基于UPLC-Q-TOF MS技术的三七中皂苷类成分质谱裂解规律研究

采用超高效液相色谱-串联四极杆飞行时间质谱(UPLC-Q-TOF MS)法快速分析三七中17种化合物,包括4对人参皂苷同分异构体,即三七皂苷R_1、R_2,人参皂苷Rg_1,人参皂苷Rg_3、Rb_1、Rb_2、Rb_3、Re、Rf、Rc、Ro、Rd、Rk_1、Rh_1和拟人参皂苷_(F11)。采用Waters Acquity UPLC~(TM)BEH C18色谱柱(2.1mm×150mm×1.7μm),以乙腈(A)-0.1%甲酸水溶液(B)为流动相进行梯度洗脱,在电喷雾负离子模式下采集数据。结果表明,17种常见的三七皂苷和人参皂苷化合物对照品(包含多种同分异构体皂苷)可被液相色谱完全分离,通过归纳总结质谱全裂解信息,探讨了其裂解规律和特征离子。该方法可为快速鉴定和分析含有三七皂苷和人参皂苷类成分的化合物提供参考,并为全面表征三七指纹图谱提供依据。

Fragmentation Pathway of Ginsenosides in Panaxnotoginseng Using Electrospray Ionization-Quadrupole/Time-of-Flight Mass Spectrometer

Panaxnotoginseng (Burk.) F.H. Chen or Sanqi in Chinese is a well-known Chinese medicinal herb, which has been used for thousands of years in China due to its good hemostatic effect. The major bioactive compounds of Panaxnotoginseng are Dammarane triterpenesaponins, especially protopanaxadiol and protopanaxatriol glycosides. While, the normal method of compounds identification in plants mainly based on the NMR spectra of the pure compounds, which obtained by isolation and purification on a scale of crude drugs. Liquid chromatography coupled with mass spectrometry (LC/MS) can identify and characterize the compounds, and has been increasingly developed for the compounds research of crude drugs. In this study, 17 compounds (notoginsenoside R₁, R₂, ginsenoside Rg₁, Rg₂, Rg₃, Rb₁, Rb₂, Rb₃, Re, Rf, Rc, Ro, Rd, Rk₁, Rh₁ and pseudoginsenoside F₁₁) in Panaxnotoginseng including four pairs of ginsenoside isomers were detected using ultra perform liquid chromatogram-electrospray ionization-quadrupole/time-of-flight mass spectrometer (UPLC-Q-TOF MS). Compounds were analyzed on Acquity UPLC^TM BEH C18 (2.1 mm×150 mm×1.7 μm) with acetonitrile (A) 0.1% formic acid aqueous solution (B) as mobile phase for gradient elution. The data were collected by negative electrospray ion mode using Q-TOF MS. The parameters of ion source were as follows: capillary voltage of 2 500 V, cracking voltage of 60-70 V, ion source temperature of 300 ℃, dry nitrogen flow rate of 800 L/h. Under this condition, all of 17 saponins were separated neatly within 1 h. The fragmentation behaviors especially the MS fragmentation rules of isomers were compared. According to the structure and the typical fragmentations, these saponins were divided into different typical types, and each type has its special fragments that can be easily identified. Meanwhile, the identification and structure of the 17 ginsenoside could provide essential and important data for the further studies on the multiple constitutions of Panaxnotoginseng as well as ginseng which also has the same or some similar constitutions. These findings are valuable for the identification of ginsenosides in plants especially Panaxnotoginseng.