BINUCLEATING TETRAPYRROLE MACROCYCLE:OXYGENASE CHEMISTRY

双核四吡咯大环：加氧酶化学

• 批准号: 3292967
• 负责人: KRISTIN Susan BOWMAN-JAMES
• 金额: $ 7.37万
• 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 1992-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3292967
• 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.

两个的结构混合融合方面两个的活性位点 突出的生物氧活化催化剂：双核 功能（如许多铜蛋白）和四吡咯 框架（如血红素铁蛋白中）被提出为氧合酶 模仿。 在进化过程中，两个系统，血红素 铁和铜蛋白与 尊重功能；而且铜和血红素铁位均为 例如，已知在细胞色素氧化酶中一起发生。 因此检查了这些平行的共同影响 交织在一起的系统是一个令人兴奋的前景 了解过去和潜在的未来的运作 进化过程。 重点将放在电子上， 吡fyolic和双核的结构含义 氧合酶活性上的环系统。 要检查的系统将 包括金属离子铜，钴，铁和唯一 烷烃和烯烃底物。 具体研究是 进行的将包括X射线晶体结构 确定活性催化剂和中间物种， 金属离子配合物的电化学和磁研究， 和氧气摄取测量与分离结合 和氧化物种的表征。

项目成果

Structure of [N,N'-propylenebis(2-pyrrolylmethyleneaminato)]nickel(II).

[N,N-亚丙基双(2-吡咯亚甲基氨基)]镍(II) 的结构。

• DOI: 10.1107/s0108270189001800
• 发表时间: 1989
• 期刊: Acta crystallographica. Section C, Crystal structure communications
• 作者: Sakon,J;Reiter,A;Mertes,KB;Takusagawa,F
• 通讯作者: Takusagawa,F