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.

一种结构混合物，融合了两种 卓越的生物氧活化催化剂：双核 能力（如在许多铜蛋白），和一个tetraphyrrolic 框架（如血红素铁蛋白），被认为是加氧酶 模仿 在进化过程中，两个系统，血红素， 铁和铜蛋白，与 关于功能;铜和血红素铁网站都是 例如，已知在细胞色素氧化酶中一起发生。 因此，检查这些平行的综合影响， 和相互交织的系统是一个令人兴奋的前景， 了解过去和未来的潜在运作 进化过程 重点将放在电子和 吡咯和双核化合物的结构意义 环系统对加氧酶活性的影响。 待审查的系统将 包括金属离子铜、钴、铁和钌， 烷烃和烯烃底物。 具体研究将 将包括X射线晶体结构 活性催化剂和中间物质的测定， 金属离子络合物的电化学和磁性研究， 以及氧摄取测量结合隔离 和含氧物质的表征。

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