Trapping and on‐column hydrolysis strategy coupled with high‐performance liquid chromatography‐tandem mass spectrometry for new ginsenosides identification and quantification

Abstract Malonyl ginsenosides (mRs) are physiologically active constituents of Asian and American ginseng ( P. quinquefolius ). They are also important quality markers for the herbs from the Panax genus. Their contents are relevant to several essential quality characteristics of ginseng, for example, the original species, the growing age, the planting areas, the cultivation methods, and the processing conditions. However, when extracted from the herb, an mR is very unstable to lose the malonyl group. This property hampers the structural and quantitative determination of an mR. Herein, We report a trapping and on‐column hydrolysis coupled with a high‐performance liquid chromatography‐tandem mass spectrometry (HPLC‐MS/MS) method. With this method, 19 mRs have been identified from Panax ginseng roots. The isomers of some mRs with identical MS/MS characteristics have been differentiated. The quantities of these mRs have also been determined without references using this method. The quantitative results can be traced to the quantity of certified neutral ginsenoside reference materials. The method has been well‐validated. In addition, unique low‐abundance acetyl ginsenoside Rg1 and malonyl pseudoginsenoside F11 were identified from P. ginseng and P. quinquefolius , respectively.