UHPLC-LTQ-Orbitrap HRMS法结合特征裂解途径分析鉴定薄荷水提物中4种类群化学成分

采用超高效液相色谱-线性离子阱-串联静电轨道阱高分辨质谱(UHPLC-LTQ-Orbitrap HRMS)法对薄荷水提物中4种类群化学成分进行分析鉴定。选取Acquity UPLC~BEH C18色谱柱(2.1mm×100mm×1.7μm),以乙腈-0.1%甲酸水溶液为流动相,流速0.30mL/min,梯度洗脱分析。根据高分辨质谱提供的准分子离子峰和碎片离子信息,获取目标化合物的相对分子质量和结构信息,并结合保留时间、对照品分析、参考文献数据和ClogP值等相关信息,鉴定了85种化学成分,包括38种黄酮、16种酚酸、7种苯丙素和24种萜类。结果表明,采用UHPLC-LTQ-Orbitrap HRMS技术能够提高中药化学成分的分析效率,该方法可为合理开发薄荷的药用和食用价值奠定化学基础。

Rapid Identification of Four Groups Chemical Constituents of Aqueous Extracts from Menthae Haplocalycis Herba by UHPLC-LTQ-Orbitrap HRMS Combined with Cleavage Pathways

Menthae Haplocalycis herba, one kind of Chinese edible herbs, has been widely adopted for the clinical use in China for thousands of years. Over the last decades, the studies on chemical constituents of Menthae Haplocalycis herba have been widely reported. However, too much attention had been paid for its volatile constituents. Non-volatile components are also responsible for its medical efficacy based on the fact that it is usually decocted with water in the clinical practice. In the present study, a method of ultra-high performance liquid chromatography coupled with linear ion trap-Orbitrap mass spectrometry (UHPLC-LTQ-Orbitrap HRMS) was developed for a comprehensive study of the chemical constituents in Menthae Haplocalycis herba aqueous extracts. Separation was performed with an Acquity UPLC^® BEH C18 column (2.1 mm×100 mm×1.7 μm) with 0.1% formic acid aqueous solution and acetonitrile as the mobile phase with the speed of 0.30 mL/min under gradient conditions. Based on the accurate mass measurement (error<5×10^-6), MS/MS fragmentation pathways, different chromatographic behaviors, an important parameter ClogP value and compared with the standards and references, 85 compounds were unambiguously identified or tentatively characterized, including 38 flavonoids, 16 phenolic acids, 24 terpenoids and 7 phenylpropanoids. The result demonstrated that UHPLC-LTQ-Orbitrap HRMS can improve the analysis efficiency of the chemical constituents of traditional Chinese medicine (TCM) extracts, which also benefit to lay the chemical foundation for rational development of medical and edible value of Menthae Haplocalycis herba.