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

职业 / SusChEM：生物放氧复合物构象灵活类似物的仿生合成：锰簇分子的重新设计方法

• 批准号: 1254545
• 负责人: Michael Zdilla
• 金额: $ 50万
• 依托单位: Temple University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2018-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1254545&HistoricalAwards=false
• 关键词: CAREER; SusChEM; Bio; inspired; synthesis

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.

凭借这一职业奖，化学合成计划将支持天普大学 Michael J. Zdilla 教授对光系统 II 的析氧复合物 (OEC) 的研究，该复合物是太阳能水分解过程中最耗能的组成部分的自然解决方案。这种催化剂是一种锰-钙-氧簇，通过 5 级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，并收获还原当量以在糖中储存能量。在这一领域，存在相对广泛的锰簇化学模型，但重排化学和簇灵活性（OEC 作用的关键组成部分）在文献中没有得到很好的体现。 Zdilla 教授的研究项目有两个主要重点：1）通过避免稳定螯合配体（将簇核锁定到位）来设计和制备具有增强灵活性的锰簇，2）研究这些系统的反应和重排化学，特别是与成熟的、更稳定的螯合物簇相比。全球能源需求持续呈指数级增长，而化石燃料储备持续枯竭。为了满足世界能源需求，必须开发新的太阳能技术。大自然选择锰簇辅助因子来实现光合作用中困难的水氧化反应，这表明这些分子对于太阳能水活化具有巨大的变革能力。拟议的工作将在工作中追求这些目标，为研究生和本科生提供培训机会，并在坦普尔大学提供少数民族培训机会，坦普尔大学是美国种族和文化最多元化的城市学校之一。该 PI 将继续通过化学遗产基金会、Nerd Nite Cafe 和费城科学节等组织参与费城地区的科学推广活动。他还将与全球晶体学界一起致力于开发急需的 X 射线晶体学教育资源数据库，供所有晶体学教师和学生使用，旨在为这一多领域学科提供广泛的教育资源。