一步法合成导电聚合物修饰含氮石墨烯及其在生物传感器上的应用

This project is aimed to prepare novel conducting polymer modified nitrogen containing graphene (CP-N-G) as catalysts for intraocular biosensors using ball milling. The ball milling technique can simplify the three complicated processes e.g. edge-functional graphite, CP polymerization and graphene exfoliation to a direct one-step method. The difficulty and cost for producing graphene and its derives will be reduced significantly with the use of this new technology, suggesting great possibility of commercialization of graphene preparation. Traditionally, N-graphene, either prepared by chemical oxidation or by chemical vapor deposition, always shows increased defects in structure and decreased electronic conductivity due to the doping of nitrogen between two carbon atoms in graphene matrix. In the proposed work, we are planning to prepare edge nitrogen doped graphene which remains good graphene structure and excellent conductivity. The doping of nitrogen between graphene and CP will allow electrons transferring from carbon to adjunct nitrogen, producing electroactive carbons. Based on these active sites, we will design a novel intraocular biosensor with good performance, biocompatibility and long-term stability, which can monitor contents from tear fluid, providing technical supports and useful information for clinic diagnosis of ocular diseases such as diabetes retinopathy.

本项目将采用全新的的球磨技术，一步法合成新型导电聚合物修饰的含氮石墨烯(CP-N-G)催化剂，并探讨其在眼内生物传感器上的应用。球磨法能够有效的将石墨的边缘氮掺杂，导电聚合物(CP)的聚合以及石墨烯的剥离三个复杂的过程简化为一步，降低石墨烯及其衍生物的生产难度和成本，为产业化生产石墨烯提供技术保障。传统的化学氧化法或化学气相沉积法制备的氮掺杂石墨烯，由于氮原子在石墨烯中间碳碳双键的掺杂，影响了石墨烯结构的完整性和电子导电性。本项目拟采用的边缘氮掺杂石墨烯，能够很好的保持石墨烯结构的完整性，提高电子的传输速度。氮原子在石墨烯和CP两个共轭碳环结构之间的掺杂，使得电子云从相邻碳原子转移到氮上，为电化学催化提供活性点。同时在此基础上构建性能优异、生物相容性好、长期稳定性强的新型眼内生物传感器，实时监测眼内液体如泪液中组分的变化，为眼部重大疾病如糖尿病眼病预防和早期诊疗提供技术保障和有用信息。

本项目开发了一种环保、简便、高效的大规模制备功能化石墨烯的新技术—边缘功能化球磨法。并在此基础上，进一步结合聚合物单体气相聚合反应，制备了一系列具有高电化学活性的聚合物修饰含氮石墨烯，如聚苯胺石墨烯、聚吡咯石墨烯、壳聚糖石墨烯等。所得到的产物由于氮原子在石墨烯边缘的掺杂而具有优异的催化活性，有望突破传统生物传感器的灵敏度瓶颈，实现生物传感器在眼内的临床应用。本项目在所制备的聚合物石墨烯基础上，构建了高性能的电化学生物传感器和光学生物传感器，并进一步将所构建的纳米生物传感器组装到眼用器件，开发了一系列可用于实时监测眼内泪液中重大疾病相关各组分（如葡萄糖、多巴胺）的高性能沿用纳米生物传感器，为眼部重大疾病如糖尿病眼病的预防和早期诊疗提供技术保障。. 本项目发表SCI学术论文12篇，累计总影响因子大于47；一篇论文入选2015年Scientific Reports百篇最受关注论文,一篇论文入选Polymer Chemistry前封面论文；获得国家授权发明专利4项；应邀参加国际学术会议并作大会发言报告7人次。