Light-driven oxygen atom transfer

光驱动的氧原子转移

• 批准号: EP/J019666/1
• 负责人: Anne-Kathrin Duhme-Klair
• 金额: $ 44.06万
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2013
• 资助国家: 英国
• 起止时间: 2013 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FJ019666%2F1
• 关键词: Light; driven; oxygen; atom; transfer

Nature uses molybdenum-containing enzymes to catalyse reactions that involve the transfer of oxygen atoms from water. The electrons that are released during the oxidation are transported from the molybdenum centre to the other side of the enzymes, where they are handed over to a terminal electron acceptor. Light absorption can cause electron transfer from one part of a molecule to another or between molecules. Indeed such processes are crucial in photosynthesis. Within this project, we aim to mimic the electron transfer processes of molybdenum enzymes by connecting Mo-centre mimics to electron transfer units, which can be activated by light. This will allow us to trigger the oxygenation reaction with a light flash and help us to learn more about the function of the enzymes. By using a variety of different molybdenum centres and photoactive units, we will identify the best combinations of components. Once the model systems are optimised, photoactivation may allow us to improve the energy and atom efficiency of industrially relevant oxidation processes and to oxygenate molecules related to DNA bases that are similar to the substrates of the molybdoenzyme xanthine oxidase.

大自然使用含钼酶来催化涉及水中氧原子转移的反应。氧化过程中释放的电子从钼中心传输到酶的另一侧，在那里它们被移交给末端电子受体。光吸收可以导致电子从分子的一个部分转移到另一部分或分子之间。事实上，这些过程对于光合作用至关重要。在这个项目中，我们的目标是通过将钼中心模拟物连接到可以被光激活的电子转移单元来模拟钼酶的电子转移过程。这将使我们能够通过闪光触发氧化反应，并帮助我们更多地了解酶的功能。通过使用各种不同的钼中心和光敏单元，我们将确定组件的最佳组合。一旦模型系统得到优化，光活化可能使我们能够提高工业相关氧化过程的能量和原子效率，并氧化与与钼酶黄嘌呤氧化酶底物相似的DNA碱基相关的分子。

项目成果

Bio-inspired Photoredox Catalysis with Mo-complexes

钼络合物的仿生光氧化还原催化

• 发表时间: 2014
• 期刊: Journal of Biological Inorganic Chemistry
• 影响因子: 3
• 作者: Ducrot A

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

• DOI: 10.1021/acs.inorgchem.6b01485
• 发表时间: 2016-10
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Aurélien Ducrot;B. Coulson;R. Perutz;A. Duhme‐Klair