该研究建立了原位电离质谱实时快速直接分析猪肉中23种兽药残留的方法,同时通过基质效应、检出限和精密度进行方法学评价。猪肉经粉碎,乙腈提取并净化,净化后采用实时直接分析离子源与三重四极杆质谱联用技术实时快速直接分析,多反应监测模式检测,外标法定量。结果表明,兽药分子结构与原位电离的基质效应包含了竞争吸附和竞争离子化2个方面,喹诺酮类竞争吸附效应占据优势,磺胺硝基咪唑类竞争离子化效应占据优势;磺胺类、喹诺酮类和硝基咪唑类23种化合物在10 μg/L均能够正常检出;方法精密度即相对标准偏差(relative standard deviation,RSD)为36.25%~112.36%,采用原位质谱技术检测肉品中喹诺酮类时,净化柱提取液RSD明显低于其他基质的RSD,因此在检测肉品中喹诺酮类时,采用净化柱净化,能够获得较好的精密度。对于磺胺类和硝基咪唑类,提高净化程度对精密度的改善不明显。该方法快捷、简便,准确性、灵敏度较好,适合对市售猪肉中23种兽药残留进行不合格快速筛查。
A method was established for 23 veterinary drugs residues in pork by direct analysis in real-time mass spectrometry. At the same time, the methodological evaluation of matrix effect, detection limit, and precision. The pork was ground, extracted with acetonitrile, and then purified. Real-time fast direct analysis was performed using direct analysis in real-time (DART) in situ ionization source combined with triple quadrupole mass spectrometry (DART-QQQ) for detection, multiple reaction monitoring (MRM) mode detection, and an external standard method for quantification. Results showed that the matrix effect in DART of the molecular structure of veterinary drugs included two aspects, which were competitive adsorption and competitive ionization. The competitive adsorption effect of quinolones and the competitive ionization effect of sulfonamides and nitroimidazole were dominant. The detection limits of 23 veterinary drug residues in the three pretreatment methods were all 10 μg/L. The relative standard deviation (RSD) of the overall precision of the method was 36.25%-112.36%. In the detection of quinolones in meat by real-time rapid and direct analysis, the RSD of extracts from the purification column were significantly lower than those of other substrates. Therefore, better precision could be obtained by using a purification column for the detection of quinolones in meat. For sulfonamides and nitroimidazoles, increasing the purification degree has no obvious improvement in the precision. The method is accurate and sensitive, and is suitable for the simultaneous and rapid screening of 23 unqualified veterinary drugs in pork.
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