利用非手性-手性色谱-预测多反应监测法分析中药前胡化学成分  

Chemical Profiling of Peucedani Radix by Achiral-chiral Liquid Chromatography-Predictive Multiple Reaction Monitoring

作　　者：许霞 李婷 曹丽波 贾金茹 龚兴成 李军[1,2] 屠鹏飞 王一涛[3] 宋月林[1,2] XU Xia;LI Ting;CAO Li-Bo;JIA Jin-Ru;GONG Xing-Cheng;LI Jun;TU Peng-Fei;WANG Yi-Tao;SONG Yue-Lin(Modern Research Center for Traditional Chinese Medicine,School of Chinese Materia Medica,Beijing University of Chinese Medicine,Beijing 100029,China;Beijing Key Lab for Quality Evaluation of Chinese Meteria Medica,Beijing University of Chinese Medicine,Beijing 100029,China;State Key Laboratory of Quality Research in Chinese Medicine,Institute of Chinese Medical Sciences,University of Macao,Taipa 999078,Macao,China)

机构地区：[1]北京中医药大学中药学院中药现代研究中心,北京100029 [2]北京中医药大学中药学院中药品质评价北京市重点实验室,北京100029 [3]澳门大学中华医药研究院中药质量研究国家重点实验室,中国澳门999078

出　　处：《分析化学》2020年第12期1717-1727,共11页Chinese Journal of Analytical Chemistry

基　　金：国家重点研发计划项目(No.2018YFC1707300);国家科学自然基金项目(Nos.81973444,817738757);中国科协青年人才托举工程项目(No.2017QNRC001);北京中医药大学青年科学家培育计划项目(No.BUCM-2019-QNKXJB006);中央高校基本科研业务费专项资金(No.2020-JYB-ZDGG-041)资助。

摘　　要：前胡等中药不仅化学成分组成复杂,而且常含有大量对映异构体,且对映异构体之间的含量常存在差异。本研究以中药前胡为例,建立了非手性-手性色谱-预测多反应监测法(Achiral-chiral LC-predictive MRM),实现了化学成分的化学选择性和立体选择性分析。非手性-手性色谱直接耦联系统结合了RP-C 18色谱柱的高效分离能力以及手性色谱柱的立体选择性分离优势,有效避免了中心切割非手性-手性二维液相构造复杂、精密度差等缺陷。采用小内径核壳型RP-C 18色谱柱作为前端化学分离柱,实现了结构类似香豆素的高效化学选择性分离;通过在手性柱前引入稀释泵,优化适用于手性选择性分离的洗脱程序;采用反相大内径AD-RH手性色谱柱,实现了对映异构体的手性拆分。采用预测多反应监测模式实现化学成分的高灵敏度检出,并利用增强子离子扫描模式采集各色谱峰的二级质谱,进行结构确证。从前胡中鉴定出61种化学成分,其中包括11对对映异构体。Achiral-chiral LC-predictive MRM为含有对映异构体的中药及其它复杂样品的深入定性和定量分析提供了可靠的方法。Peucedani radix and other herbal medicines are not only complex in chemical composition,but also often contain a large number of enantiomers,and there are often differences in content of enantiomers.In this work,a new analytical platform namely achiral-chiral liquid chromatography(LC)-predictive multiple reaction monitoring was firstly configured for chemo-and enantio-selective separation of the components in Peucedani Radix,a well-known herbal medicine.Serially coupled achiral LC and chiral LC integrated the robust separation potential of RP-C 18 column along with the enantio-separation advantage from chiral column,thus addressing the disadvantages of heart-cutting achiral-chiral two dimensional LC in terms of sophisticated instrumentation and unsatisfactory precision.The narrow-bore core-shell RP-C 18 column was served as the front tool to accomplish efficient chemo-selective separation within those coumarins bearing similar chemical structures,a dilution pump was introduced between the two columns to facilitate the optimization of optimum elution program from the chiral column,and a wide-bore chiral column offered the enantio-separation potential for those enantiomers.Predictive MRM mode was deployed to sensitively detect the chemical components,and the enhanced product ion program was utilized to acquire MS 2 spectra for all signals.Structure confirmation was conducted by matching the fragment ion species with the well-proposed fragmentation rules.As a result,61 components,in total,were found from Peucedani Radix,including eleven pairs of enantiomers.Above all,achiral-chiral LC-predictive MRM is a promising tool for the quantitative and qualitative analysis of the complicated matrices,beyond herbal medicines,which are featured by enantiomerically enriched mixtures.

关 键 词：非手性-手性色谱 预测多反应监测模式 对映异构体拆分 角型吡喃香豆素 中药 前胡 

分 类 号：R284.1[医药卫生—中药学]