基于电沉积和定向印迹技术的金刚烷胺仿生传感分析及机理研究

The illegal use of antiviral drug - amantadine in animal feeding process has led to its residue in animal derived food and a serious threat to people's health. Thus, it has important realistic significance to develop a rapid method with high sensitivity, selectivity and easy popularization for the amantadine residue determination. Biomimetic sensors using molecularly imprinted electrodeposition film as recognition element were a combination of organic synthesis, electrochemistry and biomimetic sensing technology, which have the characteristics of simple preparation, high accuracy and sensitivity, strong environmental adaptability and easy popularization, and played an important role in food safety detection. Due to the limit of template molecules number in the deposition process, conventional electrodeposited films of molecular imprinting have the drawbacks of low imprinting efficiency and poor signal response. How to improve the imprinting efficiency and signal response capacity of electrodeposition film has become an urgent problem to solve for the development of molecular imprinting biomimetic sensor. This project intends to incorporate the nano-synergic and stereospecific imprinting techniques into the preparation process of molecularly imprinted electrodeposited film to improve its imprinted efficiency and signal response strength, and simultaneously explore the synergistic and stereospecific imprinting mechanisms to reveal recognition mechanism of molecularly imprinted electrodeposited film from one side. The results of this project will provide certain theoretical reference and technical support for further development of molecular imprinting biomimetic sensing and related technologies in the field of food safety detection.

抗病毒药物金刚烷胺在动物饲养过程中非法使用，造成其在动物源性食品中残留，严重威胁着人们的身体健康。针对其残留建立快速、灵敏、特异性好、易于普及的分析检测方法具有重要的现实意义。以分子印迹电沉积膜为识别元件的仿生传感器集合了有机合成、电化学、仿生传感等多项技术，具有制备简单、检测准确灵敏、环境适应力强、便于普及等特点，在食品安全检测中发挥重要作用。传统分子印迹电沉积膜由于沉积过程模板分子数量限制，造成印迹效率低、信号响应差的缺点。如何提高电沉积膜的印迹效率和信号响应能力成为分子印迹仿生传感器发展的一个亟待解决的问题。本项目拟将纳米增效和定向印迹技术引入分子印迹电沉积膜的制备过程，提高其印迹效率和信号响应能力，并对其增效和定向印迹机制进行探究，侧面揭示分子印迹电聚合膜的分子识别机理。本项目研究对分子印迹仿生传感及相关技术在食品安全检测领域的进一步发展提供一定的理论参考和技术支持。

按照预期研究计划，本研究完成了基于“定向诱导”和“电沉积”技术的金刚烷胺分子印迹仿生电化学传感器和基于金纳米粒子和石墨烯材料的增敏型金刚烷胺分子印迹仿生压电传感器的构建，并对典型动物源性食品中抗病毒药物金刚烷胺残留开发了准确、灵敏、快速的仿生传感检测方法。第一部分研究内容以盐酸为模板质子化剂，在金盘电极表面直接电沉积邻氨基苯硫酚聚合膜，实现了对模板金刚烷胺的“定向诱导”印迹，达到高效率印迹的目的。系统考查了聚合单体与模板摩尔比例、电沉积循环次数、孵育时间等参数对电沉积分子印迹电化学传感器的检测准确度、灵敏度、选择性、重现能力等性能的影响，深入探讨了“定向诱导”手段对分子印迹膜传感器的选择识别能力、稳定性等影响规律，并证实了“定向诱导印迹”在提升分子印迹膜传感器性能方面的有效性。基于前期研究，第二部分在石英晶体微天平传感器表面构建了一种基于金纳米粒子和石墨烯复合功能材料的分子印迹仿生压电传感器，并用于抗病毒药物金刚烷胺的检测。利用金纳米粒子和石墨烯的高比表面积，较快电子传递速率等优点，结合电沉积技术手段，提出了可显著提高传感器的检测灵敏度的新方法。研究系统地优化了金纳米粒子、石墨烯电沉积过程和分子印迹聚合沉积过程的实验参数。并通过透射/扫描电镜，原子力显微镜等手段对增敏型分子印迹电沉积膜进行了形貌表征；并通过一系列实验证实了所获得的增敏型分子印迹电沉积膜对模板分子金刚烷胺具有良好的选择识别能力，且响应信号稳定，重现性好。与石英晶体微天平传感分析系统连用，可实现金刚烷胺稳定、准确、灵敏、可重复的分析检测。该研究第一次将具有高准确度和灵敏度、高选择能力、稳定的分子印迹仿生压电传感器成功用于动物源性食品中金刚烷胺残留检测。研究发表 SCI 收录论文3篇，申请发明专利3项，培养硕博研究生7人。