环境中痕量PEDCs印迹固相萃取-印迹电化学传感检测联用系统研究及应用

This project aims to develop a novel rapid, simple and convenient imprinted electrochemical sensing method combined with imprinted solid phase extraction for the determination trace phenolic endocrine disrupting chemicals in environmental pollutions. The imprinted polymers were fabricated with surface imprinting technology using bisphenol A, octylphenol and nonylphenol as the template molecules, carbon nanotubes, graphene and nano-magnetic particles as the matrix. Combined with the combination imprinting technology, imprinted composite materials with high selective adsorption performance, good stability and fast adsorption were obtained. Preferred imprinted composite materials were used as solid phase extraction materials and electrochemical sensing element to detect the phenolic endocrine disrupting chemicals. Trace phenolic endocrine disrupting environmental pollutants (mainly in soil and water) were treated with imprinted solid-phase extraction and enrichment, and then the extraction liquid was detected by the imprinted electrochemical sensor. According as the results of chromatography-mass spectrometry to optimize the extraction conditions and testing conditions, the fast-free derivative imprinted electrochemical sensor detection system combined with molecularly imprinted solid-phase extraction and enrichment will be developed. This study is to simplify the separation of phenolic endocrine disrupting chemicals and accomplish free derivative, online fast separation and determination of trace phenolic endocrine disrupting chemicals in complex environments with a simple analysis instrument, which is given a new way for trace endocrine disrupting chemicals fast analysis.

本项目旨在建立一种简便、快速的环境污染物中痕量酚类内分泌干扰物的印迹固相萃取-印迹电化学传感联用检测分析方法。拟以双酚A，辛基酚和壬基酚等为模板分子，以碳纳米管、石墨烯和纳米磁性颗粒为基体，采用新型表面印迹技术，结合组合印迹方法，研制出具有高选择吸附性能、稳定性好和吸附速度快的印迹复合材料。将优选后的印迹复合材料分别用作固相萃取材料和电化学传感元，对环境污染物中痕量酚类内分泌干扰物（主要是土壤和水中）先经过印迹固相萃取、富集，再采用印迹电化学传感器对富集液中酚类内分泌干扰物进行在线检测。参照色谱-质谱分析结果，优化萃取条件和检测条件，建立分子印迹固相萃取富集-印迹电化学传感器在线快速免衍生检测系统。该研究将简化酚类内分泌干扰物的分离富集操作步骤，实现采用简便的分析仪器对复杂环境中痕量酚类内分泌干扰物的免衍生、在线快速分离检测，为环境中痕量酚类内分泌干扰物的快速分析开辟新途径。

本项目主要以碳纳米管、氧化石墨烯和四氧化三铁纳米颗粒为基质，采用新型印迹聚合技术，优化制备工艺，先后成功制备出一系列高吸附容量、高选择性能、印迹层厚度可控、性能稳定的新型印迹复合材料，例如新型碳纳米管表面磁性印迹复合材料、二氧化硅微球表面新型印迹复合材料、石墨烯新型表面印迹复合材料。以性能优良的分子印迹复合材料为固体吸附剂，结合高效液相色谱分析，成功建立环境中印迹固相萃取富集-高效液相色谱检测联用新技术，实现环境中微量双酚A，四溴双酚A、四溴双酚S、壬基酚、辛基酚等酚类内分泌干扰物快速分离富集-检测的新方法，解决目前从环境中难以快速分离检测微量内分泌干扰物的难题。结合各种纳米增敏材料，以性能优良的分子印迹复合材料为传感元件，制备出高选择性和高灵敏的印迹电化学传感器，并成功用于环境中微量双酚A，四溴双酚A、四溴双酚S、壬基酚、辛基酚等酚类内分泌干扰物的灵敏检测。最后结合印迹磁性印迹固相萃取和印迹电化学传感器的优点，搭建一种高选择性高灵敏度的印迹固相萃取-印迹电化学联用检测系统，并成功用于环境中微量邻苯二甲酸二丁酯和四修双酚S检测。该项目在国内外发表相关研究论文18篇，其中SCI收录16 篇，影响因子大于3.0论文8篇；培养研究生共11名，毕业7人，在读4人，其中获得湖南省优秀硕士毕业论文1篇，圆满完成项目的预期目标。