基于HPLC-LTQ-Orbitraps-MS^(n)分析比较酸枣仁-五味子药对单煎液和合煎液化学成分  

Comparison of Chemical Components between Ziziphi Spinosae Semen or Schisandrae Chinensis Fructus Monodecoction and Their Co-decoction by HPLC-LTQ-Orbitraps-MS^(n)

作　　者：王晓玫 刘洁[1,2] 丁永胜 罗静[1,4] 赵程博文 姚子蔚[1] 李秋雨 刘金凤 于佳禾 魏晓嘉 李佳园 万国慧 金重先 王雨青 杨雪 吕研 边丽华 王春国[1] 石晋丽 WANG Xiao-mei;LIU Jie;DING Yong-sheng;LUO Jing;ZHAO Cheng-bo-wen;YAO Zi-wei;LI Qiu-yu;LIU Jin-feng;YU Jia-he;WEI Xiao-jia;LI Jia-yuan;WAN Guo-hui;JIN Zhong-xian;WANG Yu-qing;YANG Xue;LYU Yan;BIAN Li-hua;WANG Chun-guo;SHI Jin-li(School of Chinese Materia Medica,Beijing University of Chinese Medicine,Beijing 102488,China;Children's Hospital Affiliated to Capital Institute of Pediatrics,Beijing 100020,China;China Resources Double-Crane Pharmaceutical Co.,Ltd.,Beijing 100102,China;YaoPharma Co.,Ltd.,Chongqing 401121,China;Dongzhimen Hospital,Beijing University of Chinese Medicine,Beijing 100700,China)

机构地区：[1]北京中医药大学中药学院,北京102488 [2]首都儿科研究所附属儿童医院,北京100020 [3]华润双鹤药业股份有限公司,北京100102 [4]重庆药友制药,重庆401121 [5]北京中医药大学东直门医院,北京100700

出　　处：《中国现代中药》2021年第11期1949-1966,共18页Modern Chinese Medicine

基　　金：国家自然科学基金面上项目(81673560);北京市技术开发类横向课题(2017110031015577)。

摘　　要：目的:对酸枣仁-五味子药对单煎液、合煎液(2∶1)化学成分进行分析,探究该药对配伍合煎后化学成分的变化。方法:采用高效液相色谱-线性离子阱串联静电场轨道阱质谱法(HPLC-LTQ-Orbitraps-MS^(n)),在电喷雾离子源(ESI)的正、负离子模式下,采用傅里叶变换高分辨全扫方式(TF,Full scan,Resolution 30000)数据依赖性(data-dependent acquisistion)ddMS2和ddMS3方法分别对酸枣仁-五味子药对单煎液、合煎液(2∶1)采集数据。根据保留时间、高分辨质谱精确相对分子质量和多级碎片信息进行分析。结果:对酸枣仁单煎液中共50个色谱信号进行化学成分鉴定,指认出10个(黄酮类6个、生物碱类2个、皂苷类2个)近10年报道过指纹图谱分析或含量测定的化合物;对五味子单煎液中共32个色谱信号进行化学成分鉴定,指认出10个(均为木脂素类)近10年报道过指纹图谱分析或含量测定的成分;对酸枣仁-五味子药对(2∶1)合煎液中共50个色谱信号进行化学成分鉴定,指认出19个(黄酮类5个、生物碱类1个、皂苷类1个、木脂素类12个)近10年报道过指纹图谱分析或含量测定的成分,这些成分在各自单煎液中均已被指认。合煎液中未检出酸枣仁单煎液中检出的酸枣仁皂苷B,但检测到1个五味子单煎液中缺少的离子峰,系来自五味子药材的木脂素类同分异构体。结论:通过HPLC-LTQ-Orbitraps-MS^(n),初步发现酸枣仁-五味子药对(2∶1)配伍前后化学成分的变化,为进一步研究两者的配伍作用机制提供参考。Objective:To investigate the chemical components of Ziziphi Spinosae Semen monodecoction,Schisandrae Chinensis Fructus monodecoction,and their co-decoction(with the compatibility ratio of 2∶1)by high performance liquid chromatography-linear ion trap-orbitrap high resolution mass spectrometry(HPLC-LTQ-Orbitrap-MS^(n)).Methods:Electrospray ionization source(ESI)was applied to the analysis in positive and negative ion modes respectively.Fourier transform-infrared spectroscopy(TF,Full Scan,Resolution of 30000)and data-dependent acquisition of ddMS2 and ddMS3 spectra were employed,and the retention time,accurate mass measurements,and mass fragmentation patterns were analyzed.Results:A total of fifty chromatographic signals in the positive and negative ion modes of Ziziphi Spinosae Semen monodecoction were detected and their chemical components were identified,among which ten compounds(6 flavonoids,2 alkaloids,and 2 saponins)had been identified by fingerprint analysis or reported for content determination in the last ten years.Thirty-two chromatographic signals representing different components were identified in the positive and negative ion modes of Schisandrae Chinensis Fructus monodecoction,and ten lignans had been identified for fingerprint analysis or reported for content determination in the last ten years.Fifty chromatographic signals were identified in the positive and negative ion modes of the co-decoction of Ziziphi Spinosae Semen and Schisandrae Chinensis Fructus,and 19 compounds(5 flavonoids,1 alkaloid,1 saponin,and 12 lignans)of which had been detected in the monodecoction for fingerprint analysis or content determination in the last ten years.Jujuboside B,a saponin,was detected in Ziziphi Spinosae Semen monodecoction while not in the co-decoction.However,an ion peak representing lignan isomer in Schisandrae Chinensis Fructus was detected only in the co-decoction.Conclusion:HPLC-LTQ-Orbitraps-MS^(n)realized the qualitative analysis of the chemical composition changes of monodecoction and co-decoction of

关 键 词：酸枣仁 五味子 合煎液 高效液相色谱-线性离子阱串联静电场轨道阱质谱法 化学成分 

分 类 号：R284[医药卫生—中药学]