BINUCLEATING TETRAPYRROLE MACROCYCLE:OXYGENASE CHEMISTRY

双核四吡咯大环：加氧酶化学

• 批准号: 3292966
• 负责人: KRISTIN Susan BOWMAN-JAMES
• 金额: $ 7.35万
• 依托单位: UNIVERSITY OF KANSAS LAWRENCE
• 依托单位国家: 美国
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-03-01 至 1991-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3292966
• 关键词: X ray crystallography; alkanes; catalyst; chemical structure function; cobalt; copper; cycloalkene; cytochrome oxidase; electrochemistry; evolution; ferriheme; manganese; metalloproteins; nuclear magnetic resonance spectroscopy; oxygen; oxygenases; pyrroles; respiratory oxygenation; ruthenium; tetrapyrroles

A structural hybrid melding aspects of the active sites of two prominent biological oxygen activation catalysts: binuclear capabilities (as in many cuproproteins), and a tetraphyrrolic framework (as in heme iron proteins), is proposed as an oxygenase mimic. During the evolutionary process the two systems, heme iron and copper proteins, have been closely associated with respect to function; and both copper and heme iron sites are known to occur together in cytochrome oxidase, for example. Thus an examination of the combined influence of these parallel and intertwined systems is an exciting prospect for better understanding the workings of past and potentially future evolutionary processes. Focus will be on the electronic and structural implications of the combined pyrrolic and binuclear ring system on oxygenase activity. Systems to be examined will include the metal ions copper, cobalt, iron, and ruthenium with alkane and olefin substrates. The specific studies to be undertaken will include X-ray crystallographic structural determinations of active catalysts and intermediate species, electrochemical and magnetic studies of the metal ion complexes, and oxygen uptake measurements in conjunction with the isolation and characterization of oxygenated species.

一种结构杂化的两方面的活性位点熔接