识别铀酰的荧光共轭聚合物的制备、机理和细胞成像

It is an urgent issue that the nanomole uranyl can be monitored in situ in the environment and living cells. The classes of Salophen Schiff bases and amidoxime have been provide with the properties of strong affinity and recognition to uranyl, radiation resistance and stable and regulable structure. Moreover, fluorescent conjugated polymers possess “Molecular Wire Effect”, which its sensing signal could be amplified and increasingly improved sensitivity. This study intends to synthesize some fluorescent conjugated polymers containing function groups of Salophen Schiff bases (SCP for short) or amidoxime (AOCP for short). Then the supersensitivity fluorescent sensor of uranyl in the environment and in living cells could be obtained by structure modification. Furthermore, the real-time in situ analysis methods, which are high selectivity and extra-sensitivity, of nanomole even to picomole uranyl would be established using the SCP or AOCP fluorescent recognition of uranyl. In addition, it would be studied what was the way they act on uranyl. Finally, the mechanism of reaction between the SCP or AOCP with uranyl and the fluorescent sensor mechanism would be set up. In addition, this study could complete the theory of fluorescence and enrich the field in uranium science and provide new method for study uranium migration, action targeting, the mechanism of toxicity and so on in human body.

环境中和生物体内原位纳摩尔级铀酰的检测是亟待解决的问题。Salophen类Schiff 碱和偕胺肟对铀酰具有强的亲和能力和识别作用，且耐辐射、结构稳定可调控。而荧光共轭聚合物具有“分子导线效应”，能放大传感信号，极大地提高灵敏度。本申请拟制备Salophen类Schiff 碱或偕胺肟功能化的荧光共轭聚合物（简称SCP或AOCP），通过结构修饰获得对环境和细胞中铀酰超灵敏的探针；利用SCP或AOCP对铀酰的荧光识别，建立对纳摩尔甚至皮摩尔级铀酰具有高选择性和超灵敏的实时原位分析新方法；研究SCP和AOCP与铀酰的作用模式，并提出它们与铀酰的作用机理和荧光识别机制。同时，本申请的研究可完善荧光理论，丰富铀科学和为铀酰在人体的迁移途径、作用靶向和毒害作用机理等研究提供方法。

环境中和生物体内原位纳摩尔级铀酰的检测是亟待解决的问题。Salophen类Schiff碱和偕胺肟对铀酰具有强的亲和能力和识别作用，且耐辐射、结构稳定可调控。而荧光共轭聚合物具有“分子导线效应”，能放大传感信号，极大地提高灵敏度。本研究合成了一种新型芴和偕胺肟基团共轭聚合物（P2）、2-(4,5-二氢噻唑)-4-(4-二苯胺基)苯酚（USC-001）、2-（5′-（对-（二苯氨基）苯基）-2′-吡啶偶氮）-5-（二乙氨基）苯酚（S-LH）和2-(5-(4-(9,9‘-二辛基-4‘-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷))芴基)-2-吡啶偶氮)-5-二乙氨基酚(W1)。以P2荧光探针，建立了高选择性的纳摩尔级铀酰的荧光分析方法。同时，以USC-001为探针实现了高酸性水环境中和活细胞中铀酰的高灵敏性、高选择性检测。提出了它们检测铀酰的荧光机理。此外，通过分子设计合成得到了S-LH 和W1，以此建立了比色分析新方法，提升了铀酰比色分析法的抗干扰能力，并可在线监测。合成了Salophen类四苯乙烯基水杨醛席夫碱（BH-TPE），以它为探针建立了强酸性条件下Th4+的荧光检测新方法，获得了荧光探测机理。且该探针可实现活细胞中Th4+的成像。