磁增强管内固相微萃取/色谱在线联用新技术及其在PPCPs监测中的应用研究

In this project, an online magnetic-enhanced in-tube solid phase microextraction based on monolith (ME-IT/SPME) coupled to chromatography for the automatic monitoring of pharmaceuticals and personal-care products (PPCPs) will be developed. Modified magnetic nano Fe3O4 will be mixed with polymerization solution. According to the "in-situ" synthetical method of monolith, hybrid monolithic capillary column with functionalized magentic Fe3O4 will be synthesized. After that, the capillary column will be fixed on six-port valve and acted as microextraction column, and the capillary column will be enwinded a magnetic coil that allowed the application of a variable magnetic field. Different direction and intensity of magnetic field will be applied on the microextraction column during adsorption and desorption step. Taking the advantages of diamagnetic characters of organic compounds, the extraction efficiency and extraction capacity for PPCPs will be improved and the extraction speed will also be increased under the assistant of magnetic field. At the same time, the extractive principles of ME-IT/SPME for PPCPs will be explored. Based on above studies, the ME-IT/SPME will be on-line hyphenated with HPLC/MS or HPLC/DAD to develop automated, simple, sensitive, and environmentally friendly separation systems for the monitoring of ultra-trace PPCPs in environmental water, sediment and food samples. The implementation of present project will solve the problems in conventional IT/SPME, such as low extraction efficiency, extraction capacity and slow extraction speed. At the same time, the present study will supply a fast, simple, cost-effective and environmentally friendly sample preparation for the monitoring of PPCPs in all kinds of samples.

本项目拟将改性后的磁性纳米粒子参杂到整体材料的聚合溶液中，利用整体材料的“原位”合成技术，制备磁性纳米粒子参杂的整体毛细管柱。然后将毛细管柱固定到六通阀上作为在线管内固相微萃取柱(IT/SPME)，同时在微萃取柱外壁缠绕上磁线圈并与外置电源连接，利用有机分子的反磁性，在吸附和解析步骤中，施加不同方向和强度的电磁场，从而在磁场增强作用下提高目标物质的萃取效率和容量并加快吸附/解析速度，同时探讨在磁增强下的萃取机理。在上述基础上，建立磁增强管内固相微萃取/色谱在线联用体系，以实现对环境样品中超痕量药物及个人护理品(PPCPs)污染物的自动化高灵敏检测。本项目的实施将可有效解决目前IT/SPME中存在的萃取效率和容量低、萃取速度慢等问题，也将为PPCPs的监测提供快速、高效和环境友好的样品前处理技术和自动分离分析体系，在一定程度上提高现有的PPCPs监测技术水平，具有重要的学术价值和应用前景。

管内固相微萃取(IT-SPME)由于具有操作简便、环境友好和可以色谱分离仪器进行在线联用等优点，因此在样品前处理中发挥着重要作用。然而，现有的IT-SPME仍存在着萃取效率低，对极性化合物吸附/解析时间长等问题。为此，本项目将改性后的磁性纳米粒子参杂到整体材料的聚合溶液中，利用整体材料的“原位”合成技术，制备磁性纳米粒子参杂的毛细管整体柱。将该整体柱固定到六通阀上作为在线管内固相微萃取柱，同时在毛细管外壁缠绕上磁线圈并与外置电源连接，利用有机分子的反磁性，在吸附和解析步骤中，施加不同方向和强度的电磁场，从而在磁场增强作用下提高了目标物质的萃取效率和容量并加快吸附/解析速度，研究同时探讨了在电磁增强下的萃取机理。在上述基础上，建立电磁增强管内固相微萃取/色谱在线联用体系，实现对环境样品中超痕量烷基酚类、三嗪类除草剂、紫外防晒成份、尼泊金酯类防腐剂和重金属类污染物的自动化高灵敏检测。本项目经过四年研究，达到了预期效果，很好解决了目前IT-SPME在萃取有机物时存在的萃取效率和容量低、萃取速度慢等问题，为PPCPs及其他污染物的监测提供快速、简便、有效和环境友好的样品前处理技术和自动的分离分析平台，在一定程度上提高现有的PPCPs监测技术水平，具有重要的学术价值和应用前景。项目总发表SCI论文32篇并获四项国家发明专利。