Computational insights on crystal structures of the oxygen-evolving complex of photosystem II with either Ca²⁺ or Ca²⁺ substituted by Sr²⁺

Vogt, Leslie; Ertem, Mehmed Z.; Pal, Rhitankar; Brudvig, Gary W.; Batista, Victor S.

doi:10.1021/bi5011706

Title: Computational insights on crystal structures of the oxygen-evolving complex of photosystem II with either Ca²⁺ or Ca²⁺ substituted by Sr²⁺

Journal Article · Thu Jan 15 00:00:00 EST 2015 · Biochemistry

DOI:https://doi.org/10.1021/bi5011706· OSTI ID:1183828

Vogt, Leslie ^[1]; Ertem, Mehmed Z. ^[2]; Pal, Rhitankar ^[1]; Brudvig, Gary W. ^[1]; Batista, Victor S. ^[1]

Yale Univ., New Haven, CT (United States)
Yale Univ., New Haven, CT (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

The oxygen-evolving complex of photosystem II can function with either Ca²⁺ or Sr²⁺ as the heterocation, but the reason for differing turnover rates remains unresolved despite reported X-ray crystal structures for both forms. Using quantum mechanics/molecular mechanics (QM/MM) calculations, we optimize structures with each cation in both the resting state (S₁) and in a series of reduced states (S₀, S₋₁, and S-₂). Through comparison with experimental data, we determine that X-ray crystal structures with either Ca²⁺ or Sr²⁺ are most consistent with the S-₂ state, Mn₄[III,III,III,II] with O4 and O5 protonated. As expected, the QM/MM models show that Ca²⁺/Sr²⁺ substitution results in elongation of the heterocation bonds and displaces terminal waters W3 and W4. The optimized structures also show that hydrogen-bonded W5 is displaced in all S states with Sr²⁺ as the heterocation, suggesting that this water may play a critical role during water oxidation.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC00112704

OSTI ID:: 1183828

Report Number(s):: BNL-107849-2015-JA; R&D Project: CO045; KC0301020

Journal Information:: Biochemistry, Vol. 54, Issue 3; ISSN 0006-2960

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 29 works

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