Abstract
Chinese A method based on ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap mass spectrometry was developed for the rapid determination of 13 β-blockers in health foods. The MS fragmentation pathways of the analytes were subsequently investigated. The optimal MS conditions, extraction solvents, mobile phases, and matrix effects were evaluated in detail. The samples were extracted with methanol, filtered by high-speed centrifugation and ultrasonic treatment, and then separated on an Acquity UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm) with gradient elution using acetonitrile and 0.1% (v/v) formic acid aqueous solution as mobile phases. MS analysis was conducted in positive-ion mode, and the data were collected using full mass and data-dependent MS2 scans (Full MS/dd-MS2). The efficient separation and high-precision primary and secondary scanning of the 13 β-blockers in health foods were realized within 10 min, and accurate mass numbers and fragment-ion information were obtained. The methodological validation showed good linear relationships in the range of 0.5-100 μg/L, with correlation coefficients (r)≥0.9912. The limits of detection ranged from 1 to 10 μg/kg. When the standard substances were added to the blank sample in the amount of 10-200 μg/kg, the recoveries were in the range of 75.3%-108.4%, and the relative standard deviations ranged from 0.9% to 10.0% (n=6). The method was used to screen 30 batches of commercially available health foods, and none of the 13 β-blockers was detected. The proposed method is fast, accurate, and sensitive, and can be used for the rapid determination of β-blockers in health foods. 建立了基于超高效液相色谱-四极杆/静电场轨道阱质谱快速测定保健食品中13种β-受体阻滞剂的分析方法,并对其质谱裂解规律进行了分析研究。实验对质谱条件、色谱条件、提取溶剂及基质效应等进行了详细探究,使用甲醇对样品进行稀释提取,高速离心、超声处理,用Acquity UPLC BEH C18柱(100 mm×2.1 mm, 1.7 μm)分离,以乙腈和0.1%(v/v)甲酸水溶液作为流动相进行梯度洗脱,采用正离子模式检测,数据采集使用一级母离子全扫描和数据依赖的二级离子扫描(Full MS/dd-MS2)模式,在10 min内实现了保健食品中13种β-受体阻滞剂的分离和高精度一级、二级扫描,得到准确的质量数和准确碎片离子信息。通过方法学验证,13种β-受体阻滞剂在0.5~100 μg/L内线性关系良好,相关系数(r)均≥0.9912,检出限为1~10 μg/kg。空白加标样品中13种β-受体阻滞剂的平均回收率为75.3%~108.4%,相对标准偏差为0.9%~10.0%(n=6)。用本方法对市售的30批次保健食品进行筛查,均未检出13种β-受体阻滞剂。该方法检测速度快,准确性强,灵敏度高,可用于保健食品中β-受体阻滞剂的快速测定。