Biomolecule based fluorescent sensors for the selective detection of uranium in different oxidation states

天然水环境中铀和铀酰的检测在解释和监测迁移行为方面绝对是至关重要的，这反过来又是清理污染土地和确保长期地质处置安全的关键。目前还没有用于铀的选择性检测的基于荧光的传感器的实例，尽管用于其他有毒金属离子（例如Hg）的传感器是常见的并且现在用于环境采样工业。我们建议，通过结合选择性络合与间接荧光检测系统，铀可以检测到监测所需的水平。正在开发一系列化学和生物化学荧光探针，用于铀酰（VI）和铀（IV）离子的比率和特异性检测，以用于核退役和环境补救。具体而言，该项目涉及合成一个家庭的过渡多吡啶配合物的Re（I），Ru（II），Ir（III）和Pt（II）附加的结合位点的铀酰（VI），这里的邻苯二酚，聚氨基羧酸酯和乙二醇，评估的排放响应和斯特恩-沃尔默动力学的存在下，浓度不断增加的铀。由于光诱导电子转移，观察到过渡金属配合物的磷光衰减。然后将构建基于这些结构的具有两种不同过渡金属络合物的比率探针，并评价在铀存在下的磷光猝灭。该项目还正在开发铀酰（VI）荧光探针，使用改性的钙结合蛋白，其中铀作为钙模拟物。通过用两种荧光染料改造这样的蛋白质，在与铀酰（VI）结合时，与添加钙和其他常见金属离子相比，观察到不同的荧光响应。

The detection of uranium and uranyl in natural aqueous environments is absolutely paramount in deciphering and monitoring migration behavior, which in turn is crucial in cleaning up contaminated land sites and assuring the safety case of long-term geological disposal. Currently there are no examples of fluorescence based sensors for the selective detection of uranium, despite the fact that sensors for other toxic metal ions (e.g. Hg) are commonplace and now used in the environmental sampling industry. We propose that by combining selective complexation with indirect fluorescence detection systems, uranium can be detected at levels required for monitoring. A range of chemical and biochemical fluorescent probes for the ratiometric and specific detection of uranyl(VI) and uranium(IV) ions for potential use in nuclear decommissioning and environmental remediation are being developed. Specifically, this project involves the synthesis of a family of transition polypyridyl complexes of Re(I), Ru(II), Ir(III) and Pt(II) appended with a binding site for uranyl(VI), here catechol, polyaminocarboxylate and glycol, evaluating the emission response and Stern-Volmer kinetics in the presence of increasing concentrations of uranium. An attenuation in the phosphorescence of the transition metal complexes is observed due to photoinduced electron transfer. Ratiometric probes based on these constructs with two different transition metal complexes will then be constructed and the phosphorescence quenching in the presence of uranium evaluated. The project is also developing uranyl(VI) fluorescent probes using modified calcium binding proteins where uranium acts as a calcium mimic. By engineering such proteins with two fluorescent dyes, upon binding with uranyl(VI), a different fluorescence response is observed compared to addition of calcium and other common metal ions.