Reversible Structural Isomerization of Nature’s Water Oxidation Catalyst Prior to O–O Bond Formation. Guo, Y., Messinger, J., Kloo, L., & Sun, L. Journal of the American Chemical Society, 144(26):11736–11747, July, 2022. Publisher: American Chemical Society![Reversible Structural Isomerization of Nature’s Water Oxidation Catalyst Prior to O–O Bond Formation [link]](https://bibbase.org/img/filetypes/link.svg "link")
Paper doi abstract bibtex Photosynthetic water oxidation is catalyzed by a manganese–calcium oxide cluster, which experiences five “S-states” during a light-driven reaction cycle. The unique “distorted chair”-like geometry of the Mn4CaO5(6) cluster shows structural flexibility that has been frequently proposed to involve “open” and “closed”-cubane forms from the S1 to S3 states. The isomers are interconvertible in the S1 and S2 states, while in the S3 state, the open-cubane structure is observed to dominate inThermosynechococcus elongatus (cyanobacteria) samples. In this work, using density functional theory calculations, we go beyond the S3+Yz state to the S3nYz• → S4+Yz step, and report for the first time that the reversible isomerism, which is suppressed in the S3+Yz state, is fully recovered in the ensuing S3nYz• state due to the proton release from a manganese-bound water ligand. The altered coordination strength of the manganese–ligand facilitates formation of the closed-cubane form, in a dynamic equilibrium with the open-cubane form. This tautomerism immediately preceding dioxygen formation may constitute the rate limiting step for O2 formation, and exert a significant influence on the water oxidation mechanism in photosystem II.
@article{guo_reversible_2022,
title = {Reversible {Structural} {Isomerization} of {Nature}’s {Water} {Oxidation} {Catalyst} {Prior} to {O}–{O} {Bond} {Formation}},
volume = {144},
issn = {0002-7863},
url = {https://doi.org/10.1021/jacs.2c03528},
doi = {10.1021/jacs.2c03528},
abstract = {Photosynthetic water oxidation is catalyzed by a manganese–calcium oxide cluster, which experiences five “S-states” during a light-driven reaction cycle. The unique “distorted chair”-like geometry of the Mn4CaO5(6) cluster shows structural flexibility that has been frequently proposed to involve “open” and “closed”-cubane forms from the S1 to S3 states. The isomers are interconvertible in the S1 and S2 states, while in the S3 state, the open-cubane structure is observed to dominate inThermosynechococcus elongatus (cyanobacteria) samples. In this work, using density functional theory calculations, we go beyond the S3+Yz state to the S3nYz• → S4+Yz step, and report for the first time that the reversible isomerism, which is suppressed in the S3+Yz state, is fully recovered in the ensuing S3nYz• state due to the proton release from a manganese-bound water ligand. The altered coordination strength of the manganese–ligand facilitates formation of the closed-cubane form, in a dynamic equilibrium with the open-cubane form. This tautomerism immediately preceding dioxygen formation may constitute the rate limiting step for O2 formation, and exert a significant influence on the water oxidation mechanism in photosystem II.},
number = {26},
urldate = {2024-10-16},
journal = {Journal of the American Chemical Society},
author = {Guo, Yu and Messinger, Johannes and Kloo, Lars and Sun, Licheng},
month = jul,
year = {2022},
note = {Publisher: American Chemical Society},
pages = {11736--11747},
}
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