亲水性表面分子印迹聚合物基电化学传感器的构筑及水中四溴双酚A检测研究

As a potential endocrine disruptor, tetrabromobisphenol A (TBBPA) has drawn much attention due to its possible ecological safety issues. Electrochemical sensors based on molecularly imprinted are an effective way for detecting target molecules. Traditional molecularly imprinted polymers are generally poorly dispersible in water and result in obvious non-specific recognition, which limits their application in the detection of pollutants in water. Meanwhile, the specific surface area and the pore size of the support are also an important factor that affect the recognition performance of the imprinted polymer. In this program, the advantages of controlled / "living" free radical polymerization and the high specific surface area of the porous support will be combined. Porous support provides sufficient recognition site, while controlled / "living" free radical polymerization was an effective way to control the thickness of the imprinted shell and maximize the advantages of porous carriers and facilitate hydrophilic modification to effectively avoiding non-specific identification. By preparing a series of pore-size nanosupports and optimizing the reaction conditions, the influence of pore size on the detection limit of the sensor system was systematically investigated. Meanwhile, balance the relationship between hydrophilicity post-modification and recognition performance to construct a electrochemical sensors with highly sensitive and good selectivity to qualitative and quantitative detection of TBBPA in water, and providing a new idea for the efficient detection of trace organic pollutants in water meanwhile.

作为一种潜在的内分泌干扰物，四溴双酚A（TBBPA）由于其可能引发的生态安全问题而备受关注。分子印迹基电化学传感器是一种检测目标分子的有效手段。传统分子印迹聚合物一般在水中分散性较差、存在较明显的非特异性识别而限制了其在水体污染物检测方面的应用，同时载体比表面积及孔尺寸也成为影响印迹聚合物识别性能的重要因素。本项目拟将可控/“活性”自由基聚合及多孔载体高比表面积的优势进行结合，多孔载体保证所制备聚合物具有丰富的识别位点，而可控/“活性”自由基聚合可以很好的控制印迹壳层厚度，最大限度发挥多孔载体的优势，且方便亲水性修饰，有效避免非特异性识别。通过制备系列孔尺寸的印迹基体，优化反应条件，系统研究孔结构对于传感器检测限的影响，同时平衡后修饰中亲水性与识别性能之间的关系，从而构建高灵敏度、良好选择性的电化学传感器，并对水中微量TBBPA进行定性、定量检测，为水中微量有机污染物的高效检测提供新思路。

本项目将可控/“活性”自由基聚合物以及多孔载体的优势进行结合，设计合成了系列组成及孔径结构的多孔载体，并采用不同的手段将RAFT试剂修饰到载体表面，通过RAFT聚合制备了基于多孔载体的分子印迹聚合物，并研究了其对模板分子的选择性识别效果。同时，将合成的分子印迹聚合物通过滴涂的手段修饰到经贵金属纳米粒子、二维材料或者二维材料与贵金属纳米粒子形成的复合材料修饰的玻碳电极表面，构筑分子印迹基电化学传感器，实现了对目标分子的电化学检测。同时，为了避免环境条件对于检测结果的影响，在电化学传感器的构筑过程中引入了聚硫堇作为参比信号，获得了基于分子印迹聚合物的率电化学传感器，实现了对目标化合物的准确检测。除了将分子印迹聚合物的选择性识别功能与电信号结合构筑电化学传感器之外，项目实施过程中也对研究领域进行了适当的拓展，将分子印迹聚合物与荧光信号结合，构筑了分子印迹荧光传感器，同时为了达到可视化检测效果，在荧光传感中引入参比信号，利用响应信号与参比信号的叠加，实现对目标分子的可视化检测。项目实施过程中构建了系列高灵敏度、良好选择性的电化学及荧光传感器，并成功将其应用于抗生素及水体污染物的定性定量检测，为水中微量有机污染物的高效检测提供了新思路。