共价有机聚合物固相微萃取结合高效液相色谱-串联质谱法检测牛奶中黄曲霉毒素

目的 建立基于共价有机聚合物固相微萃取(solid phase microextraction, SPME)前处理结合高效液相色谱-串联质谱法(high performance liquid chromatography-tandem mass spectrometry, HPLC-MS/MS)快速、高灵敏检测牛奶中6种黄曲霉毒素残留的分析方法。方法 以1,3,5-三(4-氨苯基)苯(1,3,5-tri (4-aminophenyl) benzene, TAPB)和1,3,5-三甲酰基间苯三酚(1,3,5-triformyl-phloroglucinol, Tp)为单体制备了共价有机聚合物材料(covalent organic polymer, COP)并固定在木签表面，用于黄曲霉毒素的固相微萃取前处理。在萃取时间为20 min、洗脱溶剂为乙腈、洗脱时间为6 min时，对黄曲霉毒素的萃取和洗脱效果最佳。结果 6种黄曲霉毒素在0.05~100 ng/mL的浓度范围内线性关系良好，相关系数均大于0.9995。日内和日间精密度的相对标准偏差(relative standard deviations, RSDs)分别为4.39%~8.21%和4.97%~9.12%。将开发的方法用于实际牛奶样品中黄曲霉毒素残留检测，加标回收率为80.01%~92.71%，RSDs为3.12%~9.54%。结论 制备的共价有机聚合物固相微萃取材料对6种黄曲霉毒素吸附性能强，开发的SPME-HPLC-MS/MS适用于牛奶中黄曲霉毒素的快速、高灵敏定量检测。

Determination of aflatoxins in milk by covalent organic polymer solid phase microextraction combined with high performance liquid chromatography-tandem mass spectrometry

Objective To establish a rapid and highly sensitive method for the determination of six aflatoxins in milk by covalent organic polymer solid phase microextraction (SPME) combined with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Methods The 1,3,5-tri (4-aminophenyl) benzene (TAPB) and 1,3,5-triformyl-phloroglucinol (Tp) were used as monomers to prepare covalent organic polymers (COP) and fixed on the wooden tip surface, then used for solid phase microextraction pretreatment of aflatoxin. When the extraction time was 20 min, the desorption solvent was acetonitrile, and the elution time was 6 min, the optimal extraction and desorption effects of aflatoxin were obtained. Results The linear relationship of aflatoxins in the concentration range of 0.05-100 ng/mL was good, and the correlation coefficients were greater than 0.9995. The relative standard deviations (RSDs) of intra-day and inter-day precision were 4.39%-8.21% and 4.97%-9.12%, respectively. The developed SPME-HPLC-MS/MS method was used to detect the aflatoxins residue in real milk samples. The recoveries of aflatoxins in spiked milk samples were 80.01%-92.71%, and RSDs were 3.12%-9.54%. Conclusion The prepared covalent organic polymer solid phase microextraction material has strong adsorption performance for six aflatoxins. The proposed SPME-HPLC-MS/MS method is suitable for rapid and highly sensitive quantitative detection of aflatoxins in milk.