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Characterization of...
Characterization of Oxygen Bridged Manganese Model Complexes Using Multifrequency (17)O-Hyperfine EPR Spectroscopies and Density Functional Theory
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Rapatskiy, Leonid (författare)
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Ames, William M. (författare)
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Pérez-Navarro, Montserrat (författare)
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Savitsky, Anton (författare)
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- Griese, Julia J. (författare)
- Stockholms universitet,Institutionen för biokemi och biofysik,Stockholms universitet, Institutionen för biokemi och biofysik
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Weyhermüller, Thomas (författare)
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Shafaat, Hannah S. (författare)
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- Högbom, Martin (författare)
- Stockholms universitet,Institutionen för biokemi och biofysik
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Neese, Frank (författare)
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Pantazis, Dimitrios A. (författare)
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Cox, Nicholas (författare)
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(creator_code:org_t)
- 2015-08-26
- 2015
- Engelska.
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 119:43, s. 13904-13921
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https://uu.diva-port... (primary) (Raw object)
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- Multifrequency pulsed EPR data are reported for a series of oxygen bridged (μ-oxo/μ-hydroxo) bimetallic manganese complexes where the oxygen is labeled with the magnetically active isotope (17)O (I = 5/2). Two synthetic complexes and two biological metallocofactors are examined: a planar bis-μ-oxo bridged complex and a bent, bis-μ-oxo-μ-carboxylato bridge complex; the dimanganese catalase, which catalyzes the dismutation of H2O2 to H2O and O2, and the recently identified manganese/iron cofactor of the R2lox protein, a homologue of the small subunit of the ribonuclotide reductase enzyme (class 1c). High field (W-band) hyperfine EPR spectroscopies are demonstrated to be ideal methods to characterize the (17)O magnetic interactions, allowing a magnetic fingerprint for the bridging oxygen ligand to be developed. It is shown that the μ-oxo bridge motif displays a small positive isotropic hyperfine coupling constant of about +5 to +7 MHz and an anisotropic/dipolar coupling of -9 MHz. In addition, protonation of the bridge is correlated with an increase of the hyperfine coupling constant. Broken symmetry density functional theory is evaluated as a predictive tool for estimating hyperfine coupling of bridging species. Experimental and theoretical results provide a framework for the characterization of the oxygen bridge in Mn metallocofactor systems, including the water oxidizing cofactor of photosystem II, allowing the substrate/solvent interface to be examined throughout its catalytic cycle.
Ämnesord
- NATURVETENSKAP -- Biologi -- Biofysik (hsv//swe)
- NATURAL SCIENCES -- Biological Sciences -- Biophysics (hsv//eng)
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Rapatskiy, Leoni ...
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Ames, William M.
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Pérez-Navarro, M ...
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Savitsky, Anton
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Griese, Julia J.
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Weyhermüller, Th ...
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visa fler...
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Shafaat, Hannah ...
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Högbom, Martin
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Neese, Frank
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Pantazis, Dimitr ...
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Cox, Nicholas
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visa färre...
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- NATURVETENSKAP
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NATURVETENSKAP
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och Biologi
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och Biofysik
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Journal of Physi ...
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Stockholms universitet
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