本研究建立了一种基于超高效液相色谱-四级杆/静电场轨道阱高分辨质谱法快速筛查和定量分析酒类样本中64种非法添加化合物的方法。样品经加热除去酒精，再加入甲醇进行超声提取并定容，经微孔滤膜过滤后上机分析。利用Thermo Hypersil GOLD C18 （100 mm×2.1 mm，1.9 μm）柱进行色谱分离，甲酸铵溶液和乙腈为流动相进行梯度洗脱。质谱条件采用正离子和负离子同时扫描，全扫描/数据依赖的二级扫描（Full MS/dd-MS2）模式，以分析物的保留时间和一级母离子以及自动触发采集的二级碎片离子信息建立数据库，进行高通量筛查和定量分析，并对市售酒类样品进行筛查测定。结果表明各目标化合物在一定的质量浓度范围内线性关系良好（相关系数r2>0.99），定量限为0.1~2.5 mg/kg，回收率为88.3%~127.9%，相对标准偏差为0.2%~6.2%（n=6）。该方法操作简单，灵敏度高，分析时间短，结果准确可靠，适用于酒类样本中64种非法添加化合物的快速筛查和确证。

In this study, a method for rapid screening and quantitative analysis of 64 kinds of illegally added compounds in alcohol samples by ultra-performance liquid chromatography-quadrupole/electrostatic field orbitrap high-resolution mass spectrometry (UPLC-HRMS) was established. The samples were heated to remove alcohol, and then methanol was added for ultrasonic extraction. The resulting extract was topped up to a fixed volume, filtered through a microporous membrane, and separated by a ThermoHypersil GOLD C18 column (100 mm×2.1 mm, 1.9 μm; ammonium formate and acetonitrile as the mobile phase for gradientelution), before analysis. Mass spectrometry conditions were: simultaneous scanning of positive and negative ions, and full scan/data-dependent secondary scan (Full MS/dd-MS2) mode. High-throughput screening and quantitative analysis of commercially available alcohol samples were carried out with the database set up based on the retention time of the analyte, primary parentions, and automatically collected secondary fragment ions. The results showed a good linear relationship for each target compound within a certain mass concentration range, with correlation coefficients (r2) >0.99, limits of quantitation (LOQs) ranging from 0.1 to 2.5 mg/kg, recoveries in the range of 88.3%~127.9%, and relative standard deviations as 0.2%~6.2% (n=6). This method is simple, highly selective, rapid, accurate and reliable, there by suitable for rapid screening and verification of 64 kinds of illegally added compounds in alcohol samples.

国家自然科学基金项目（21577042）