Photoassembly of the Water-Oxidizing Complex in Photosystem II
Overview
Affiliations
The light-driven steps in the biogenesis and repair of the inorganic core comprising the O(2)-evolving center of oxygenic photosynthesis (photosystem II water-oxidation complex, PSII-WOC) are reviewed. These steps, known collectively as photoactivation, involve the photoassembly of the free inorganic cofactors to the cofactor-depleted PSII-(apo-WOC) driven by light and produce the active O(2)-evolving core comprised of Mn(4)CaO(x)Cl(y). We focus on the functional role of the inorganic components as seen through the competition with non-native cofactors ("inorganic mutants") on water oxidation activity, the rate of the photoassembly reaction, and on structural insights gained from EPR spectroscopy of trapped intermediates formed in the initial steps of the assembly reaction. A chemical mechanism for the initial steps in photoactivation is given that is based on these data. Photoactivation experiments offer the powerful insights gained from replacement of the native cofactors, which together with the recent X-ray structural data for the resting holoenzyme provide a deeper understanding of the chemistry of water oxidation. We also review some new directions in research that photoactivation studies have inspired that look at the evolutionary history of this remarkable catalyst.
Alexander Wheeler T, Don Tilley T J Am Chem Soc. 2024; 146(29):20279-20290.
PMID: 38978206 PMC: 11273651. DOI: 10.1021/jacs.4c05367.
Photosynthetic Efficiency of L. in Response to Copper, Iron, and Zinc.
Sorce C, Bellini E, Bacchi F, Sanita di Toppi L Plants (Basel). 2023; 12(15).
PMID: 37570930 PMC: 10420882. DOI: 10.3390/plants12152776.
Smythers A, Crislip J, Slone D, Flinn B, Chaffins J, Camp K Sci Rep. 2023; 13(1):11301.
PMID: 37438371 PMC: 10338473. DOI: 10.1038/s41598-023-35895-x.
Drosou M, Comas-Vila G, Neese F, Salvador P, Pantazis D J Am Chem Soc. 2023; 145(19):10604-10621.
PMID: 37137865 PMC: 10197136. DOI: 10.1021/jacs.3c00489.
Mimicking the Oxygen-Evolving Center in Photosynthesis.
Chen Y, Xu B, Yao R, Chen C, Zhang C Front Plant Sci. 2022; 13:929532.
PMID: 35874004 PMC: 9302449. DOI: 10.3389/fpls.2022.929532.