摘要
利用高效液相色谱|(HPLC)-Q Exactive-Orbitrap高分辨质谱(HRMS)技术分析12-磷钨酸化学转化柴胡皂苷c(SSc)的产物结构和转化途径。HPLC可以快速分离结构相近的转化产物。利用HRMS获得产物分子及其碎片离子的精确质量数,鉴定产物结构并分析转化途径。结果表明,在12-磷钨酸产生的酸性环境中,SSc主要通过C_(18)位的环醚开环和羟基消除反应生成具有异环双烯结构的柴胡皂苷h(SSh),并伴随着C_(3)位的去糖基化反应生成去鼠李糖-SSc和去鼠李糖-SSh。转化反应6 h后趋于稳定。HPLC-Q Exactive-Orbitrap技术能够快速准确地分析柴胡皂苷及其转化产物结构,并可以区分转化得到的异环双烯和同环双烯柴胡皂苷同分异构体。
The structure and transformation pathway of the products generated by chemical transformation of saikosaponin c(SSc)using dodeca phosphotungstic acid were analyzed by high-performance liquid chromatography(HPLC)coupled with Q Exactive-Orbitraphigh resolution mass spectrometry(HRMS).HPLC could rapidly separate transformation products with similar structures.HRMS was used to identify the product structures and analyze the transformation pathways via acquiring the exact mass of the products and their fragment ions.The results showed that in acidic environment generated by dodeca tungstophosphoric acid,SSc was transformed to saikosaponin h(SSh)with hetero-cyclodiene structure through cycloether ring-opening and hydroxyl elimination reactions at position C_(18)of aglycone,and was further transformed to derhamnose-SSc and derhamnose-SSh through deglycosylation reaction at position C_(3).The transformation reaction was stabilized after 6 h.The employed HPLC-Q Exactive-Orbitrap method enables the rapid and accurate identification of saikosaponins and their transformation products,as well as the differentiation of transformed cyclodiene isomers.
作者
王震寰
赵孟雅
田璐
陈思键
焦丽丽
刘淑莹
赵幻希
修洋
WANG Zhenhuan;ZHAO Mengya;TIAN Lu;CHEN Sijian;JIAO Lili;LIU Shuying;ZHAO Huanxi;XIU Yang(Jilin Ginseng Academy,Changchun University of Chinese Medicine,Changchun 130117,China;Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China)
出处
《分析试验室》
EI
CAS
CSCD
北大核心
2023年第7期853-859,共7页
Chinese Journal of Analysis Laboratory
基金
国家自然科学基金(21475012)
吉林省科技发展计划项目(20210204098YY,20200201093JC)资助
作者简介
王震寰,女(1995-),硕士研究生。研究方向:中药分析新方法与新技术研究,847637379@qq.com;通信作者:赵幻希,女(1987-),硕士,助理研究员。研究方向:中药活性物质筛选,phoenix8713@sina.com;通信作者:修洋,男(1983-),博士,副研究员。研究方向:天然产物化学研究,ys830805@sina.com
