Rapid Differentiation of Asian and American Ginseng by Differential Ion Mobility Spectrometry-Tandem Mass Spectrometry Using Stepwise Modulation of Gas Modifier Concentration
This study reports a rapid and robust method for the differentiation of Asian and American ginseng samples based on differential ion mobility spectrometry-tandem mass spectrometry (DMS-MS/MS). Groups of bioactive ginsenoside/pseudo-ginsenoside isomers, including Rf/Rg1/F11, Rb2/Rb3/Rc, and Rd/Re, in the ginseng extracts were sequentially separated using DMS with stepwise changes in the gas modifier concentration prior to MS analysis. The identities of the spatially separated ginsenoside/pseudo-ginsenoside isomers were confirmed by their characteristic compensation voltages at specific modifier loading and MS/MS product ions. As expected, Asian ginseng samples contained some Rf and an insignificant amount of F11, whereas American ginseng samples had a high level of F11 but no Rf. The origin of the whole and sliced ginseng could further be confirmed using the quantitative ratios of three sets of ginsenoside markers, namely, Rg1/Re, Rb1/Rg1, and Rb2/Rc. Based on our results, new benchmark ratios of Rg1/Re < 0.15, Rb1/Rg1 > 2.15, and Rb2/Rc < 0.26 were proposed for American ginseng (as opposed to Asian ginseng).
KeywordsDifferential ion mobility spectrometry Tandem mass spectrometry Collision-induced dissociation Isomeric ginsenosides
This work was supported by The National Key Research and Development Program of China (2018YFC1603500), Research Grant Council of the Hong Kong Special Administrative Region (Research Grant Direct Allocation, Ref. 3132667 and 4053152), Key R&D Program of Shandong Province (2019GSF111009, 2019GSF111001), and Natural Science Foundation of Shandong Province (ZR2017MB011).
Compliance with Ethical Standards
Conflict of Interests
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
- 19.Liu, C., Ríos, G.A.G., Schneider, B.B., Blanc, J.C.Y.L., Garcés, N.R., Arnold, D.W., Covey, T.R., Pawliszyn, J.: Fast quantitation of opioid isomers in human plasma by differential mobility spectrometry/mass spectrometry via SPME/open-port probe sampling interface. Anal. Chim. Acta. 991, 89–94 (2017)CrossRefGoogle Scholar
- 21.McCooeye, M., Ding, L.Y.G., Gardner, J., Fraser, C.A., Lam, J., Sturgeon, R.E., Mester, Z.: Separation and quantitation of the stereoisomers of ephedra alkaloids in natural health products using flow injection-electrospray ionization-high field asymmetric waveform ion mobility spectrometry-mass spectrometry. Anal. Chem. 75, 2538–2542 (2003)CrossRefGoogle Scholar
- 29.Mie, A., Karlsson, M.J., Axelsson, B.O., Ray, A., Reimann, C.T.: Enantiomer separation of amino acids by complexation with chiral reference compounds and high-field asymmetric waveform ion mobility spectrometry: preliminary results and possible limitations. Anal. Chem. 79, 2850–2858 (2007)CrossRefGoogle Scholar
- 33.Liang, Z.T., Chen, Y.J., Xu, L., Qin, M.J., Yi, T., Chen, H.B., Zhao, Z.J.: Localization of ginsenosides in the rhizome and root of Panax ginseng by laser microdissection and liquid chromatography-quadrupole/time of flight-mass spectrometry. Pharmaceut. Biomed. 105, 121–133 (2015)CrossRefGoogle Scholar
- 34.Song, Y.L., Zhang, N., Jiang, Y., Li, J., Zhao, Y.F., Shi, S.P., Tu, P.F.: Simultaneous determination of aconite alkaloids and ginsenosides using online solid phase extraction hyphenated with polarity switching ultra-high performance liquid chromatography coupled with tandem mass spectrometry. RSC Adv. 5, 6419–6428 (2015)CrossRefGoogle Scholar