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Charge transfer in the K proton pathway linked to electron transfer to the catalytic site in cytochrome c oxidase

机译:钾质子途径中的电荷转移与电子转移至细胞色素c氧化酶的催化位点有关

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摘要

Cytochrome c oxidase couples electron transfer from cytochrome C to 02 to proton pumping across the membrane. In the initial part of the reaction of the reduced cytochrome c oxidase with 02, an electron is transferred from heme a to the catalytic site, parallel to the membrane surface. Even though this electron transfer is not linked to proton uptake from solution, recently Belevich et al. [(2006) Nature 440, 829] showed that it is linked to transfer of charge perpendicular to the membrane surface (electrogenic reaction). This electrogenic reaction was attributed to internal transfer of a proton from Glu286, in the D proton pathway, to an unidentified protonatable site "above" the heme groups. The proton transfer was proposed to initiate the sequence of events leading to proton pumping. In this study, we have investigated electrogenic reactions in structural variants of cytochrome c oxidase in which residues in the second, K proton pathway of cytochrome c oxidase were modified. The results indicate that the electrogenic reaction linked to electron transfer to the catalytic site originates from charge transfer within the K pathway, which presumably facilitates reduction of the site.
机译:细胞色素C氧化酶使电子从细胞色素C到02的传递与质子泵送穿过膜耦合。在还原的细胞色素C氧化酶与O 2反应的初始阶段,电子从血红素a转移到平行于膜表面的催化部位。即使这种电子转移与溶液中质子的吸收没有关系,最近Belevich等人也提出了。 [(2006)Nature 440,829]表明,它与垂直于膜表面的电荷转移有关(电发生反应)。该电原性反应归因于质子在D质子途径中从Glu286的质子内部转移到血红素基团“上方”的未知质子化位点。提出质子转移以引发导致质子泵送的事件的顺序。在这项研究中,我们研究了细胞色素C氧化酶结构变体中的电源反应,其中细胞色素C氧化酶的第二个K质子途径中的残基被修饰。结果表明,与电子转移至催化位点相关的电致反应起源于K途径内的电荷转移,这可能促进了位点的还原。

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