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    Sin-QuEChERS净化-超高效液相色谱-串联质谱法测定鱼肉中8种喹诺酮类药物残留量

    Determination of 8 Quinolone Drugs in Fish with Sin-QuEChERS Purification

    • 摘要: 将粉碎后的鱼肉样品2.00 g置于50 mL离心管中,加入100 μg·L-1内标溶液200 μL和水5 mL,涡旋1 min后,用含5%(体积分数)乙酸的乙腈溶液10 mL超声提取10 min,加盐包(6 g无水硫酸镁、1.5 g氯化钠)使水相和乙腈相进行分层。涡旋、离心后,使用Sin-QuEChERS快速滤过柱直接插入离心管内,待提取液透过净化层上升至净化柱内时,移取5 mL提取液置于15 mL离心管内,加入体积比1:1的乙腈-正己烷混合液5 mL,混匀静置,取上层正己烷层涡旋,离心,于40℃氮气吹至近干,用0.2%(体积分数)甲酸溶液定容至1 mL,过滤后上机UHPLC-MS/MS,在多反应监测模式下测定8种喹诺酮类药物的残留量。结果显示:该净化方法溶剂消耗降低至10 mL,前处理时间缩短至20~25 min。环丙沙星、培氟沙星、诺氟沙星、二氟沙星和达氟沙星标准曲线的线性范围均为1.00~500.0 μg·L-1,检出限(3S/N)均为1.0 μg·kg-1;氧氟沙星、恩诺沙星和沙拉沙星标准曲线的线性范围为0.50~500.0 μg·L-1,检出限(3S/N)均为0.5 μg·kg-1。用此法平行测定同一样品7次,测定值的相对标准偏差为1.3%~6.3%。按标准加入法进行回收试验,回收率为92.0%~108%。此法用于抽检兰州4家超市的3种鱼类,8种喹诺酮类药物均未检出,说明兰州市的鱼类食品中的药物残留问题相对安全。同时,与国家农业部1077号公告-1-2008中方法进行比对,测定结果基本一致。

       

      Abstract: The crushed fish sample (2.00 g) was placed in a 50 mL-centrifuge tube, and 200 μL of 100 μg·L-1 internal standard solution and 5 mL of water were added. After vortex for 1 min, the above mixture was extracted ultrasonically for 10 min with 10 mL of acetonitrile solution containing 5% (φ) acetic acid, and the salts (6 g of anhydrous magnesium sulfate and 1.5 g of sodium chloride) were added to separate the aqueous phase and acetonitrile phase. After vortex and centrifugation, Sin-QuEChERS rapid filtration column was directly inserted into the centrifuge tube. When the extract rose to the purifying column through the purifying layer, 5 mL of the extract was transferred into a 15 mL-centrifuge tube, a mixture of acetonitrile and n-hexane at the volume ratio of 1:1 was added, and then the mixture was mixed well and settled. The upper n-hexane layer of was taken, then swirl, centrifuged and blown to nearly dry at 40℃ with nitrogen. The residue was made its volume to 1 mL with 0.2% (φ) formic acid solution. After filtration, 8 quinolones residues were determined by ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) under multi-reaction monitoring mode. As shown by the results, the consumption of the solvent was reduced to 10 mL and the pretreatment time was shortened to 20-25 min by this purification method. The linear ranges of the standard curves of ciprofloxacin, pefloxacin, norfloxacin, difloxacin and danofloxacin were 1.00-500.0 μg·L-1, with the same detection limits (3S/N) of 1.0 μg·kg-1. The linear ranges of the standard curves of ofloxacin, enrofloxacin and sarafloxacin were 0.50-500.0 μg·L-1, with the same detection limits (3S/N) of 0.5 μg·kg-1. The same sample was determined 7 times in parallel by this method, with RSDs of the determined values in the range of 1.3%-6.3%. Test for recovery was made by standard addition method, giving results in the range of 92.0%-108%. This method was applied for sampling inspection of 3 kinds of fish from 4 supermarkets in Lanzhou, and 8 quinolones were not detected, showing that drug residues in fish food in Lanzhou were relatively safe. At the same time, the results were basically consistent with those of the method in Proclamation No. 1077-1-2008 of the State Ministry of Agriculture.

       

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