Q-Orbitrap高分辨质谱用于降血脂类中成药和保健食品中非法添加物的快速筛查、鉴定和定量

Application of Q-Orbitrap high resolution mass spectrometry to the detection of illegal adulterated antihyperlipidemics in herbal medicines and dietary supplements

目的:建立Q-Orbitrap高分辨质谱(HRMS)法用于降血脂类中成药和保健食品中非法添加烟酸、洛伐他汀和辛伐他汀的快速筛查、确证和定量。方法:采用Hypersil GOLD a Q C18色谱柱(100 mm×2.1 mm,1.9μm),线性梯度洗脱,流动相A为10 mmol·L-1的乙酸铵溶液,流动相B为甲醇,流速300μL·min-1。采用正离子检测,全扫描/数据依赖的二级扫描(Full MS/dd-MS2)扫描模式,在1个分析周期(10 min)内完成对样品中分析物的分离和高精度一级、二级质谱扫描,得到准确质量数(accurate mass,AM)和准确碎片离子信息。通过比较样品与对照品的色谱保留时间、一级质谱、二级质谱,确定样品中是否掺杂了降血脂化学药物,并对阳性样品进行定量分析。结果:建立的Q-Orbitrap HRMS法简便快速、定性能力强,检测限为0.1 ng·m L-1,线性、准确度、精密度皆符合要求,非常适合高通量非法添加筛查。在38批降血脂类中成药和保健食品中检出2批阳性样品,不符合率为5.26%;检出的非法添加物含量均>10 mg·g-1。结论:Q-Orbitrap HRMS用于降血脂类中成药和保健食品中非法添加化学药物的快速筛查、确证和定量,具有快速、准确、高选择性的特点,为打击日益猖獗的非法添加行为提供了新工具、新技术。

Objective： To establish a Q-Orbitrap high resolution mass spectrometry （HRMS） method for the screening, confirmation and quantitation of illegal adulterated antihyperlipidemics in herbal medicines and dietary supplements. Methods： Hypersil GOLD aQ C18 chromatographic column （100 mm ×2. 1 mm, 1.9 μm）was adopted for chromatographic separation with gradient elution. The mobile phase consisted of 10 mmol . L-l ammonium acetate solution（A） and methanol （B）at a flow rate of 300μ L . min-1. The analytes were detected by positive ion ESI in Full MS/dd - MS2mode. 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,precursorions and product ions were compared with the standard. Samples that illegally adulterated with antihyperlipidemics were identified. Results：The established Q - Orbitrap HRMS method possessed powerful qualitative ability and high sensitivity. The LOD was 0. 1 ng .mL-1 ,while the linearity, accuracy,precision and recovery were in compliance with the requirements. Among 38 herbal medicines and dietary supplements, 5.26% of the studied samples were positive. The content of illegal adulterants detected was more than 10 mg . g-1. Conclusion： This new Q-Orbitrap HRMS method was rapid, accurate and high selective, which provides a novel powerful tool for the combating with rampant illegal adulteration behaviors.