高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (8): 1566.

• 研究论文 • 上一篇    下一篇

4种儿茶素类化合物电喷雾质谱裂解规律的研究

刘国强1, 董静2, 王弘1, 万乐人2, 端裕树2, 陈世忠1   

  1. 1. 北京大学药学院, 北京 100191;
    2. 岛津国际贸易(上海)有限公司北京分析中心, 北京 100020
  • 收稿日期:2008-12-12 出版日期:2009-08-10 发布日期:2009-08-10
  • 通讯作者: 陈世忠, 男, 博士, 副教授, 主要从事天然药物化学研究. E-mail: chenshizhong66@163.com; 端裕树, 男, 博士, 研究员, 主要从事仪器分析方面的研究. E-mail: y-hashi@shimadzu.co.jp
  • 基金资助:

    国家“九七三”计划(批准号: 2006CB504707)资助.

ESI Fragmentation Studies of Four Tea Catechins

LIU Guo-Qiang1, DONG Jing2, WANG Hong1, WAN Le-Ren2, HASHI Yuki2*, CHEN Shi-Zhong1*   

  1. 1. School of Pharmaceutical Science, Peking University, Beijing 100191, China;
    2. Shimadzu International Trading(Shanghai) Co. Limited, Beijing Office, Beijing 100020, China
  • Received:2008-12-12 Online:2009-08-10 Published:2009-08-10
  • Contact: CHEN Shi-Zhong. E-mail: chenshizhong66@163.com; HASHI Yuki. E-mail: y-hashi@shimadzu.co.jp
  • Supported by:

    国家“九七三”计划(批准号: 2006CB504707)资助.

摘要:

利用离子阱飞行时间质谱仪的高质量精度、高分辨率及多级测定性能, 对儿茶素类化合物(二组对映异构体)质谱裂解进行研究, 并利用氢/氘交换法对裂解方式进行确证. 发现儿茶素对映异构体间具有相同的质谱裂解途径, 多级质谱无明显区别. 在二级质谱中, 表儿茶素/儿茶素(EC/C)丢失的CO2发生在A环, 丢失的C2H2O发生在B环. 1,4A-, 1,3A-, 1,2A-和[M-H-B环]-4个碎片离子为EC/C特征离子, 通过这4个离子质量数变化, 推测A环上的取代情况. 因表儿茶素没食子酸酯/儿茶素没食子酸酯(ECG/CG)结构上都含有没食子酸取代基, 在二级质谱中均可见m/z 169特征峰, 此离子可用于ECG/CG和EC/C区分.

关键词: 表儿茶素/儿茶素; 表儿茶素没食子酸酯/儿茶素没食子酸酯; 氢/氘交换; 质谱裂解

Abstract:

The fragmentation pathways of tea catechins(two group stereoisomers ) were studied via the ion-trap time-of-flight(IT-TOF) mass spectrometer with the advantages of high mass accuracy, high resolution, multistage analysis. Hydrogen/deuterium exchange method was used to elucidate the fragmentation processes. The results show that catechin stereoisomers possess the same fragmentation pathways and cannot be differen-tiated even in MSn spectra. We can locate the loss of CO2 and C2H2O in MS2 spectra from EC/C to A ring and B ring, respectively. The ions of 1,4A-, 1,3A-, 1,2A- and [M-H-B ring]- were characteristic product ions for EC/C, and it could be used to propose the substituent group of A ring through the m/z shift of these ions. The ion at m/z 169 corresponding to the gallic acid anion was characteristic fragmentation of ECG/CG, which was great helpful for differentiating ECG/CG and EC/C.

Key words: EC/C; ECG/CG; Hydrogen/deuterium(H/D) exchange; Mass fragmentation

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