New triterpene saponins from the roots of Glycyrrhiza yunnanensis and their rapid screening by LC/MS/MS

• Seven new triterpene saponins were isolated from Glycyrrhiza yunnanensis.
• (−)-ESI-MS/MS fragmentation behaviors of triterpene saponins were studied.
• NL and PR scans by LC/MS/MS allowed detection of 50 saponins in G. yunnanensis.

The roots of Glycyrrhiza yunnanensis Cheng f. et L. K. Dai ex P. C. Li are used as licorice in traditional medicine of Southwest China. Triterpene saponins are the major chemical constituents. In this study, one new oleanane-type triterpenoid, glyyunnansapogenin I (I), seven new triterpene saponins, yunganosides E3 (II), L (III), M (IV), N1 (V), O (VI), P (VII) and N2 (VIII), together with four known saponins (IX–XII) were isolated from the roots of G. yunnanensis by preparative chromatography. Their structures were identified by spectroscopic analysis including NMR and HR-MS. Based on (−)-ESI-MS/MS fragmentation behaviors of these reference standards, an LC/MS/MS method using neutral loss scan and precursor ion scan on a triple quadrupole mass spectrometer was established to rapidly and comprehensively analyze triterpene saponins in G. yunnanensis. Combined with high-accuracy qTOF mass spectrometry analysis, a total of 50 saponins were detected, and their structures were identified or tentatively characterized. This is the first systematic study on triterpene saponins in G. yunnanensis.

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