Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å.
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The crystal structure of photosystem II is reported, finding that five oxygen atoms served as oxo bridges linking the five metal atoms, and that four water molecules were bound to the Mn4CaO5 cluster; some of them may therefore serve as substrates for dioxygen formation.Abstract:
Photosystem II is the site of photosynthetic water oxidation and contains 20 subunits with a total molecular mass of 350 kDa. The structure of photosystem II has been reported at resolutions from 3.8 to 2.9 angstrom. These resolutions have provided much information on the arrangement of protein subunits and cofactors but are insufficient to reveal the detailed structure of the catalytic centre of water splitting. Here we report the crystal structure of photosystem II at a resolution of 1.9 angstrom. From our electron density map, we located all of the metal atoms of the Mn(4)CaO(5) cluster, together with all of their ligands. We found that five oxygen atoms served as oxo bridges linking the five metal atoms, and that four water molecules were bound to the Mn(4)CaO(5) cluster; some of them may therefore serve as substrates for dioxygen formation. We identified more than 1,300 water molecules in each photosystem II monomer. Some of them formed extensive hydrogen-bonding networks that may serve as channels for protons, water or oxygen molecules. The determination of the high-resolution structure of photosystem II will allow us to analyse and understand its functions in great detail.read more
Citations
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Ca K‑Edge XAS as a Probe of Calcium Centers in Complex Systems
Vlad Martin-Diaconescu,Marcello Gennari,Bertrand Gerey,Emily Y. Tsui,Jacob S. Kanady,Rosalie Tran,Jacques Pécaut,Dimitrios Maganas,Vera Krewald,Eric Gouré,Carole Duboc,Junko Yano,Theodor Agapie,Marie-Noëlle Collomb,Serena DeBeer,Serena DeBeer +15 more
TL;DR: Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers and is found to be a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation.
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Designing Self‐Supported Metal Organic Framework Derived Catalysts for Electrochemical Water Splitting
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TL;DR: The basic principles of catalyst design from self-supported MOF, structural and interface engineering by controlling the electronic structure of the catalysts to improve the water splitting activity are described.
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Modification of the pheophytin redox potential in Thermosynechococcus elongatus Photosystem II with PsbA3 as D1
Miwa Sugiura,Chizuko Azami,Kazumi Koyama,A. William Rutherford,Fabrice Rappaport,Alain Boussac +5 more
TL;DR: In Photosystem II (PSII) of the cyanobacterium Thermosynechococcus elongatus, glutamate 130 in the high-light variant of the D1-subunit (PsbA3) was changed to glutamine in a strain lacking the two other genes for D1, psbA1 and psb a2, reflecting differential sensitivities to high light.
Journal ArticleDOI
D1-Asn-298 in photosystem II is involved in a hydrogen-bond network near the redox-active tyrosine YZ for proton exit during water oxidation
TL;DR: Results suggest that the D1-N298A substitution inhibits the proton transfer processes in the S2 → S3 and S3 → S0 transitions, which indicates that the hydrogen-bond network near YZ can be functional as a protonTransfer pathway during photosynthetic water oxidation.
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