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Reversible Structur...
Reversible Structural Isomerization of Nature's Water Oxidation Catalyst Prior to O-O Bond Formation
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- Guo, Y. (författare)
- Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, Hangzhou 310024, China;Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou 310024, China
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- Messinger, Johannes, 1963- (författare)
- Uppsala universitet,Umeå universitet,Kemiska institutionen,Molecular Biomimetics, Department of Chemistry Ångström Laboratory, Uppsala University, Uppsala, Sweden,Molekylär biomimetik,Department of Chemistry, Umeå University, Linnaeus väg 6 (KBC huset), SE-90187 Umeå, Sweden
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- Kloo, Lars (författare)
- KTH,Kemi,Department of Chemistry, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, SE-10044 Stockholm, Sweden
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- Sun, L. (författare)
- Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, Hangzhou 310024, China;Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou 310024, China
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(creator_code:org_t)
- 2022-06-24
- 2022
- Engelska.
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 144:26, s. 11736-11747
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Abstract
Ämnesord
Stäng
- 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 S3states. The isomers are interconvertible in the S1 and S2states, while in the S3state, 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+Yzstate to the S3nYz•→ S4+Yzstep, and report for the first time that the reversible isomerism, which is suppressed in the S3+Yzstate, 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 O2formation, and exert a significant influence on the water oxidation mechanism in photosystem II.
Ämnesord
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
- NATURVETENSKAP -- Biologi -- Biofysik (hsv//swe)
- NATURAL SCIENCES -- Biological Sciences -- Biophysics (hsv//eng)
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Nyckelord
- Chemical bonds
- Density functional theory
- Isomers
- Lime
- Oxidation
- Stereochemistry
- Bond formation
- Cubanes
- Cyanobacterium
- Light driven
- Photosynthetic water oxidation
- Reaction cycles
- S state
- Structural flexibilities
- Structural isomerizations
- Water oxidation catalysts
- Ligands
- manganese
- oxygen
- water
- ligand
- Article
- catalyst
- chemical analysis
- chemical bond
- chemical structure
- correlational study
- isomerism
- isomerization
- tautomer
- catalysis
- chemistry
- oxidation reduction reaction
- photosystem II
- Oxidation-Reduction
- Photosystem II Protein Complex
- Chemistry with specialization in Bioorganic Chemistry
- Chemistry with Specialisation in Theoretical Chemistry
- Chemistry with specialization in Biophysics
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- art (ämneskategori)
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