分散固相萃取-液相色谱-串联质谱法测定饼干中的6种玉米赤霉醇类化合物

Rapid Determination of Six Zeranols in Biscuits by Dispersive Solid-phase Extraction Coupled with High Performance Liquid Chromatography-tandem Mass Spectrometry

建立了一种简单、快速测定饼干中6种玉米赤霉醇类化合物（α-玉米赤霉醇、β-玉米赤霉醇、α-玉米赤霉烯醇、β-玉米赤霉烯醇、玉米赤霉酮和玉米赤霉烯酮）的分散固相萃取净化-液相色谱串联质谱分析方法。样品加入同位素内标后,经水分散,以1%甲酸乙腈（V/V）提取,混合吸附剂（PSA、C18和Mg SO4）分散净化,氮吹浓缩后用1 m L 30%乙腈水溶液（V/V）复容,经正已烷（乙腈饱和）除脂后采用色谱分离,串联四极杆电喷雾离子源负模式及多反应监测模式检测,内标法定量。6种玉米赤霉醇类化合物在0.20-50.0μg/L范围内线性关系良好,相关系数均大于0.996,方法的检出限为0.03-0.11μg/kg,定量限为0.11-0.31μg/kg,回收率为70.9%-107.1%,日内精密度（n=6）为0.4%-11.4%,日间精密度（n=5）小于12%。该方法具有净化效果好、定量准确、灵敏快速的特点,适用于饼干中6种玉米赤霉醇类化合物的定量分析检测。

A simple and rapid analytical method was established for the determination of six zeranols （α-zearalanol, β-zearalanol, α-zearalenol, β-zearalenol, zearalanone, and zearalenone） in biscuits by dispersive solid phase extraction （α-SPE） coupled with high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS）. After the addition of the isotopic internal standard, the sample was dispersed in water, and zeranols were extracted using a solvent mixture of acetonitrile/formic acid （99：1）. Subsequently, the sample was mixed with sorbents PSA, C18, and MgSO4 to conduct d-SPE. The solution was concentrated under a nitrogen stream and reconstituted in a 30% acetonitrile （v/v） solution. After being defatted with n-hexane, the sample was separated and analyzed by HPLC-MS/MS. Negative electrospray ionization was used on a quadrupole mass spectrometer operating under multiple reaction monitoring （MRM） mode. The quantitation was carried out using the internal standard method. The calibration curves of the zeranols were linear in the range 0.20-50.0 μg/L with correlation coefficients higher than 0.996. The limits of detection （LODs） and the limits of qualification （LOQs） of the method varied from 0.03 to 0.11 μg/kg and from 0.11 to 0.31 μg/kg, respectively. The mean recoveries of the zeranols ranged from 70.9% to 107.1%, with intraday precisions （n = 6） and interday precisions （n = 5） less than 12%. This method provides good purification and accurate quantification, and is sensitive, rapid, and suitable for the identification and quantification of the six zeranols in biscuits.