人参皂苷Rd酸水解产物的RRLC-Q-TOF MS研究

Study on the Hydrolysis of Ginsenoside Rd by RRLC-Q-TOF MS

  • 摘要: 利用高分离快速液相色谱-四极杆-飞行时间质谱(RRLC-Q-TOF MS)联用技术对人参皂苷Rd酸水解产物进行了分析研究。通过化合物的保留时间、精确分子质量信息、串联质谱碎片信息,分析鉴定了7种Rd酸水解产物,分别为C-Y1、C-Y2、F2、20(S)-Rg3、20(R)-Rg3、Rk1和Rg5。串联质谱分析水解产物获得了原人参二醇苷元特征离子m/z 459(20(S)-Rg3,20(R)-Rg3,F2),Δ20(21)或Δ20(22)位脱水原人参二醇型苷元特征离子m/z 441(Rk1,Rg5),C-24、C-25位水合原人参二醇苷元特征离子m/z 477(C-Y1和C-Y2)。研究表明,人参皂苷Rd在酸性条件下发生化学转化,包括取代糖基的水解反应,Δ20(21)或Δ20(22)位脱水反应和C-24,C-25位水合加成反应。本实验可为研究人参在配位方面的化学物质基础提供方法参考。

     

    Abstract: Rapid resolution liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry (RRLC-Q-TOF MS) method was developed for analyzing the hydrolysis of ginsenoside Rd in acidic condition. The hydrolysis products were identified by comparison with the retention time of the standard compounds, the accurate mass and the characteristic fragment ions obtained from RRLC-Q-TOF-MS/MS analysis, including C-Y1, C-Y2, F2, 20(S)-Rg3, 20(R)-Rg3, Rk1 and Rg5. The specific product ions of aglycone PPD (m/z 459), Δ20 (21)-or Δ20 (22)-dehydration-PPD (m/z 441) and C-24, C-25 hydratedPPD (m/z 477) by MS/MS were discussed for structural characterization. The chemical transformation mechanisms of ginsenoside Rd were demonstrated in acidic condition, include saccharide hydrolysis, Δ20(21)- or Δ20(22)-dehydration and hydration addition reactions at C-24, C-25. The hydrolysis transformation pathway of ginsenoside Rd was summarized. The developed RRLC-Q-TOF-MS/MS method was applied for comparative analysis of ginsenoside Rd and related hydrolysis transformation products.

     

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