**A**), ginsenoside -R1 (**B**), ginsenoside -Ro (**C**), and chikusetsu saponin -IV (**D**).