Q-Orbitrap高分辨质谱快速筛查及定量分析改善睡眠类保健品中非法添加的18个药物成分

目的：建立高效液相色谱-四极杆/静电场轨道阱质谱法（UPLC-Q-Orbitrap）快速筛查及定量分析改善睡眠类保健品中常见非法添加的18个药物成分。方法：保健品样品以甲醇为提取溶剂进行超声提取，离心取上清后，采用Waters HSS T3色谱柱（100 mm×2.1 mm，1.8μm）进行分离，乙腈（含0.1%甲酸）和水（含2 mmol·L^-1乙酸铵，0.2%甲酸）为流动相，梯度洗脱（0~1 min，35% B；1~7 min，35% B → 85% B；7~7.5 min，85% B → 35% B；7.5~10 min，35% B）；流速为0.3 mL·min^-1；柱温：35℃。质谱采用正离子和负离子切换扫描，全扫描/数据依赖的二级扫描（Full MS/dd-MS²）模式，在1个分析周期（10 min）内完成对样品中分析物的分离和一级、二级质谱扫描。通过比较样品与对照品的色谱保留时间、一级质谱和二级质谱，确定样品中是否掺杂了化学药物，并对阳性样品进行定量分析。结果：建立的UPLC-Q-Orbitrap方法简便快捷，定性能力强，非常适合高通量非法添加筛查。18个化学药物在0.15~300 ng·mL^-1范围内具有良好的线性（线性相关系数均大于0.993），各类药物的检测下限为0.05~20 ng·mL^-1，回收率为72.2%~118.7%，RSD为2.4%~9.2%。结论：该方法操作简单，分析时间短，灵敏度高，准确可靠，为打击日益猖獗的非法添加行为提供了新的手段。

Objective: To establish a Q-Orbitrap high resolution mass spectrometry method for the screening, confirmation and quantitation of 18 kinds of illegally added drugs in improving sleep health foods. Methods: The health food samples were extracted using methanol by sonication. After centrifugation, the supernatants were separated on a Waters HSS T3 column(100 mm×2.1 mm, 1.8 μm). Acetonitrile containing 0.1% formic acid(B) and water containing 2 mmol·L^-1 ammonium acetate combined with 0.2% formic acid (A) were used as mobile phase by gradient elution(0-1 min, 35%B; 1-7 min, 35%B → 85%B; 7-7.5 min, 85%B → 35%B;7.5-10 min,35%B) at a flow rate of 0.3 mL·min^-1,and the column temperature was 35℃. The analytes were detected by both positive and negative ion ESI in Full MS/dd-MS² mode. The accurate mass and MS² fragment ions were simultaneously attained within an analysis cycle(10 min), while the potential positive samples were quantified. The chromatographic retention time, precursor ions and product ions were compared with the standard,Samples that illegally adulterated were identified. Results: The established Q-Orbitrap method possessed powerful qualitative ability and high sensitivity. The results indicated that the linearity of all the 18 kinds of drugs ranged from 0.15 ng·mL^-1 to 300 ng·mL^-1 with the correlation coefficients of greater than 0.993. The limits of detection were confirmed by spiked samples, and were between 0.05 and 20 ng·mL^-1 for the 18 drugs. The recoveries were in the range of 72.2% to 118.7%,with the relative standard deviations in the range of 2.4% to 9.2%. Conclusion: This new Q-Orbitrap method was rapid,accurate and high selective, which provides a novel powerful tool for the combating with rampant illegal adulteration behaviors.

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