Identification and comparison of triterpene saponins in Aralia elata leaves and buds by the energy-resolved MS technique on a liquid chromatography/quadrupole time-of-flight mass spectrometry.

In this study, we identify the triterpene saponins (TSs) extracted from the leaves and buds of Aralia elata (Miq.) Seems using ultra-performance liquid chromatography and positive ionization electrospray quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF). The energy-resolved MS (erMS) technique is applied in order to simultaneously collect the diverse precursors attributed to [M+H], [M + NH] and [M + Na] ions. A practical and effective erMS workflow is established to rapidly identify and compare the saponins in the analyzed samples. In total, 111 TSs of structure are estimated, including 44 new compounds that had not been identified previously in A. elata. Of the five aglycones detected in the samples, a sapogenin 3β, 16α, 23-trihydroxyoleana-11,13-dien-28-oic acid (A5) that is identified for the first time in A. elata leaves. Compared to the buds, the leaves number twice as many hederagenin-type (A2) compounds. Although the number of other aglycones does not vary significantly between the buds and the leaves, A5 compounds are exclusively detected in the latter. Moreover, the C-3 sugar chains of TSs in A. elata leaves are mainly neutral (e.g., Hex+Hex, Hex+Hex+Hex and Hex+Hex+Hex+Hex), whereas those of bud TS compounds are primarily acidic (e.g., Pen+HexA, Hex+HexA and Hex+Pen+HexA). Some of the identified TS compounds, e.g., 27, 28, 32, 46, 54, 57, 71 and 105 can be used as indices to evaluate the quality of the plant leaves and buds. Overall, this study is of great significance for the comparative study of triterpenoid saponins in the leaves and buds of Aralia elata.