Kinetics and Mechanisms of Oxygen and Peroxide Activation by Non-heme Iron Complexes

非血红素铁络合物活化氧和过氧化物的动力学和机制

• 批准号: 0111202
• 负责人: Elena Rybak-Akimova
• 金额: $ 24万
• 依托单位: Tufts University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-10-01 至 2005-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0111202&HistoricalAwards=false
• 关键词: Kinetics; Mechanisms; Oxygen; Peroxide; Activation

Elena Rybak-Akimova of Tufts University is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program to conduct research on kinetics and mechanisms of oxygen and peroxide activation by non-heme iron complexes. She has not previously been PI of NSF research grants. A main aim of the proposal is to elucidate the difference between iron-mediated biological oxidations that involve free radicals and those that proceed through 'radical-free' pathways. Kinetic and mechanistic studies of high-valent iron oxo species supported by tris-picolyamine (TPA) ligands will be carried out at low temperatures, using cryogenic stopped-flow techniques (single and double mixing) with spectrophotometric and EPR registration. Research under this project will clarify obscure aspects of important biochemical processes and provide insights that potentially will lead to development of environmentally benign processes using oxygen and/or hydrogen peroxide in chemical synthesis and oxidative detoxification of wastes. Sophisticated stopped-flow kinetic studies, such as those proposed here, are necessary to demonstrate the relationship of synthetic models of enzyme active sites to actual biological function. Few laboratories now have the capability to carry out such studies. This program will provide especially valuable training for students and postdoctoral researchers.

塔夫茨大学的Elena Rybak-Akimova在无机化学、生物无机化学和金属有机化学项目的支持下，开展了非血红素铁络合物激活氧和过氧化氢的动力学和机理研究。她之前从未担任过美国国家科学基金会研究拨款的PI。该提案的一个主要目的是阐明铁介导的涉及自由基的生物氧化与那些通过‘自由基’途径进行的生物氧化之间的区别。利用低温停流技术(单混合和双混合)、分光光度和EPR配准，将在低温下对三吡唑胺(TPA)配体支撑的高价铁氧物种进行动力学和机理研究。该项目下的研究将澄清重要生化过程的模糊方面，并提供可能导致开发在化学合成和废物氧化解毒中使用氧气和/或过氧化氢的对环境无害的过程的见解。复杂的停流动力学研究，如这里提出的那些，是必要的，以证明酶活性部位的合成模型与实际生物功能的关系。现在很少有实验室有能力进行这样的研究。该项目将为学生和博士后研究人员提供特别有价值的培训。