Rationale: Acylated monosaccharide residues are structural subunits of natural products or synthetic intermediates that have received much attention in past years. Determination of the acylation sites of these residues still relies heavily on the comparison of their characteristic NMR signals with those of known standards and synthesized acylated glycosides. It is important to develop a rapid analytical method for determining the acylation sites for these compounds, and this is described in this study.
Methods: Six known polyphenolic glycosides were used for the electrospray ionization and collision-induced dissociation tandem mass spectrometry (ESI-CID-MS/MS) discrimination of the acylated monosaccharide residues with different acylation sites. A combination of ESI-CID-MS/MS, using a triple quadrupole mass spectrometer, with ultra-performance liquid chromatography (UPLC) and photo-diode array (PDA) detection (UPLC-PDA) has been applied to the identification or characterization of polyphenolic glycosides in Polygonum capitatum that possess an acylated monosaccharide residue.
Results: An ESI-MS and CID-MS/MS method has been developed for the determination of the acylation sites of polyphenolic glycosides that possess an acylated monosaccharide residue. Twelve polyphenolic glycosides including four new ones have been identified or characterized in P. capitatum. Eight (including the new ones) of the twelve glycosides were reported for the first time from this plant.
Conclusions: The developed ESI-MS and CID-MS/MS method provided a very useful strategy for the determination of the sites of polyphenolic glycosides that possess an acylated monosaccharide residue. The acylation site could be determined by the characteristic product ion spectra of the in-source CID-generated O-acyl monosaccharide ion [B(1)](+). The presented work may facilitate the structural characterization of these types of compounds.
Copyright © 2012 John Wiley & Sons, Ltd.