Rapid Differentiation of Asian and American Ginseng by Differential Ion Mobility Spectrometry-Tandem Mass Spectrometry U
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J. Am. Soc. Mass Spectrom. (2019) DOI: 10.1007/s13361-019-02317-0
RESEARCH ARTICLE
Rapid Differentiation of Asian and American Ginseng by Differential Ion Mobility Spectrometry-Tandem Mass Spectrometry Using Stepwise Modulation of Gas Modifier Concentration Ri Wu,1 Xiangfeng Chen,1,2 Wei-Jing Wu,1 Ze Wang,1 Y.-L. Elaine Wong,1 Y.-L. Winnie Hung,1 H.-T. Wong,1 Minli Yang,3 Feng Zhang,3 T.-W. Dominic Chan1 1
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong SAR, People’s Republic of China Shandong Analysis and Test Centre, Qilu University of Technology (Shandong Academy of Sciences), Jinan, Shandong, People’s Republic of China 3 Institute of Food Safety, Chinese Academy of Inspection and Quarantine, Beijing, 100123, China 2
Abstract. 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 ( DM S-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). Keywords: Differential ion mobility spectrometry, Tandem mass spectrometry, Collision-induced dissociation, Isomeric ginsenosides Received: 19 March 2019/Revised: 21 July 2019/Accepted: 10 August 2019
Introduction
G
inseng is a well-known natural product and has been used as a traditional Chinese medicine (TCM) for thousands of years in Asian countries. Many of the pharmacological effects
Electronic supplementary material The online version of this article (https:// doi.org/10.1007/s13361-019-02317-0) contains supplementary material, which is available to authorized users. Correspondence to: Xiangfeng Chen; e-mail: [email protected], T.– W. Chan; e-mail: [email protected]
that have been reported for ginseng, including anticancer and antioxidant properties and the modulation of cardiovascular conditions and immune function, have been attributed primarily to the presence of various ginsenosides as the major bioactive components [1]. Ginsenosides are a diverse group of steroidal saponins. Over 100 ginsenosides have been isolated from various species of ginseng [2]. Extensive phytochemical researchs on the structural characterization
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