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Photosynthetic water oxidation vs. mitochondrial oxygen reduction: distinct mechanistic parallels

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Abstract

The photosynthetic oxygen evolving complex (PSII-OEC) and the mitochondrial cytochrome c oxidase (CcO) not only catalyze anti-parallel reactions (the OEC oxidizes water to dioxygen, whereas CcO reduces dioxygen to water), they also share a number of uncanny molecular and mechanistic similarities. Both feature a redox-active polymetallic cluster that includes a key tyrosine, and both utilize a two-phase mechanism. In one phase the polymetallic cluster undergoes four sequential one-electron transfers: In the PSII-OEC, four successive photooxidations of the photosystem II reaction center P680 (to P680+) allows acceptance of 4 × 1e- from the Mn4Ca cluster; in CcO, four reduced cytochrome c Fe2+ cations donate 4 × 1e- to the bimetallic center. In the second phase for each enzyme, the polymetallic cluster undergoes a single four-electron transfer with the O2/2 H2O redox couple. Intriguing mechanistic similarities between these two complex redox enzymes first delineated over a decade ago by Hoganson/Proshlyakov/Babcock et al. are updated and expanded in this article.

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  1. Chemistry Department, Willamette University, Salem, OR, 97301, USA

    Todd P. Silverstein

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Correspondence to Todd P. Silverstein.

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Silverstein, T.P. Photosynthetic water oxidation vs. mitochondrial oxygen reduction: distinct mechanistic parallels. J Bioenerg Biomembr 43, 437–446 (2011). https://doi.org/10.1007/s10863-011-9370-7

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