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  

Research on Structures and Pathways of Chemical Transformation Products of Dammarane-type Saponin in Ginseng

作　　者：王秋颖 吴冬雪 赵幻希 李雪 孙秀丽 修洋 刘淑莹 WANG Qiu-ying;WU Dong-xue;ZHAO Huan-xi;LI Xue;SUN Xiu-li;XIU Yang;LIU Shu-ying(Jilin Ginseng Academy,Changchun University of Chinese Medicine,Changchun 130117,China;Changchun Institute of Applied Chemistry,Chinese Academy of Science,Changchun 130022,China)

机构地区：[1]长春中医药大学,吉林省人参科学研究院,吉林长春130117 [2]中国科学院长春应用化学研究所,吉林长春130022

出　　处：《分析测试学报》2020年第1期99-107,共9页Journal of Instrumental Analysis

基　　金：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)。

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。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,i.e.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.

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-MS^n) 

分 类 号：O657.63[理学—分析化学] R914.1[理学—化学]