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Synthetic Fe/Cu Complexes: Toward Understanding Heme-Copper Oxidase Structure and Function
Chemical Reviews ( IF 51.4 ) Pub Date : 2018-10-29 00:00:00 , DOI: 10.1021/acs.chemrev.8b00074
Suzanne M Adam 1 , Gayan B Wijeratne 1 , Patrick J Rogler 1 , Daniel E Diaz 1 , David A Quist 1 , Jeffrey J Liu 1 , Kenneth D Karlin 1
Affiliation  

Heme-copper oxidases (HCOs) are terminal enzymes on the mitochondrial or bacterial respiratory electron transport chain, which utilize a unique heterobinuclear active site to catalyze the 4H+/4e reduction of dioxygen to water. This process involves a proton-coupled electron transfer (PCET) from a tyrosine (phenolic) residue and additional redox events coupled to transmembrane proton pumping and ATP synthesis. Given that HCOs are large, complex, membrane-bound enzymes, bioinspired synthetic model chemistry is a promising approach to better understand heme–Cu-mediated dioxygen reduction, including the details of proton and electron movements. This review encompasses important aspects of heme–O2 and copper–O2 (bio)chemistries as they relate to the design and interpretation of small molecule model systems and provides perspectives from fundamental coordination chemistry, which can be applied to the understanding of HCO activity. We focus on recent advancements from studies of heme–Cu models, evaluating experimental and computational results, which highlight important fundamental structure–function relationships. Finally, we provide an outlook for future potential contributions from synthetic inorganic chemistry and discuss their implications with relevance to biological O2-reduction.

中文翻译:


合成铁/铜复合物:了解血红素铜氧化酶的结构和功能



血红素铜氧化酶 (HCO) 是线粒体或细菌呼吸电子传递链上的末端酶,它利用独特的异双核活性位点催化 4H + /4e -将分子氧还原为水。该过程涉及来自酪氨酸(酚)残基的质子耦合电子转移(PCET)以及与跨膜质子泵和 ATP 合成耦合的额外氧化还原事件。鉴于 HCO 是大型、复杂的膜结合酶,受生物启发的合成模型化学是一种有前途的方法,可以更好地理解血红素-铜介导的双氧还原,包括质子和电子运动的细节。本综述涵盖了血红素-O 2和铜-O 2 (生物)化学的重要方面,因为它们与小分子模型系统的设计和解释有关,并提供了基础配位化学的观点,可应用于理解 HCO 活性。我们重点关注血红素-铜模型研究的最新进展,评估实验和计算结果,这些结果强调了重要的基本结构-功能关系。最后,我们对合成无机化学的未来潜在贡献进行了展望,并讨论了它们对生物 O 2还原的影响。
更新日期:2018-10-29
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