| 人参中达玛烷型皂苷的化学转化产物结构和转化途径研究 |
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| 基金项目:国家自然科学基金(21475012)；吉林省教育厅“十三五”科学技术项目(JJKH20181274KJ) |
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| 中文摘要:利用高效液相色谱-电喷雾-多级串联质谱(HPLC-ESI-MSn)技术分析人参中3种达玛烷型皂苷(三七皂苷R1,人参皂苷Rd、20(S)-Rg3)在12 磷钨酸环境中转化的产物结构和转化途径。由原人参三醇型皂苷R1转化获得9种产物：20(S)-25-OH-R2、20(R)-25-OH-R2、25-OH-T5、20(S)-R2、20(R)-R2、20(S)-25-epoxy-R2、20(R)-25-epoxy-R2、T5、3β，12β 二羟基 6α (2 O β D 吡喃木糖基 β D 吡喃葡糖氧基)达玛烷-20(22)，24 二烯。由原人参二醇型皂苷Rd和20(S)-Rg3转化得到10种产物：20(S)-25-OH-Rg3、20(R)-25-OH-Rg3、25-OH-Rk1、25-OH-Rg5、20(S)-Rg3、20(R)-Rg3、(20S,25)-epoxy-Rg3、(20R,25)-epoxy-Rg3、Rk1、Rg5。通过分析转化产物结构，并考察主要产物含量随转化时间的变化趋势，总结了人参中达玛烷型皂苷在酸性水溶液环境中的转化途径，即通过C20位去糖基化和差向异构化反应，以及烯烃链的水合、脱水、环合反应转化为稀有皂苷。 |
| 中文关键词:人参 达玛烷型皂苷 化学转化 高效液相色谱-电喷雾-多级串联质谱(HPLC-ESI-MSn) |
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| Research on Structures and Pathways of Chemical Transformation Products of Dammarane type Saponin in Ginseng |
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| Abstract:Three dammarane types of saponins,including notoginsenoside R1,Rd and 20(S)-Rg3 were transformed using dodeca phosphotungstic acid.The chemical structures and transformation pathways of their products were analyzed by high performance liquid chromatography coupled with electrospray ionization multi stage mass spectrometry(HPLC-ESI-MSn).Totally,protopanaxatriol type saponin R1 was transformed into nine products,ie.20(S)-25-OH-R2,20(R)-25-OH-R2,25-OH-T5,20(S)-R2,20(R)-R2,20(S)-25-epoxy-R2,20(R)-25-epoxy-R2,T5 and 3β,12β dihydroxy 6α (2 O β D xylopyranosyl β D glucopyranosyloxy) dammar-20(22),24 diene,while ten identical products were obtained from protopanaxadiol type saponin Rd and 20(S)-Rg3,including 20(S)-25-OH-Rg3,20(R)-25-OH-Rg3,25-OH-Rk1,25-OH-Rg5,20(S)-Rg3,20(R)-Rg3,(20S,25)-epoxy-Rg3,(20R,25)-epoxy-Rg3,Rk1 and Rg5.Based on the structural identification,the relative content variations of major products with the reaction time were determined,and the transformation pathways for dammarane type saponin in acid solution were sequentially summarized.Results showed that dammarane type saponin could be readily transformed into rare ginsenosides via deglycosylation and epimerization reaction at C20 position,followed by hydration,dehydration and cyclization reactions on the olefin chain of dammarane type aglycone. |
| Key Words:ginseng dammarane type saponin chemical transformation HPLC-ESI-MSn |
| 引用本文：王秋颖，吴冬雪，赵幻希，李雪，孙秀丽，修洋，刘淑莹.人参中达玛烷型皂苷的化学转化产物结构和转化途径研究[J].分析测试学报,2020,39(1):99-107. |
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