摘要
目的采用电喷雾离子阱质谱(ESI-IT-MS)对白术内酯Ⅰ进行解析鉴定,并建立液相色谱-离子阱质谱串联法(LC-IT-MS)测定白术中白术内酯Ⅰ的含量。方法白术内酯Ⅰ标准品经蠕动泵直接进样,ESI-IT-MS正离子模式下测定,获得质谱图,并对其主要碎片进行分析,采用DL-C18反相色谱柱(250 mm×4.6mm,5.0μm),甲醇-0.5%乙酸水溶液(75∶25)为流动相,样品采用80%甲醇提取,在正离子模式下,采用选择离子监测(SIM)方式,其监测离子对为m/z 233→215,使用LC-IT-MS测定其中白术内酯Ⅰ含量。结果白术内酯Ⅰ的ESI-MS获得m/z 233[M+H]+,255[M+Na]+和487[2M+Na]+,而ESI-MS2获得m/z 215、205、187、177、160和151等碎片离子,在0.5~50μg/mL范围内白术内酯Ⅰ获得良好线性关系(r=0.9995),检测限为2.0 ng/mL,平均回收率为96.5%。结论 ESI-MS正离子模式下适用于白术内酯Ⅰ结构解析鉴定,归属了主要的碎片裂解途径,所建立的LC-IT-MS方法快速灵敏,适用于白术中白术内酯Ⅰ的检测,研究结果可为白术质量控制体系,药代动力学和结构修饰等研究提供科学的参考依据。
Objective To develop an electron spray ionization-ion trap mass spectrometry(ESI-MS) method for the characterization of atractylenolide Ⅰ and an high performance liquid chromatography coupled with ion trap-mass spectrometry(LCIT-MS) method for analysis of atractylenolide Ⅰ in rhizome of Atractylodes macrocephala.Methods A syringe pump was used for the direct loop injections of atractylenolide Ⅰ and MS was obtained by using ESI-IT-MS to analyze the main fragments of atractylenolide Ⅰ in positive ion mode.The chromatographic separation was carried out on a DL-C18 column(250 mm×4.6 mm,5.0 μm).The gradient elution was implemented with the mobile phase containing methanol and water with 0.1% acetic acid(75:25,v/v).The samples were extracted with 80% methanol and atractylode Ⅰ was determined by LC-IT-MS.Under the positive ion mode,selective ion monitoring(SIM) mode was used with the ion pair was m/z 233→215.Results Molecular ion peak m/z 233 [M+H]+,255 [M+Na]+and 487 [2 M+Na]+and the main fragment ions of m/z 215,205,187,177,160 and 151 were detected by ESI-MS and ESI-MS2,respectively.Good linearity was obtained in the range of 0.5-50 μg/mL,with detection limit of 2.0 ng/mL.The average recovery was 96.5%.Conclusion It is suitable for determination the fragmentation and investigation of the fagmentation pathways of atractylenolide Ⅰ by ESI-MS in positive mode.The developed LC-IT-MS method is rapid,sensitive and suitable for analysis of atractylenolide Ⅰ in rhizome of Atractylodes macrocephala,which can provide scientific reference for its subsequent quality control,pharmacokinetics,modifying structure basis study.
作者
曹扶胜
余飞
陈琴华
CAO Fushen;YU Fei;CHEN Qinhua(Department of General Surgery,Shiyan Hospital of Integrated Traditional and Western Medicine,Shiyan 442011;Medical Laboratory Center,Affiliated Dongfeng Hospital,Hubei University of Medicine,Shiyan 442008;Hubei Key Laboratory of Wudang Local Chinese Medicine Research,Hubei University of Medicine,Shiyan 442000)
出处
《湖北中医药大学学报》
2020年第2期45-48,共4页
Journal of Hubei University of Chinese Medicine
基金
湖北省卫生健康委员会中医药科研项目面上项目(项目编号:ZY2019M034)
湖北医药学院武当特色中药研究湖北省重点实验室开放课题(项目编号:WDCM2018004)
湖北省十堰市科技局指导性项目(项目编号:19Y87和19Y88)。
