Provincial Key Laboratory of Pharmaceutics in Guizhou Province, School of Pharmacy, Guiyang Medical College, Guiyang, Guizhou, PR China.
Rapid Commun Mass Spectrom. 2012 Nov 15;26(21):2483-92. doi: 10.1002/rcm.6366.
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.
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.
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.
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.
酰化单糖残基是天然产物或合成中间体的结构单元，近年来受到了广泛关注。这些残基的酰化位点的确定仍然很大程度上依赖于它们的特征 NMR 信号与已知标准和合成酰化糖苷的特征 NMR 信号的比较。因此，开发一种快速分析方法来确定这些化合物的酰化位点是很重要的，本研究对此进行了描述。
使用六种已知的多酚糖苷，通过电喷雾电离和碰撞诱导解离串联质谱（ESI-CID-MS/MS），对具有不同酰化位点的酰化单糖残基进行区分。采用三重四极杆质谱仪，结合超高效液相色谱（UPLC）和光电二极管阵列（PDA）检测（UPLC-PDA）的 ESI-CID-MS/MS 组合，已应用于鉴定或表征具有酰化单糖残基的虎杖中的多酚糖苷。
建立了一种测定具有酰化单糖残基的多酚糖苷酰化位点的 ESI-MS 和 CID-MS/MS 方法。从虎杖中鉴定或表征了 12 种多酚糖苷，包括 4 种新的多酚糖苷。这 12 种糖苷中有 8 种（包括新的糖苷）是首次从该植物中报道的。
所开发的 ESI-MS 和 CID-MS/MS 方法为确定具有酰化单糖残基的多酚糖苷的酰化位点提供了一种非常有用的策略。酰化位点可以通过源内 CID 产生的 O-酰化单糖离子B(1)的特征产物离子谱来确定。本研究结果可能有助于这些类型化合物的结构表征。
