磁性固相萃取-气相色谱-串联质谱法测定黄酒中16种邻苯二甲酸酯

Determination of 16 phthalate esters in yellow rice wine by magnetic solid-phase extraction combined with gas chromatography-tandem mass spectrometry

目的制备聚吡咯修饰磁性复合纳米材料,建立黄酒中16种邻苯二甲酸酯的磁性固相萃取-气相色谱-串联质谱法(GC-MS/MS)检测方法。方法通过水热合成方法制备Fe_(3)O_(4)磁核,再利用化学氧化法将吡咯修饰在磁核表面形成功能化纳米材料(PPy@Fe_(3)O_(4)),合成的纳米粒子在黄酒中具有很好的磁响应度和分散能力。应用透射电子显微镜及红外光谱对材料进行表征。对影响萃取效率的一些因素如材料用量、黄酒酒精度、离子效应、萃取时间和解吸条件等进行优化。建立了采用40 mg的磁性纳米材料作为萃取剂萃取20 min,2 ml乙酸乙酯作为洗脱剂洗脱10 min的前处理方法,并结合GC-MS/MS仪器在MRM模式下进行分析。结果16种邻苯二甲酸酯的质量浓度在50 ng/ml~5000 ng/ml时,线性相关系数(r)均≥0.9995,3种加标水平下16种邻苯二甲酸酯的回收率为70.5%~102.7%,相对标准偏差(RSD)为3.4%~7.5%,检出限(LOD)为0.01μg/kg~0.49μg/kg。结论聚吡咯修饰磁性复合纳米粒子对黄酒中邻苯二甲酸酯具有良好的吸附性能,结合GC-MS/MS,可用于富集、分离和测定黄酒中的邻苯二甲酸酯。

Objective To prepare magnetic nanomaterials modified by polypyrrole and establish a method of separating and determining of 16 phthalate esters in yellow rice wine by magnetic solid-phase extraction combined with gas chromatography-tandem mass spectrometry(GC-MS/MS).Methods Fe_(3)O_(4)magnetic nuclei was prepared by hydrothermal synthesis.Then the pyrrole was modified to form functionalized nanomaterials on magnetic core surface by chemical oxidation method.The results showed that the synthesized nanoparticles had great magnetic responsiveness and dispersibility in yellow rice wine.The microspheres had been characterized by transmission electron microscopy and infrared spectroscopy.Subsequently,the main factors influencing the extraction efficiency were optimized including the amount of nanoparticles,the alcohol strength,the ionic strength,the extraction time and the desorption conditions.Then the pretreatment method was established by using 40 mg magnetic nanomaterials as extractant for 20 min and 2 ml ethyl acetate as eluent for 10 min.After all 16 phthalate esters were detected by GC-MS/MS in MRM mode.Results The calibration curves of phthalate esters showed good linearity in the range of50 ng/ml-5000 ng/ml with the correlation coefficients(r)≥0.9995.Under the optimal conditions,the average recoveries ranged from 70.5%to 102.7%for three spiked levels and the relative standard deviations(RSD)were within 3.4%-7.5%.The detection limits(LOD)of the method were within 0.01μg/kg-0.49μg/kg.Conclusion The results indicated that the synthesized nanoparticles had good adsorption performance for phthalate esters and the developed method coupled with GC-MS/MS could be used for the enrichment,separation and determination of 16 phthalate esters in yellow rice wine.