蜂蜜中呋喃西林代谢物氨基脲的检测技术与形成机理研究

Detection technology and formation mechanism of nitrofurazone metabolites semicarbazide in honey

本研究创新性地引入平行液相色谱串联质谱技术,并系统地优化了前处理过程,开发出一套快速测定蜂蜜中呋喃西林代谢物氨基脲(SEM)的方法。经方法学验证,SEM在0.5~25 ng/mL线性关系良好,相关系数为0.9994,检出限为0.1μg/kg,定量限为0.3μg/kg;3个水平的加标实验,平均回收率分别为98.5%、98.5%、100.1%,相对标准偏差分别为2.94%、1.19%、3.70%。利用新建方法对市售蜂蜜进行抽检,检出SEM4批次,其形成机理为:玻璃罐包装中瓶盖的密封垫圈含有的发泡剂偶氮二甲酰胺(Azodicarbonamide,ADA)经受热分解形成SEM,蜂蜜在高温密封处理产生的水蒸气接触到密封垫圈,冷却后落回将溶解的SEM迁移至蜂蜜,或者在运输途中蜂蜜与密封垫圈直接接触,SEM随着蜂蜜中的水分迁移至蜂蜜中。

A novel method utilizing parallel liquid chromatography-tandem mass spectrometry was developed for a rapid determination of nitrofuracillin metabolites semicarbazide(SEM)in honey.After the optimization of pretreatment process,verification experiments showed a good linear relationship for SEM within the range of 0.5〜25 ng/mL,with a correlation coefficient of 0.9994,a limit of detection of 0.1μg/kg,and a limit of quantification of 0.3μg/kg.Average recoveries at three spike levels were 98.5%,98.5%,100.1%,respectively,with standard deviations(RSD)of 2.94%,1.19%,3.70%,respectively.Utilizing the newly developed method to sample commercially available honey,SEM was detected in 4 batches.The formation mechanism was identified as follows:the foaming agent azodicarbonamide(ADA)in the sealing gasket of glass jar packaging decomposed under heat to form SEM,which then migrated to honey upon contact with water vapor generated during high-temperature sealing or direct contact during transportation.