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首页> 外文期刊>Journal of mass spectrometry: JMS >Silver (I)-assisted enantiomeric analysis of ginsenosides using electrospray ionization tandem mass spectrometry
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Silver (I)-assisted enantiomeric analysis of ginsenosides using electrospray ionization tandem mass spectrometry

机译：人参皂苷的银（I）辅助对映体的电喷雾电离串联质谱分析

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摘要

For identification of ginsenoside enantiomers, electrospray ionization mass spectrometry (ESI-MS) was used to generate silver complexes of the type [ginsenoside + Ag] ~+. Collision induced dissociation of the silver-ginsenoside complexes produced fragment ions by dehydration, allowing differentiation of ginsenoside enantiomers by the intensity of [M + Ag - H _2O] ~+ ion. In the meanwhile, an approach based on the distinct profiles of enantiomer-selective fragment ion intensity varied with collision energy was introduced to refine the identification and quantitation of ginsenoside enantiomers. Five pairs of enantiomeric ginsenosides were distinguished and quantified on the basis of the distribution of fragment ion [M + Ag - H _2O] ~+. This method was also extended to the identification of other type of ginsenoside isomers such as ginsenoside Rb2 and Rb3. For demonstrating the practicability of this novel approach, it was utilized to analyze the molar ratio of 20-(S) and 20-(R) type enantiomeric ginsenosides in enantiomer mixture in red ginseng extract. The generation of characteristic fragment ion [M + Ag - H _2O] ~+ likely results from the reduction of potential energy barrier of dehydration because of the catalysis of silver ion. The mechanism of enantiomer identification of ginsenosides was discussed from the aspects of computational modeling and internal energy.
机译：为了鉴定人参皂苷对映体，使用电喷雾电离质谱法（ESI-MS）生成人参皂苷+ Ag]〜+型银络合物。碰撞诱导的银-人参皂甙配合物解离，通过脱水产生碎片离子，从而使人参皂甙对映异构体通过[M + Ag-H _2O]〜+离子的强度进行分化。同时，引入了一种基于对映体选择性片段离子强度随碰撞能量变化而变化的独特方法，以改进人参皂苷对映体的鉴定和定量。根据碎片离子[M + Ag-H _2O]〜+的分布，区分并定量了五对对映体人参皂苷。该方法还扩展到了其他类型的人参皂苷异构体的鉴定，例如人参皂苷Rb2和Rb3。为了证明这种新方法的实用性，它用于分析红参提取物中对映体混合物中20-（S）和20-（R）型对映体人参皂苷的摩尔比。特征性碎片离子[M + Ag-H _2O]〜+的产生可能是由于银离子的催化作用而降低了脱水的势能垒。从计算模型和内部能量的角度讨论了人参皂甙对映体鉴定的机理。

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