CAREER / SusChEM: Bio-inspired synthesis of conformationally flexible analogues of the biological oxygen evolving complex: A redesigned approach to manganese cluster molecules

有了这一职业奖，化学合成计划将支持坦普尔大学的迈克尔·J·兹迪拉教授对光系统II的放氧复合体(OEC)的研究，OEC是自然界解决太阳水分裂中最耗能的成分的方案。这种催化剂是一个锰-钙-氧簇合物，它通过5个阶段的催化循环进行结构重排，将水氧化为氧气，将质子泵过类囊体膜，并获得还原当量以储存能量在糖中。在这一领域，有相对广泛的锰团簇模型化学，但重排化学和团簇柔性，这两个OEC作用的关键成分，在文献中没有得到很好的描述。Zdilla教授的研究计划主要有两个重点：1)设计和制备通过避免稳定的螯合配体来增强灵活性的锰簇，该配体将簇核锁定在适当的位置；2)研究这些体系的反应和重排化学，特别是与成熟的、更稳定的螯合簇相比。全球能源需求继续呈指数级增长，而化石燃料储备继续枯竭。为了满足世界能源需求，必须开发新的太阳能技术。自然界选择了一种锰簇辅助因子来实现困难的光合作用水氧化反应，这表明这些分子拥有巨大的太阳能水活化变革力。拟议中的工作将在为研究生和本科生提供培训机会的工作中追求这些目标，并为坦普尔提供少数族裔培训机会，坦普尔是美国种族和文化最多元化的城市学校之一。PI将通过化学遗产基金会、Nerd Nite咖啡馆和费城科学节等组织继续参与费城地区的科学推广活动。他还将与世界结晶界一道，开发一个亟需的X射线结晶学教育资源数据库，供所有结晶学教师和学生使用，目的是为这一多领域学科提供广泛的教育资源。

With this CAREER award, the Chemical Synthesis Program will support the research of Professor Michael J. Zdilla of Temple University on the oxygen evolving complex (OEC) of photosystem II that is nature's solution to the most energetically taxing component of solar water splitting. This catalyst is a manganese-calcium-oxo cluster which undergoes structural rearrangements via a 5-stage catalytic cycle whereby it oxidizes water to oxygen, pumps protons across the thylakoid membrane, and harvests reducing equivalents for energy storage in sugars. In this area there is relatively extensive model chemistry of manganese clusters but the rearrangement chemistry and cluster flexibility, key components to the action of the OEC, are not well represented in the literature. Prof Zdilla's research program has two main foci: 1) the design and preparation of manganese clusters of enhanced flexibility via the avoidance of stabilizing chelating ligands, which lock cluster cores in place, and 2) study of reaction and rearrangement chemistry of these systems, especially in comparison to the well-established, more stable chelate clusters. Global energy demand continues to grow exponentially while fossil fuel reserves continue to be depleted. To meet world energy demands, new solar energy technology must be developed. Nature's selection of a manganese cluster cofactor to achieve the difficult water oxidation reaction of photosynthesis suggests these molecules possess enormous transformative power for solar-powered water activation. The proposed work will pursue these goals in work that affords the opportunity for training of graduate and undergraduate students, and also provides minority training opportunities at Temple, one of the most ethnically and culturally diverse urban schools in the United States. The PI will continue his involvement in science outreach in the Philadelphia area through organizations like the Chemical Heritage Foundation, Nerd Nite Cafe, and the Philadelphia Science Festival. He will also pursue, along with the worldwide crystallographic community, the development of a much needed database of X-ray crystallographic educational resources, accessible to all teachers and students of crystallography, with the aim of providing extensive educational resources for this multi-field discipline.