间氨基苯硼酸修饰磁性碳纳米管-超高效液相色谱-串联质谱法测定太湖水产品中9种微囊藻毒素残留

Simultaneous determination of 9 kinds of microcystins in Taihu aquatic products based on APBA@Fe3O4/MWCNTs magnetic nanoparticlescoupled with ultra performance liquid chromatography-tandem mass spectrometry method

目的建立基于间氨基苯硼酸修饰磁性多壁碳纳米管复合纳米粒子前处理技术的磁性固相萃取-超高效液相色谱-串联质谱(UPLC-MS/MS)法测定水产品中9种微囊藻毒素。方法通过水热合成方法制备磁性多壁碳纳米管(Fe3O4/MWCNTs)复合纳米粒子,利用化学氧化法将间氨基苯硼酸修饰在磁性碳纳米管表面形成功能化纳米材料(APBA@Fe3O4/MWCNTs)。应用透射电子显微镜及红外光谱对材料进行表征。通过对萃取效率的影响因素进行优化,建立了乙酸-PBS缓冲溶液-甲醇(2∶49∶49,V/V)溶液作为提取溶液,使用50 mg的磁性纳米材料萃取15 min,采用5%氨化甲醇作为洗脱溶剂,洗脱时间为10 min的前处理方法。结果9种微囊藻毒素在5~200 ng/mL范围内,线性关系良好,相关系数(r)均>0.998,检出限(LOD)为0.15~8.71μg/kg。3个加标水平的平均回收率为91.8%~103.2%,相对标准偏差(RSD)为3.1%~9.5%。结论该方法可同时测定水产品中9种微囊藻毒素,前处理简单、灵敏度高、相对回收率高,优于国标方法,为水产品中微囊藻毒素的监测提供有力的技术保障。

Objective To develop a multiwalled carbon nanotube(MSPE)method coupled with ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)by preparing a magnetic multiwall carbon nanotube composite nanoparticles modified with 3-aminobenzeneboronic acid for simultaneous determination of 9 kinds of microcystins in aquatic products.Methods Magnetic multiwall carbon nanotubes(Fe3O4/MWCNTs)composite nanoparticles were prepared by hydrothermal synthesis.Then,the 3-aminobenzeneboronic acid was modified on the prepared magnetic carbon nanotubes through the chemical oxidation method.The nanoparticles have been characterized by transmission electron microscopy and infrared spectroscopy.The main factors influencing the extraction efficiency were optimized.And then a preprocessing method with acetic acid-PBS buffer solution-methanol(2∶49∶49,V/V)was selected as the extraction solution,and 50 mg magnetic nanomaterials were used for extraction for 15 min,5%ammoniated methanol was used as the eluting solvent within 10 min.Results The calibration curves of microcystins showed a good linearity in the range of 5-200 ng/mL with correlation coefficients above 0.998.The detection limits(LOD)of the method were in the range of 0.15-8.71μg/kg.The average relative recoveries of three spiked levels ranged from 91.8%to 103.2%with the relative standard deviations of 3.1%-9.5%.Conclusion The method has the characteristics of simple pretreatment,high sensitivity and high recoveries,superior to national standard method.It could simultaneously determine 9 kinds of microcystins in aquatic products and provides a powerful technical guarantee for the monitoring of microcystins in aquatic products.