UPLC-Q-TOF-MS^E结合相对保留时间在线快速鉴定麦冬中甾体皂苷类成分

Identification of Steroidal Saponins in Ophiopogonis Radix by UPLC-Q-TOF-MSE Combined with Relative Retention Time

目的:采用超高效液相色谱-飞行时间质谱(UPLC-Q-TOF-MSE)表征并快速在线鉴定麦冬中甾体皂苷类成分;结合呋甾皂苷在反向色谱上的保留规律,鉴别同分异构体。方法:运用2种反相色谱柱(ACQUITY UPLC HSS T3和Agela Venusil XBP C18-2),在2种溶剂系统(0.1%甲酸/水-0.1%甲酸/乙腈,丙酮-水)和3个洗脱条件下对系列呋甾皂苷的色谱保留规律进行总结。利用UPLC-Q-TOF-MSE对麦冬成分进行分析,获得质谱数据。结果:3种色谱条件下呋甾皂苷的相对保留时间一致,呈现如下保留规律:甾体皂苷中糖链结构相同,苷元上羟基的数目越多保留时间越短;仅羟基位置不同时,保留时间为1位羟基<17位羟基<14位羟基;仅C-26位糖链糖基连接位置不同时,葡萄糖-(1→6)-葡萄糖<葡萄糖-(1→2)-葡萄糖;从麦冬表征的图谱中共鉴定了21个色谱峰,其中14个呋甾皂苷,7个为螺甾皂苷。结论:色谱保留时间能为呋甾皂苷同分异构体的液质联用在线鉴定提供有益的数据支持。

Objective： To identify the steroidalsaponins in the tubers of Ophiopogonis Radix by ultraperformance liquid chromatography tandem with time-of-fight mass spectrometry（ UPLC-Q-TOF-MSE） combined with the relative retention time（ RRT） of furostanolsaponins in reverse chromatography. Method： The retention time of several furostanolsaponins was tested on two kinds of reversed-phase column,Acquity UPLC HSS T3 and Agelavenusil XBP C18-2,using water（ 0. 1% formic acid）-acetonitrile（ 0. 1% formic acid） and acetone-water,respectively. The mass spectrometric data of Ophiopogonis Radix were obtained by UPLC-Q-TOF-MSE. Result：The RRT of furostanolsaponins was consistently in three chromatographic conditions. When the sugar parts were identical,the RRT was shorter alone with the increase number of hydroxyl; location of hydroxyl affected the RRT,the orders were asfollow： 1-hydroxyl 17-hydroxyl 14-hydroxyl. When only the sugar chain at C-26 was different,the RRT was as follow： glucosyl-（ 1 →6）-glucosyl glucosyl-（ 1 →2）-glucosyl. UPLC-Q-TOF-MSEcombined with RRT,a total of 21 compounds were identifiedincluding 14 furostanolsaponins and 7 spirostanolsaponins.Conclusion： The RRT of furostanolsaponins provide supportive data for rapidly identify isomers of steroidalsaponins from Ophiopogonis Radix by UPLC-Q-TOF-MSE.