DLLME-UPLC-MS/MS法测定食用油中的双酚类化合物

Rapid Determination of Seven Bisphenols in Edible Oils with Dispersive Liquid-Liquid Microextraction and Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

基于分散液液微萃取(DLLME)技术和同位素稀释-超高效液相色谱-质谱/质谱(ID-UPLC-MS/MS),建立了一种快速测定食用油中7种双酚类化合物的方法。优化了萃取剂种类及体积、涡旋分散时间等影响萃取的关键因素;优化了UPLC分离条件和质谱定性定量参数。优化条件为:400μL甲醇/乙腈(1∶1,v/v)混合溶液作为萃取剂,涡旋分散萃取1 min;以C18色谱柱和甲醇-0.05%氨水梯度洗脱分离,质谱多反应监测模式(MRM)测定。结果表明,7种双酚类化合物在0.5μg/L^500μg/L内线性关系良好,相关系数均在大于0.998,方法定量限(S/N=10)在0.2μg/L^3.0μg/kg之间,3个添加水平的平均回收率为80.1%~93.7%,相对标准偏差(n=6)为4.4%~9.1%。本方法前处理简单,节省溶剂和时间,准确灵敏,适用于食用油中7种双酚类化合物的检测。

A simple and rapid method for determination of seven bisphenols in edible oils using dispersive liquid -liquid microextraction （DLLME） and ultra performance liquid chromatography -tandem mass spectrometry with isotope dilution （ID-UPLC-MS/MS） was developed. In the paper, related critical factors that may influence extraction efficiency, such as the type and volume of extraction solvent and vortex-assisted dispersive extraction time, and the separation condition of UPLC, qualitative and quantitative parameters of mass spectrometry were investigated and optimized. The optimum extraction condition was：extracting agent was 400μL mixed solution （methanol：acetonitrile=1∶1, v/v）, and vortex extraction 1 min. Targets were separated with a C18 chromatographic column by gradient elution with methanol-0.05%ammonia , and determined by UPLC-MS/MS under ESI at negative and multiple reaction monitoring （MRM） mode. The results indicated that 7 bisphenols were in the range of 0.5μg/L-500μg/L with the correlation coefficients greater than 0.998 , the method quantitation limit （LOQ, S/N=10） of the analytes were ranged from 0.2μg/kg to 3.0μg/kg. The average recoveries were from 80.1%to 93.7%, and the relative standard deviation （RSD, n=6） were in a range of 4.4%-9.1%when three levels of standard were spiked into edible oil sample. The method was simple, fast, saving solvent and time, accurate and senstive, which was suitable for the detection of 7 bisphenols in edible oils.