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Conformationally-flexible, reactive manganese clusters to probe possible mechanisms of oxygen-oxygen bond formation in photosystem II

构象灵活的反应性锰簇探索光系统 II 中氧-氧键形成的可能机制

基本信息

批准号：
1800105
负责人：
Michael Zdilla
金额：
$ 42万
依托单位：
Temple University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-09-01 至 2022-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800105&HistoricalAwards=false
关键词：
Conformationally flexible reactive manganese clusters

项目摘要

In the early stages of the development of life on earth, perhaps the most significant evolutionary breakthrough was the sunlight-driven oxidation of water to oxygen (O2) by the ancient ancestors of cyanobacteria and modern plants. These organisms discovered a way to make their own food using the virtually limitless supply of water and sunlight available near the surface of the oceans. As far as science knows, organisms have found only one way to perform this water oxidation process, and it is possible that modern plants and photosynthetic organisms are still using that same evolutionary innovation from billions of years ago, although presumably significantly evolved. The enzyme that performs this reaction is called Photosystem II, and despite the central importance of this reaction to the fields of biology and energy, many questions remain about how this enzyme works. Professor Zdilla is working to build molecular models of the enzyme active site, which is a cube-shaped cluster of metal atoms containing manganese and calcium. The working models developed by Professor Zdilla may lead to insights on how photosynthetic organisms are able to perform this important reaction. Professor Zdilla continues his community engagement of youth and adult communities through talks during the Philadelphia Science Festival and at Philadelphia elementary schools. Professor Zdilla also develops the Database of Educational Crystallographic Online Resources (DECOR), a free, downloadable source of educational materials for the study of crystallography. The primary source of cellular energy on earth is the sun, whose visible light energy is harvested by photosynthetic organisms to drive the oxidation of water to O2 and drive the concomitant reduction of carbon dioxide(CO2) to organic molecules, which are then used as fuel and as raw materials for the construction of living things. Photocatalytic water oxidation coupled to proton reduction is also an important goal for the generation of sustainable solar fuels. The enzyme responsible for the biological water oxidation reaction is photosystem II (PSII), a multi-subunit enzyme containing a tetramanganese-calcium-oxo cluster as the catalytic active site. Since enzymes are often a challenge to study directly due to their complexity, bioinorganic chemists frequently turn to biomimetic model complexes. Despite hundreds of examples of synthetic manganese oxo-cluster, very few show compelling reactivity that models PSII. Professor Zdilla and his group develop new approaches to designing biomimetic manganese clusters by prioritizing low-coordination number(to provide water binding sites) and cluster flexibility (to promote molecular rearrangement). These approaches have resulted in clusters that perform a diverse set of difficult reactions including N-N, C-H, C-N, and O=O bond making/breaking reactions, and catalytic water oxidation. This project seeks to further mechanistically investigate their molecular mechanisms, which may inform understanding of the function of the enzyme, and provide clues on how to design superior water oxidation catalysts for energy purposes. Professor Zdilla continues his community engagement of youth and adult communities through talks during the Philadelphia Science Festival and at Philadelphia elementary schools. Professor Zdilla also develops the Database of Educational Crystallographic Online Resources (DECOR), a free source of educational materials for the study of crystallography.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在地球生命发展的早期阶段，最重要的进化突破也许是蓝细菌和现代植物的远古祖先在阳光驱动下将水氧化成氧气（O2）。这些生物体发现了一种利用海洋表面附近几乎无限的水和阳光来制造自己食物的方法。据科学所知，生物体只找到了一种方法来执行这种水氧化过程，并且现代植物和光合生物体可能仍在使用数十亿年前的相同进化创新，尽管可能已经发生了显着的进化。进行这种反应的酶被称为光系统 II，尽管这种反应对于生物学和能源领域至关重要，但关于这种酶如何工作的问题仍然存在。 Zdilla 教授正在致力于建立酶活性位点的分子模型，该酶活性位点是含有锰和钙的金属原子的立方体簇。 Zdilla 教授开发的工作模型可能有助于了解光合生物如何执行这一重要反应。兹迪拉教授通过费城科学节期间和费城小学的演讲，继续促进青少年和成人社区的社区参与。 Zdilla 教授还开发了教育晶体学在线资源数据库 (DECOR)，这是一个免费的、可下载的晶体学研究教育材料来源。地球上细胞能量的主要来源是太阳，光合生物收集可见光能量，将水氧化为 O2，并同时将二氧化碳 (CO2) 还原为有机分子，然后将有机分子用作燃料和构建生物的原材料。光催化水氧化与质子还原相结合也是生产可持续太阳能燃料的一个重要目标。负责生物水氧化反应的酶是光系统 II (PSII)，这是一种多亚基酶，含有四锰-钙-氧簇作为催化活性位点。由于酶的复杂性，直接研究通常是一个挑战，生物无机化学家经常转向仿生模型复合物。尽管合成锰氧簇的例子有数百个，但很少有表现出模拟 PSII 的令人信服的反应性。 Zdilla 教授和他的团队通过优先考虑低配位数（以提供水结合位点）和簇灵活性（以促进分子重排），开发了设计仿生锰簇的新方法。这些方法产生的簇可以执行一系列不同的困难反应，包括 N-N、C-H、C-N 和 O=O 键形成/断裂反应，以及催化水氧化。该项目旨在进一步从机械角度研究它们的分子机制，这可能有助于理解酶的功能，并为如何设计用于能源目的的优质水氧化催化剂提供线索。兹迪拉教授通过费城科学节期间和费城小学的演讲，继续促进青少年和成人社区的社区参与。 Zdilla 教授还开发了教育晶体学在线资源数据库 (DECOR)，这是晶体学研究教育材料的免费来源。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。