用于水中痕量PPCPs富集分离的磁性多胺石墨烯分子印迹聚合物的制备及应用基础研究

This project is originated from the urgent requirement of the drinking water national safety and the key problem of nanoscience. The novel graphene magnetic molecularly imprinted polymers (GM-MIPs), prepared with the functionalized magnetic particles and graphene by using the ultrasound-assisted surface molecules imprinted polymerization, such as active controlled radical polymerization, are high capacity and high selectivity. Their structural parameters (i.e.the composition, the shape, the pore size and the surface modification) are fully characterized by the modern analytical instruments, e.g. transmission electron microscopy (TEM). Furthermore, considering with the preparation conditions and the adsorption data for pharmaceuticals and personal care products (PPCPs), the relationship between the ultrasound-assisted paratmers and the adsorption properties is discussed, the microscopic mechanisms and the interaction law in the process of coupling graphene with magnetic particles are explored. The intrinsic relationship between the nano-materials microstructure with the adsorption properties for PPCPs is investigated, the semi-empirical mathematical model is proposed, and the selective adsorption mechanism is clarified. Based on the above study, the controllable synthesis for the GM-MIPs will be come true, and the GM-MIPs with the independent intellectual property rights will be obtained. At last, a new and simple analytical system is established for the determination of trace PPCPs in the drinking water by liquid chromatography - tandem mass spectrometry coupled with the molecular imprinted polymers dispersive solid-phase extraction (MIPs-dSPE). This project will play an important scientific significance in the pollution prevention and elimination of PPCPs, and it will establish a solid scientific foundation for the evaluation.

本项目从饮水安全的国家重大需求和纳米科学的关键问题出发。通过对磁性粒子和石墨烯的功能化修饰，采用超声强化活性可控自由基聚合等表面分子印迹聚合方法，制备高容量、高选择性的磁性石墨烯分子印迹聚合物（GM-MIPs）。利用透射电镜等分析手段表征纳米材料的组成、形状、尺寸、孔径和表面修饰等特征参数，结合制备条件和PPCPs吸附数据，探讨超声强化对GM-MIPs吸附性能的内在影响，探索石墨烯与磁性粒子耦合过程的微观机制及相互作用规律，研究GM-MIPs微观特征与吸附特性之间的内在联系，构建半经验数学模型，阐明吸附机理，实现GM-MIPs的可控制备，开发拥有自主知识产权的GM-MIPs。在此基础上，建立新颖、简便的水中痕量PPCPs的GM-MIPs/分散固相萃取/液相色谱-串联质谱联用检测体系。项目成果可为PPCPs污染的风险评估奠定科学基础，对PPCPs微污染水的防治具有重要的科学意义。

本项目从饮水安全的国家重大需求和纳米科学的关键问题出发。通过对磁性纳米粒子和氧化石墨烯的功能化修饰，采用超声强化活性可控自由基聚合和“点击化学”等表面聚合技术，制备了高容量、高选择性的磁性石墨烯分子印迹聚合物（GM-MIPs）、磁性碳纳米管微球（Fe3O4@SiO2–MWCNTs）和氨基化磁性石墨烯复合材料（NH2-MP@GO）。利用透射电镜、扫描电镜、红外光谱等分析手段表征了制备的纳米材料的组成、形状、尺寸、孔径和表面修饰等特征参数，结合制备条件和PPCPs吸附数据，研究探讨了超声强化对GM-MIPs等材料的吸附性能的内在影响，初步探索了石墨烯、碳纳米管与磁性纳米粒子耦合过程的微观机制及相互作用规律，研究了GM-MIPs、Fe3O4@SiO2–MWCNTs和NH2-MP@GO微观特征与吸附特性之间的内在联系，阐明了分散固相萃取的吸附机理，初步实现了GM-MIPs、Fe3O4@SiO2–MWCNTs和NH2-MP@GO材料的可控制备，开发了拥有自主知识产权的GM-MIPs、Fe3O4@SiO2–MWCNTs和NH2-MP@GO新型吸附材料。在此基础上，建立了新颖、简便的水中痕量58种PPCPs、水中痕量氯酚系列和水中痕量微囊藻毒素等的分散固相萃取/液相色谱-串联质谱联用检测技术体系。项目共发表论文27篇（其中SCI收录论文24篇），申请国家发明专利9件（获授权发明专利3件），培训专业技术人员280名（受益机构80多家）。项目成果可为PPCPs污染的风险评估奠定科学基础，对PPCPs微污染水的防治具有重要的科学意义。