石墨烯固相萃取-液相色谱-质谱联用法测定食品接触材料中9种双酚-二环氧甘油醚的迁移量

Using Graphene as Solid Phase Extraction Adsorbent to Determinate 9 Bisphenol Diglycidyl Ethers in Food Contact Materials

摘要:

基于石墨烯固相萃取, 以实际样品为研究对象, 建立了食品接触材料中内分泌干扰物双酚A-二缩水甘油醚(BADGE)及其衍生物BADGE·H2O、BADGE·HCl、BADGE·2H2O、BADGE·2HCl、BADGE·H2O·HCl和双酚F-二缩水甘油醚(BFDGE)及其衍生物BFDGE·2HCl、BFDGE·2H2O 等9种双酚-二环氧甘油醚迁移量的高效液相色谱-串联质谱(HPLC-MS/MS)检测方法。样品以叔丁基甲醚为提取溶剂, 超声提取, 提取液经石墨烯固相萃取柱富集、净化。质量分数0.1％乙酸的5 mmol/L醋酸铵溶液和甲醇为流动相, 经COSMOSIL C18分析柱分离后, 采用电喷雾串联四级杆质谱检测。9种双酚-二环氧甘油醚中2种在0.5～50 ng/mL范围内线性关系良好; 2种在5.0～100.0 ng/mL范围内线性关系良好; 其他5种在2.0～100.0 ng/mL范围内线性关系良好(r2＞0.992 2)。对牛肉、橘片两种罐头食品进行3个水平的添加回收实验, 9种目标化合物的回收率分别为：60.0%～97.6%(牛肉)和65.7%～111.3%(橘片), 相对标准偏差小于20%。方法的检测低限为0.1～1.0 μg/kg。该方法操作简单, 灵敏度高, 成功应用于食品接触材料中双酚-二环氧甘油醚迁移量的快速检测。

Abstract:

A comprehensive analytical method based on high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) was developed in this manuscript, for measuring 9 exogenous endocrine disruptors-bisphenol diglycidyl ethers, including BADGE, BADGE·H2O, BADGE·HCl, BADGE·2H2O, BADGE·2HCl, BADGE·H2O·HCl, BFDGE, BFDGE·2H2O and BFDGE·2HCl. The samples were extracted with methyl tertiary butyl ether by ultrasonic wave assistant extraction(UAE). The extracts were cleaned up and concentrated on graphene SPE column. The targeted compounds were analyzed by HPLC-MS/MS under positive ion mode using COSMOSIL C18 column as analytical column. Under the optimal conditions, 2 analytes had a good linearity in the concentration range of 0.5~10.0 ng/mL. 2 analytes had a good linearity in the concentration range of 5.0~100.0 ng/mL; and the other 5 analytes had a good linearity in the concentration range of 2.0~20.0 ng/mL. The correlation coefficients(r2) were higher than 0.992 2. Recoveries of 9 analytes in canned meat at three spiked level ranged from 60.0%~97.6%, the recoveries of 9 analytes in canned oranges at three spiked level ranged from 65.7%~111.3%, with RSDs less than 20％. The detection limits of the method ranged from 0.1 to 1.0 μg/kg. The method was sensitive, simple, and suitable for the rapid determination of exogenous endocrine disruptors-bisphenol diglycidyl ethers in food contact materials.