Separation and Characterization of Triterpenoid Saponins in Gleditsia sinensis by Comprehensive Two-Dimensional Liquid Chromatography Coupled with Mass Spectrometry

Abstract

A comprehensive two-dimensional liquid chromatography coupled with mass spectrometry method was established to separate and characterize triterpenoid saponins in , the Chinese herbal medicine Zhu-Ya-Zao used for the treatment of apoplexy. The saponins were separated on an Agilent Zorbax Eclipse plus C column (2.1 mm × 150 mm, 1.8 µm) for the first dimension, and a Poroshell 120 phenyl-hexyl column (3.0 mm × 50 mm, 2.7 µm) for the second dimension. Methanol and acetonitrile were used as the organic mobile phase for D andD, respectively. The theoretical peak capacity was 640, and the orthogonality was 57 %. Particularly, saponins with different numbers of monoterpene groups could be well separated on the second dimension. The structures were characterized by electrospray ionization tandem mass spectrometry in both positive and negative ion modes. In the MS/MS spectra, the relative abundances for [B + Na] and [Y + Na] were closely correlated with the number of sugar residues of the -chain and-chain, respectively, which facilitated the differentiation of isomers. Finally, a total of 72 saponins with molecular weights greater than 1500 Da were characterized. Among them, 49 compounds, including 2 acetylated saponins, were detected from for the first time.

Identification of potential genes involved in triterpenoid saponins biosynthesis in Gleditsia sinensis by transcriptome and metabolome analyses

“…The elution peak (Rt =11.00 min, m/z = 1453.6849) detected and speculated as saponin of gleditsioside I which is compared to data of compound no. 0.43 of Wang et al [ 20 ]. Glc: glucose, Ara: arabinose, Rha: rhamnose, Xyl: xylose.…”

“…All data obtained from the HPLC–MS analysis were acquired with the Xcalibur™ software (Thermo Fisher Scientific). Detection and structural prediction of saponins were determined by comparing the obtained data with the accurate mass, MS/MS spectra, and retention time from the previous data set (Supplementary Table S3) [ 20 ]. Full MS data and MS 2 analysis for gleditsioside I are shown in Supplementary Fig.…”

Profiling of widely targeted metabolomics for the identification of chemical composition in epidermis, xylem and pith of Gleditsiae Spina

“…The differential primary metabolites analysis among Gs-E, Gs-X and Gs-P. (a) Venn diagram of the differential primary metabolites for Gs-E vs. Gs-X, Gs-E vs. Gs-P, and Gs-X vs. Gs-P. (b) Heatmap of the common differential primary metabolites for Gs-E vs. Gs-X, Gs-E vs. Gs-P, and Gs-X vs. Gs-P major bioactive constituents (Lian & Zhang, 2013;Wang et al, 2016).…”

Characterization of Flavonoids and Saponins from Gleditsia triacanthos by LC-ESI/MS/MS Analysis: Pharmacological Assessment of the Anti-hyperglycemic and Anti-ulcerogenic Activities of G. triacanthos methanolic Fruit Extract and its n-Butanol Fraction

“…The saponin structures were established based on their MS data 48 and guided by their characteristic sugar pattern [10][11][12][13][14][15][16][17][18][19][20]51 . The identified saponins reported here for the first time were caspicaoside F previously isolated from G. caspica fruits 10 , Gleditsia saponin C' was previously isolated from G. sinensis 12,20,21 and also obtained after partial alkaline hydrolysis of Gleditsia saponin C from G. japonica 52 , Gledtsioside J was isolated before from fruits of G. sinensis 20 and gleditsia saponin G' was previously obtained from G. japonica after alkaline hydrolysis of Gleditsia saponin G 51 .…”

“…The structures of the triperpenoidal saponins were established based on the [M-H]and their fragment ions corresponding to the loss of 132 (pentoses) and 162 (hexoses) mu and after considering the characteristic sugar pattern and aglycones of Gleditsia saponins 48,49 .…”