Mechanistic Studies of Oxygen Evolution and Hydrogen Atom Transfer in Enzymes and Biomimatic Models

酶和仿生模型中析氧和氢原子转移的机理研究

• 批准号: 0749572
• 负责人: Mahdi Abu-Omar
• 金额: $ 43.5万
• 依托单位: Purdue University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-08-01 至 2012-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0749572&HistoricalAwards=false
• 关键词: Mechanistic; Studies; Oxygen; Evolution; Hydrogen

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Mahdi Abu-Omar at Purdue University to investigate metal mediated hydrogen atom transfer (HAT) and to study the reactions involved with chlorite dismutase. The objectives of the HAT chemistry are to: (1) study the kinetics and mechanism(s) of hydrogen atom transfer (HAT) in a series of tosylimido complexes of corrole (Mn, Cr, and V) and their oxo analogs, and (2) expand the utility of HAT with these novel imido complexes to achieve catalytic amination of C-H bonds. A second project is concerned with the reaction chemistry (dismutation/destruction) of the chlorite ion (ClO2 -), which is formed by perchlorate respiring bacteria. The mechanism of chlorite dismutation in the enzyme chlorite dismuatse (Cld) will be studied and compared with water soluble prophyrinoid models. Understanding reaction rates and mechanisms of metal mediated HAT reactions relates to harnessing these reactions for benign functionalization of C-H bonds. The study of chlorite dismutation in enzyme and models has ramifications for the chemistry of chloride oxyanions in the environment. Postdoctoral, graduate, and undergraduate researchers will learn to make molecules, measure kinetics, perform state-of-the art spectroscopic experiments, and analyze data to gain molecular (mechanistic) insight, and present their research findings.

无机，生物无机和有机化学计划的这一奖项支持普渡大学Mahdi Abu-Omar教授的研究，以研究金属介导的氢原子转移（HAT）并研究与歧化酶有关的反应。HAT化学的目的是：（1）研究一系列对甲苯磺酰亚胺配合物及其氧代类似物中氢原子转移（HAT）的动力学和机理;（2）拓展HAT与这些新型亚胺配合物在实现C-H键催化胺化中的应用。 第二个项目涉及高氯酸盐呼吸细菌形成的氯离子（ClO 2-）的反应化学（歧化/破坏）。 本文将研究酶Cld的歧化机理，并与水溶性类藜芦醇模型进行比较。理解金属介导的HAT反应的反应速率和机制涉及利用这些反应进行C-H键的良性官能化。 酶和模型中的氯离子歧化研究对环境中氯氧阴离子的化学有着重要的影响。博士后，研究生和本科生研究人员将学习制造分子，测量动力学，进行最先进的光谱实验，并分析数据以获得分子（机械）见解，并展示他们的研究成果。