超高效液相色谱-四极杆飞行时间质谱法用于食物中毒的快速筛查与确证

建立了一种利用超高效液相色谱-四极杆飞行时间质谱筛查食物中毒的方法。试样用乙腈提取,QuEChERS净化,以0.1%(v/v)甲酸水溶液和0.1%(v/v)甲酸乙腈溶液为流动相进行梯度洗脱,经Acquity UPLC BEH C18柱(100 mm×2.1 mm,1.7μm)分离。采用四极杆飞行时间质谱信息依赖性扫描(information dependent acquisition,IDA)模式进行分析。该模式可以实现一次进样分析同时获得分析物的一级和二级碎片的精确质量质谱图,结合SCIEX OS软件可对581种目标物质进行快速筛查,其中包括546种农药、24种真菌毒素、11种鼠药,以一级离子精确质量数、一级离子同位素丰度比以及二级碎片进行标准质谱库匹配。应用建立的快速筛选确认检测方法对一起突发性食物中毒安全事件样本进行检测,共检测11份样本,其中9份均检测出呋喃丹。进一步以呋喃丹标准品确认保留时间,结果表明,样品与标准品保留时间一致。呋喃丹的精确质量数偏差均小于3.7×10-6,在0.5~500 ng/mL范围内线性关系良好,相关系数为0.998,仪器检出限(S/N=3)为0.3μg/kg,定量限(S/N=10)为1μg/kg,在10、50、200μg/kg 3个添加水平的回收率为75.6%~95.9%,相对标准偏差为3.6%~6.9%(n=6)。该方法快速、简便、准确、灵敏,适用于突发性公共安全事件的快速筛查与检测要求。

Rapid screening and identification of food poisonings by ultra high performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry

A method was developed for the screening and detection of food poisonings by ultra high performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry (UHPLC-Q-TOF MS). After extracted by acetonitrile and cleaned-up by QuEChERS, the extract was separated on a Waters Acquity UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm) with the gradient elution of 0.1% (v/v) formic acid in water and 0.1% (v/v) formic acid in acetonitrile. TOF-MS scan-information dependent acquisition (IDA)-product ion scan was performed in positive electrospray ionization (ESI) mode to acquire high resolution MS and MS/MS spectra in one injection, and rapidly screen 581 target compounds by SCIEX OS software, including 546 pesticides, 24 mycotoxins, 11 rodenticides. The target compounds were qualitatively confirmed by mass accuracy of precursor, isotope distribution of precursor, fragment ions of precursor, and library search. Carbofuran was detected in 9 out of 11 samples with the proposed method. The retention time was further confirmed by the standard of carbofuran. The results showed the retention times were coincident between the samples and reference standard, and the deviations of accurate mass numbers were all less than 3.7×10^-6. The scope of the relationship was good and the correlation coefficient was 0.998. The instrumental limit of detection (S/N=3) was 0.3 μg/kg, and the limit of quantification (S/N=10) was 1 μg/kg. The recoveries at 10, 50, 200 μg/kg levels were 75.6%-95.9%, and the RSDs (n=6) were 3.6%-6.9%. The method is rapid, simple, accurate and sensitive. It is suitable for the rapid screening and detection of public safety incidents.