Light-driven oxygen atom transfer

自然界使用含钼酶来催化涉及氧原子从水中转移的反应。在氧化过程中释放的电子从钼中心转移到酶的另一边，在那里它们被移交给终端电子受体。光吸收会导致电子从分子的一部分转移到另一部分，或在分子之间转移。事实上，这些过程在光合作用中是至关重要的。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。这将使我们能够用闪光灯触发氧化反应，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活性单元，我们将确定组分的最佳组合。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，并使与DNA碱基相关的分子氧化，这些分子与钼酶黄嘌呤氧化酶的底物相似。

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.