新型分子印迹荧光传感器对海水中邻苯二甲酸二(2-乙基)己酯的快速检测技术研究

A novel molecularly imprinted fluorescence sensor for rapid detection of bis-(2-ethylhexyl)phthalate in seawater

构建对邻苯二甲酸二(2-乙基)己酯(Bis(2-ethylhexyl)phthalate,DEHP)具有特异荧光响应的分子印迹-量子点传感器,应用于实际样品中DEHP的残留检测.采用改进的反相微乳液法,制备了对DEHP具有较高选择性和灵敏性响应的分子印迹-量子点纳米结构聚合物(MIP-QDs),通过扫描电镜、红外光谱、X射线光电子能谱、选择性分析等方法对获得的MIP-QDs理化特性进行分析,成功将印迹层锚定在QDs上.进一步通过响应体系优化,结果表明,构建的MIP-QDs在V(水):V(乙醇)=8:2、pH为8.0体系中,对DEHP具有较高的选择性响应;并在0.005~25.0 mg·L^(-1)的DEHP质量浓度范围内,DEHP质量浓度与荧光猝灭效率(F_(0)/F-1)间存在良好线性关系,相关系数为0.9901,检测限低至1.5μg·L^(-1),加标回收率为92.0%~96.8%,相对标准偏差低于8.2%;且在实际海水检测与GC-MS/MS检测结果之间具有良好的一致性.充分表明本文构建的MIP-QDs荧光传感器可用于海水中DEHP的实时定量检测.

A molecularly imprinted polymer based on bis-(2-ethylhexyl)phthalate(DEHP)was prepared by an improved reverse micro emulsion method.A molecularly imprinted quantum dot fluorescence sensor(MIP-QDs)with specific fluorescence response to DEHP was constructed by embedding CdSe/ZnS quantum dots.The morphology of MIP-QDs was analyzed by SEM,FT-IR and X-ray photoelectron spectroscopy,and the detection system was optimized on this basis.The results showed that MIP-QDs had a high selective response to DEHP in V(water):V(ethanol)=8:2 and pH 8.0 system,and had a good linear relationship with F_(0)/F-1 in the range of DEHP concentration from 0.005-25.0 mg·L^(-1),with the correlation coefficient being 0.9901 and the detection limit being as low as 1.5μg·L^(-1).In actual seawater,the spiked recoveries of MIP-QDs ranged from 92.0%-96.8%,and the RSD was lower than 8.21%.There was no significant difference between MIP-QDs and GC-MS/MS in actual seawater detection,and the accuracy rate was not lower than 87.23%.In conclusion,MIP-QDs fluorescence sensor constructed in this paper can be used for real-time detection of DEHP in Marine water.