双功能结构集成策略构筑对中性芳香客体应答的水溶性荧光传感器

Neutral aromatic substances, such as nitroaromatics is typical class of organic pollutants. The application of fluorescent sensors to detect neutral aromatic substances is very important to environment science, analytical chemistry and life science. The development of fluorescent sensors which selectively recognize the neutral aromatic guests is very difficult as the lack of sufficient charge changes. Existing researches are mainly work in non-aqueous media, which greatly limit thier access to the actual application..Based on the bis-functionalized structure integrated strategy of recognition performance and water-soluble ability, this project focuses on the exploration of water-soluble rigid aromatic molecular clips as fluorescent sensors recognizing neutral aromatic guests. Firstly, diverse fluorescent chromophores such as, aryl, alkynyl/alkenyl substituted aryl, coumarin and fluorescein are introduced into the framework of aromatic molecular clips. The synthesized molecular clips will be assayed for their fluorescence properties and recognition ability to found the potent molecular clip type. Further structure optimization of the framework, linker of chromophores, substituted group and water-soluble ability will resulte in the discovery of visualized water-soluble fluorescent moleculer clips with specific recognition performance of neutral aromatic guests in aqueous phase. The preliminary application of the potent molecular clips as fluorescent sensors will also be carried out.

中性芳香类物质，如硝基芳烃是一类常见的有机污染物。利用荧光传感器有效地检测该类物质对环境科学、分析化学以及生命科学都有着重大意义。该类中性客体由于缺乏足够的电荷变化，其选择性识别的荧光传感器的研究一直是比较困难的课题。现有的相关研究也主要是在非水介质中进行的，极大的限制了其进入实际应用。.本项目采取荧光识别性能和水溶性的双功能结构集成策略，探索将对中性芳香客体有较好识别能力的水溶性刚性多芳环分子夹应用为荧光传感器。本项目基于多芳香环类分子夹骨架，先引入芳基、炔/烯取代芳基、香豆素、荧光素等类型的荧光发色团；通过荧光性质及识别中性芳香客体性能的初步研究，发现有优化潜力的分子夹类型；再进一步开展荧光分子夹的结构优化（分子夹骨架、发色团的连接方式和取代基的多样性改造）和水溶性调节，最终发现能在水相中实现对中性芳香客体特异性识别、有可视化应用前景的水溶性荧光分子夹；并将开展初步的应用研究。

本项目研究工作总体进展顺利，完成了计划任务的主要研究任务。本项目基于荧光识别性能和水溶性的双功能结构集成策略，采用分子Lego的汇聚式合成方法构筑了含可修饰官能团的多芳环分子夹中间体；利用各类交叉偶联反应、缩合反应等手段成功构筑了发色团类型丰富的系列荧光分子夹；深入研究了这些荧光分子夹的光谱性质，开展对不同中性芳香客体和其他客体的识别性能的研究。研究结果表明，部分分子夹对常见有机污染物硝基芳烃、苯胺类化合物、金属离子以及富勒烯类大分子客体具有专一选择性的荧光响应能力。在此基础上，为了提升该类荧光分子夹的实际应用价值，我们通过在荧光分子夹的骨架上引入了水溶性基团，成功的调节了其水溶性。初步的应用研究显示该类荧光分子夹有望实现在水相中对中性芳香客体以及金属离子，富勒烯等客体的特异性识别功能。后续的研究工作还在进行中。. 本项目已在Chem. Eur. J. 和Bioorg. Med. Chem. Lett.等国际知名学术期刊上发表论文4篇，获得授权中国发明专利1项，另有4篇相关研究论文正在整理投稿中，待发表。