卫生研究

目的建立C₁₈-Al_2O₃复合填料固相萃取柱净化,同时检测植物油及谷类制品中玉米赤霉烯酮和α-玉米赤霉烯醇的超高效液相色谱串联质谱方法。方法谷类制品先用正己烷-乙酸乙酯(50:50,V/V)提取,然后和植物油一样用乙腈-水(90:10,V/V)萃取玉米赤霉烯酮类真菌毒素,进一步用C₁₈-Al_2O₃固相萃取柱净化,以乙腈-水为流动相梯度洗脱,以C₁₈色谱柱(2.1 mm×100 mm,1.6μm)进行色谱分离,电喷雾离子化负离子多反应监测模式检测,¹³C₁₈-玉米赤霉烯酮为内标定量。结果玉米赤霉烯酮和α-玉米赤霉烯醇的线性范围为1.0~500 ng/mL,在植物油和谷类制品中的检出限分别为0.3和0.2μg/kg,定量限为1.0和0.5μg/kg。当添加量为1~100μg/kg时,玉米赤霉烯酮和α-玉米赤霉烯醇的平均回收率分别为93.5%~108.0%和92.0%~105.0%,相对标准偏差分别为3.2%⁸.5%和4.6%⁷.8%(n=6)。采用该方法对市售的55份样品进行测定,以玉米油中玉米赤霉烯酮和α-玉米赤霉烯醇含量、检出率最高,最高含量分别为453.1和5.0μg/kg,中位值分别为126.2和2.0μg/kg。结论该方法操作简便快速,净化效果好,灵敏准确,检测成本低,适于植物油和谷类制品中玉米赤霉烯酮和α-玉米赤霉烯醇的快速检测。

Objective To develop a method for simultaneous determination of zearalenone( ZEN) and α-zearalenol( α-ZEL) in vegetable oil and grain products by solid phase extraction column purification coupled with ultra-performance liquid chromatography tandem mass spectrometry.Methods Firstly,ZEN and α-ZEL in grain products were extracted by hexane/ethyl acetate( 50 : 50,V/V),and then extracted as vegetable oil by acetonitrile-water solution( 90: 10,V/V),and purified by C₁₈-Al_2O₃ solid phase extraction column.ZEN and α-ZEL was separated by UPLC with acetonitrile-water gradient elution on C₁₈ column( 2.1 mm × 100 mm,1.6 μm), and qualified/quantified by mass spectrometry with ESI negative MRM mode with ¹³C₁₈-zearalenone as internal standard.Results The linearity of ZEN and α-ZEL ranged from 1.0-500 ng/mL.The limit of detection for ZEN and α-ZEL in vegetable oil and grain products was 0.3 and 0.2 μg/kg,respectively.The limit of quantification for ZEN and α-ZEL in vegetable oil and grain products was 1.0 and 0.5 μg/kg.The average recoveries of ZEN and α-ZEL for spiked samples of 1.0-100 μg/kg were 93.5%-108.0% and 92.0%-105.0%.The relative standard deviations of ZEN and α-ZEL were 3.2%-8.5% and 4.6%-7.8%( n = 6).55 samples sold in Hangzhou supermarkets were analyzed.ZEN was detected in all corn germ oil with median and maximum contents of 126.2 and 453.1 μg/kg.α-ZEL was detected in 50% corn germ oil with median and maximum contents of 2.0 and 5.0μg/kg.Conclusion The method possesses several advantages including sensitivity,precision,good efficiency of purification,simplicity and economy,and it is applicable to the batch analysis of zearalenone and α-zearalenol in vegetable oil and grain products.