Understanding Nature's Photosynthetic Water Oxidation Reaction by Combining Molecular Modelling and Magnetic Resonance Spectroscopy.

公认的生物学“圣杯”之一是光合作用中水氧化为分子氧的详细机制。最近在晶体结构测定、光谱学和计算化学方面的进展已经使详细的机制触手可及。该项目将在这方面发挥关键作用，将电子顺磁共振（EPR）光谱结果与破缺对称密度泛函理论（BS-DFT）计算相结合，研究水氧化循环的最后阶段，并研究自然界的水氧化催化剂（CaMn 4 O 5/6复合物）使两个水分子的氧去质子化和氧化，并在室温下将它们结合以产生分子氧。此外，还将研究一种接近自然系统的钴基模拟物。该项目属于生物能源领域，目的是模仿绿色植物利用太阳能生产高能燃料的能力。使用光谱学和分子建模的组合，我们将研究自然界最基本的反应之一的机制，即光合电子转移，提供数学和计算建模，生物光谱学和生物模拟合成的独特技能培训。合作将在美国的田口教授和迪卡诺夫教授的研究小组之间进行，从而促进国际合作。

One of the recognised "Holy Grails" of biology is the detailed mechanism of water oxidation to molecular oxygen in photosynthesis. Recent progress in crystallographic structure determination, spectroscopy and computational chemistry have now put the detailed mechanism within reach. This project will play a key role in this by combining Electron Paramagnetic Resonance (EPR) spectroscopy results with broken symmetry density functional theory (BS-DFT) calculations to study the final stages in the water oxidation cycle and examine the details of how Nature's water oxidising catalyst (a CaMn4O5/6 complex) deprotonates and oxidises the oxygens of two water molecules and combines them to produce molecular oxygen at room temperature. In addition a close Cobalt-based mimic of the natural system will be investigated. The project is within the bioenergy area with the aim of mimicking the ability of green plants to use solar energy to produce high energy fuels. Using a combination of spectroscopy and molecular modelling we will investigate the mechanism of one of nature's most fundamental reactions i.e. photosynthetic electron transfer providing unique skills training in mathematical and computational modelling, biological spectroscopy and synthesis of biological mimics. Collaboration will take place between the USA based research groups of Profs Taguchi and Dikanov thereby fostering international collaboration.