ArticleInorganic chemistry2008
Where water is oxidized to dioxygen: structure of the photosynthetic Mn4Ca cluster from X-ray spectroscopy.
Article in Inorganic chemistry, 2008. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 29 papers.
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29 citing papers in PubMed, 142 citations in OpenAlex.
- Structure Function Studies of Photosystem II Using X-Ray Free Electron Lasers.Annual review of biophysics · 2024Review
- Ionizing Radiation: Effective Physical Agents for Economic Crop Seed Priming and the Underlying Physiological Mechanisms.International journal of molecular sciences · 2022Review
- Optimizing Crystal Size of Photosystem II by Macroseeding: Toward Neutron Protein Crystallography.Crystal growth & design · 2018Article
- Theoretical study of the EPR spectrum of the SPhotosynthesis research · 2016Article
- Detecting the oxyl radical of photocatalytic water oxidation at an n-SrTiO3/aqueous interface through its subsurface vibration.Nature chemistry · 2016Article
- Light-dependent production of dioxygen in photosynthesis.Metal ions in life sciences · 2015Review
- Serial time-resolved crystallography of photosystem II using a femtosecond X-ray laser.Nature · 2014Article
- Taking snapshots of photosynthetic water oxidation using femtosecond X-ray diffraction and spectroscopy.Nature communications · 2014Article
- Mn4Ca cluster in photosynthesis: where and how water is oxidized to dioxygen.Chemical reviews · 2014Review
- Towards accurate structural characterization of metal centres in protein crystals: the structures of Ni and Cu T(6) bovine insulin derivatives.Acta crystallographica. Section D, Biological crystallography · 2014Article
- L-Edge X-ray Absorption Spectroscopy of Dilute Systems Relevant to Metalloproteins Using an X-ray Free-Electron Laser.The journal of physical chemistry letters · 2013Article
- Kinetic modeling of the X-ray-induced damage to a metalloprotein.The journal of physical chemistry. B · 2013Article
- Structural changes of the oxygen-evolving complex in photosystem II during the catalytic cycle.The Journal of biological chemistry · 2013Article
- Entangled quantum electronic wavefunctions of the Mn₄CaO₅ cluster in photosystem II.Nature chemistry · 2013Article
- Simultaneous femtosecond X-ray spectroscopy and diffraction of photosystem II at room temperature.Science (New York, N.Y.) · 2013Article
- From natural to artificial photosynthesis.Journal of the Royal Society, Interface · 2013Article
- Fast Detection Allows Analysis of the Electronic Structure of Metalloprotein by X-ray Emission Spectroscopy at Room Temperature.The journal of physical chemistry letters · 2012Article
- Room temperature femtosecond X-ray diffraction of photosystem II microcrystals.Proceedings of the National Academy of Sciences of the United States of America · 2012Article
- Synthetic model of the asymmetric [Mn3CaO4] cubane core of the oxygen-evolving complex of photosystem II.Proceedings of the National Academy of Sciences of the United States of America · 2012Article
- Amorphous manganese-calcium oxides as a possible evolutionary origin for the CaMn₄ cluster in photosystem II.Origins of life and evolution of the biosphere : the journal of the International Society for the Study of the Origin of Life · 2011Article
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2 authors at 1 institution in 1 country.
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Abstract
Light-driven oxidation of water to dioxygen in plants, algae, and cyanobacteria is catalyzed within photosystem II (PS II) by a Mn 4Ca cluster. Although the cluster has been studied by many different methods, its structure and mechanism have remained elusive. X-ray absorption and emission spectroscopy and extended X-ray absorption fine structure studies have been particularly useful in probing the electronic and geometric structures and the mechanism of the water oxidation reaction. Recent progress, reviewed here, includes polarized X-ray absorption spectroscopy measurements of PS II single crystals. Analysis of those results has constrained the Mn 4Ca cluster geometry to a set of three similar high-resolution structures. The structure of the cluster from the present study is unlike either the 3.0- or 3.5-A-resolution X-ray structures or other previously proposed models. The differences between the models derived from X-ray spectroscopy and crystallography are predominantly because of damage to the Mn 4Ca cluster by X-rays under conditions used for the structure determination by X-ray crystallography. X-ray spectroscopy studies are also used for studying the changes in the structure of the Mn 4Ca catalytic center as it cycles through the five intermediate states known as the S i states ( i = 0-4). The electronic structure of the Mn 4Ca cluster has been studied more recently using resonant inelastic X-ray scattering spectroscopy (RIXS), in addition to the earlier X-ray absorption and emission spectroscopy methods. These studies are revealing that the assignment of formal oxidation states is overly simplistic. A more accurate description should consider the charge density on the Mn atoms, which includes the covalency of the bonds and delocalization of the charge over the cluster. The geometric and electronic structures of the Mn 4Ca cluster in the S states derived from X-ray spectroscopy are leading to a detailed understanding of the mechanism of O-O bond formation during the photosynthetic water-splitting process.
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