Discrimination of Ginseng Origins and Identification of Ginsenoside Markers Based on HPLC-MS Combined with Multivariate Statistical Analysis

High performance liquid chromatography-mass spectrometry combined with multi-variate statistical analysis was employed to discriminate 45 ginseng samples harvested from 5 different main cultivation areas in Northeast China and to identify the differential ginsenoside markers. A total of 41 ginsenosides, which included 15 protopanaxatriol type , 24 protopanaxadiol type and 2 oleanolic type ginsenosides , were identified based on the elution order of total ginsenosides in the reverse-phase C-18 column coupled with the tandem MS analysis and comparison with authentic standard. Multivariate statistical analysis was further used to extract the information of HPLC-MS data sets. Orthogonal partial least squares-discriminate analysis revealed that the established analysis model had high goodness of fit and predictability. All the 45 ginseng samples were discriminated according to their origins. And 18 ginsenosides were identified as the differential markers, which contributed most to the simultaneous discrimination of the 5 ginseng origins. In addition, the differential ginsenoside markers which could distinguish any two origins were mainly those of high content in wild ginseng, such as Rb1 , Rg1, Re, Rc , Rd, Ro , and m-Rb1. In the results of hierarchical clustering analysis, the ginseng samples of Heilongjiang and Jilin Province gathered separately except 14 the samples from Suihua city, which showed similarity to those of Jilin Province. This discrepancy may be attributed to the geographical location. Suihua city is relatively closer to Jilin Province and hence results in the similar growth environment of ginseng and the facility to exchange germplasm resources.