三维共价有机骨架材料的构筑及其在神经毒剂荧光检测中的应用研究

As an emerging class of crystalline porous materials, covalent organic frameworks (COFs) have been developed rapidly in the past 10 years. However, the research on 3D COFs is limited and mostly focused on their gas adsorption applications. The detection of chemical warfare agents (CWAs), such as nerve agents, is of vital important concerning homeland security and civilian safety. Most of the fluorescent probes for the nerve agents sensing are small organic molecules, showing intrinsic limitations such as long response time and a lack of sufficient chemical sensitivity. Therefore, in this proposal, we will design and synthesize a series of functional 3D COFs and investigate their applications in the fluorescent detection of nerve agents. The sensitivity and selectivity towards nerve agents will be improved by taking advantages of the structural features of 3D COFs, i.e. high surface areas, ease of modification, regular arrangement of porous channels, and tunable inner environment of cavities. We will firstly design functional building blocks that can react or interact with nerve agents to construct 3D COFs and explore the effects of reaction conditions on the structure of the resultant polymers; secondly, clarify the influence of organic building blocks and topological structure of the designed materials on the detection performance; finally, develop 3D COFs based fluorescent probes and sensor arrays that can achieve rapid and facile sensing of nerve agents. These investigations will offer instructions to utilize COFs for bio sensing and energy storage applications.

共价有机骨架材料（COFs）作为一类新型结晶性多孔材料在过去十年间得到飞速发展，但是三维COFs材料的研究进展却极为有限，并且其应用研究集中在气体吸附方面。神经毒剂等化学战剂检测和预警与国家安全、社会稳定密切相关，现有荧光探针主要为小分子化合物，存在着灵敏度不高、响应时间较长等问题。因此，申请人拟设计、制备功能性三维COFs材料用于神经毒剂的荧光检测。利用三维COFs材料比表面积高、孔道结构规整、空腔内部化学环境可控等优势，提高对于神经毒剂荧光检测的灵敏度与选择性。首先设计能与神经毒剂分子发生相互作用的功能性构筑单元构筑三维COFs材料，探索反应条件等对于所得聚合物结构的影响；阐明有机构筑单元种类、拓扑学结构等对于检测性能影响规律；从而开发、制备可实现快捷、便携式神经毒剂荧光检测的荧光探针分子材料以及传感阵列。这些研究同时将为高效制备COFs材料并将其用于生物传感、能量存储等领域提供参考。

共价有机框架（COF）是一类由有机构筑单元通过共价键连接的可预先设计的晶态多孔聚合物，在催化、传感、气体存储与分离等领域已经被广泛研究。神经毒剂等化学战剂检测和降解与国家安全、社会稳定密切相关。利用COF规整的孔道结构以及可调的孔内环境，将对神经毒剂具有降解或荧光响应功能的分子作为连接单元，有望实现神经毒剂的特异性检测和高效降解。基于此，申请人在COF的结构设计、制备及性能研究等方面取得了以下原创性研究成果：1）利用构筑单元多维度调控策略，制备系列新型具有发光性质的二维、三维COF等多孔材料，成功调控客体分子和骨架之间的相互作用，实现选择性荧光检测；2）精准、连续控制二维COF层间距离，实现光、电物理性质的系统调变；3）连接基元功能化，建立官能化调控—性能之间的关系，实现神经毒剂的高效降解。在此基础上，为了解决其在呼吸防护、皮防等实际应用中的问题，我们发展了多种制备机多孔材料薄膜的策略，如“刚柔并济”、“限域聚合”、热致相分离-热压法成膜等，为开发具有神经毒剂特异性选择的COF薄膜用于神经毒剂的荧光检测或降解领域提供了一定的研究基础。在此项目资助期间内，申请人以通讯作者身份（含共同）发表包括1篇Nat. Commun.、2篇J. Am. Chem. Soc.、5篇Angew. Chem. Int. Ed.、1篇Adv. Mater.等17篇文章，并申请专利11项，其中授权专利2项。