功能化石墨烯/导电分子印迹聚合物的电化学传感器构建及其在芳香胺检测中的应用研究

Aromatic amines are a kind of mutagenic, teratogenic, carcinogenic and harmful substances, so establishing new method for rapid detection of aromatic amines in environmental samples is very necessary. There are some drawbacks including bad selectivity or low sensitivity for current electrochemical detection methods of aromatic amines. In order to solve this problem, this project is proposed to combine functionalized graphene and conducting polymers with surface molecular imprinting technique, and study nanocomposites with specific recognition and highly conductive property. It aims to find new principles and technologies to serve the detection of aromatic amines. Functionalized graphene and ionic liquids are designed and synthesized at first. Through free radical polymerization, functionalized graphene/conducting molecularly imprinted polymer composites are prepared using functionalized graphene as the support, aromatic amines as the template molecules, and functionalized vinyl ionic liquid and vinyl ferrocene as the monomers. Functionalized graphene exhibits excellent conducting property and large surface area. In addition, conducting polymers are good conductive and porous materials. The imprinted composites are expected to exhibit good conductive property, stable porous structure and more recognition sites. Electrochemical sensors based on these composites are expected to achieve high selectivity, high sensitivity, rapid and accurate detection of aromatic amines.

芳香胺是一类容易致突变、致畸形、致癌的有害物质，建立环境中芳香胺的快速检测新方法十分必要。目前芳香胺的电化学检测存在选择性不好或灵敏度不高的缺点，为了解决该问题，本项目将功能化石墨烯和导电聚合物进行复合，采用表面分子印迹技术，开展具有特异性识别和高导电性的纳米复合材料的研究和应用，寻找适合于芳香胺特异性、高灵敏、快速检测的新原理、新技术。我们首先设计和合成功能化石墨烯和烯基离子液体，然后以功能化石墨烯为分子印迹载体，功能化烯基离子液体、烯基二茂铁为功能单体，芳香胺为模板分子，自由基聚合法制备功能化石墨烯/导电分子印迹聚合物的复合材料。功能化石墨烯具有优良导电性和大的比表面，导电聚合物具有导电性好和多孔的特点，两者的复合材料预计具有较好的导电性、稳定的多孔结构和较多的识别位点；构建该复合材料的电化学传感器，有望实现高选择性、高灵敏、快速、准确的芳香胺检测。

表面分子印迹技术是一种制备对模板分子具有识别性能聚合物的技术，该技术制备的聚合物是基于载体的印迹材料，由于印迹位点位于材料的表层，它可提高目标分子的识别响应速度，降低非特异性吸附。本项目主要采用表面分子印迹技术制备石墨烯/导电分子印迹聚合物的复合材料，开展具有特异性识别和高导电性的纳米复合材料的研究和检测应用。研究主要成果与进展包括：（1）基于离子液体具有导电性好的优点，制备了咪唑类烯基离子液体。以石墨烯为载体，烯基离子液体、烯基二茂铁为分子印迹功能单体，咪唑类烯基离子液体为交联剂，采用表面分子印迹技术制备石墨烯/导电分子印迹聚合物的复合材料，考察了这些复合材料电化学催化性能，构建复合材料的电化学传感器用于芳香胺、6-苄氨基嘌呤、氧氟沙星等环境分析对象的检测。结果表明，较传统的交联剂，基于离子液体交联剂的分子印迹聚合物具有最高的电化学响应。（2）合成苯基的烯基离子液体，采用自由基聚合法制备了苯基的聚离子液体材料，将聚离子液体材料应用于环境水中邻苯三酚的检测。（3）合成了基于铂纳米粒子、碳纳米管等导电载体的表面分子印迹材料，构建这些分子印迹材料的电化学传感器应用于检测。（4）制备了离子液体螺旋碳纳米管的材料，并将其与二茂铁共同构建电化学免疫传感器。研究期间在Biosensors and Bioelectronics、Sensors and Actuators B: Chemical、Talanta、Microchimica Acta、Polymers、Analytical Methods等发表SCI收录论文6篇，获得授权专利2项。研究结果对分子印迹技术、离子液体的基础应用研究具有重要意义。