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采用高效液相色谱-二极管阵列检测、飞行时间质谱和四极杆离子阱质谱法分析五味子及大鼠血浆中的木脂素。

Analysis of lignans in Schisandra chinensis and rat plasma by high-performance liquid chromatography diode-array detection, time-of-flight mass spectrometry and quadrupole ion trap mass spectrometry.

作者信息

Lou Ziyang, Zhang Hai, Gong Chungui, Zhu Zhenyu, Zhao Liang, Xu Yuanjie, Wang Bin, Zhang Guoqing

机构信息

School of Pharmacy, Second Military Medical University, and Department of Pharmacy, Eastern Hepatobiliary Surgery Hospital, Shanghai 200433, China.

出版信息

Rapid Commun Mass Spectrom. 2009 Mar;23(6):831-42. doi: 10.1002/rcm.3931.

Abstract

High-performance liquid chromatography/diode-array detection (HPLC/DAD), time-of-flight mass spectrometry (HPLC/TOFMS) and quadrupole ion trap mass spectrometry (HPLC/QIT-MS) were used for separation, identification and structural analysis of lignans in Schisandra chinensis and rat plasma after oral administration of the herbal extract. Six lignans in Schisandra chinensis extract were identified unambiguously by comparing the retention time, their characteristic ultraviolet (UV) absorption and accurate mass measurement. A formula database of known lignans in Schisandra chinensis was established, against which the other 15 lignans were identified effectively based on the accurate extract masses and formulae acquired by HPLC/TOFMS. In order to distinguish the isomers, multi-stage mass spectrometry (ion trap mass spectrometry, MSn) was also used. The fragmentation behavior of the lignans in the ion trap mass spectrometer was studied by the six lignan standards, and their fragmentation rules in MSn spectra were summarized. These deduced fragmentation rules of lignans were successfully implemented in distinguishing the three groups of isomers in Schisandra chinensis by HPLC/QIT-MS. By using the three different analytical techniques, 21 lignans in Schisandra chinensis were identified within 30 min. After oral administration of the extract, 11 lignans in rat plasma were detected and identified by comparing their retention time, characteristic UV absorption and accurate mass measurement of peaks in HPLC/TOFMS chromatograms of the herbal extract. Finally, HPLC/TOFMS fingerprints of Schisandra chinensis in vitro and rat plasma in vivo were established. It is concluded that a rapid and effective method based on three analytical techniques for identification of chemical components was established, which is useful for rapid identification of multiple components in Schisandra chinensis in vitro and in vivo. In addition, it can provide help for further pharmacology and action mechanism study of lignans in Schisandra chinensis.

摘要

采用高效液相色谱/二极管阵列检测(HPLC/DAD)、飞行时间质谱(HPLC/TOFMS)和四极杆离子阱质谱(HPLC/QIT-MS)对五味子及大鼠口服该草药提取物后的血浆中的木脂素进行分离、鉴定和结构分析。通过比较保留时间、特征紫外(UV)吸收和精确质量测定,明确鉴定出了五味子提取物中的6种木脂素。建立了五味子已知木脂素的分子式数据库,并根据HPLC/TOFMS获得的精确提取物质量和分子式,有效鉴定出了另外15种木脂素。为了区分异构体,还采用了多级质谱(离子阱质谱,MSn)。通过6种木脂素标准品研究了木脂素在离子阱质谱仪中的裂解行为,并总结了它们在MSn谱图中的裂解规律。这些推导的木脂素裂解规律成功应用于通过HPLC/QIT-MS区分五味子中的三组异构体。通过使用这三种不同的分析技术,在30分钟内鉴定出了五味子中的21种木脂素。口服提取物后,通过比较大鼠血浆中各峰在草药提取物HPLC/TOFMS色谱图中的保留时间、特征UV吸收和精确质量测定,检测并鉴定出了11种木脂素。最后,建立了五味子体外和大鼠体内血浆的HPLC/TOFMS指纹图谱。结论是建立了一种基于三种分析技术的快速有效的化学成分鉴定方法,该方法有助于快速鉴定五味子体外和体内的多种成分。此外,它可为进一步研究五味子中木脂素的药理作用和作用机制提供帮助。

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