WFRF:(Lubitz S.)
Sökning: WFRF:(Lubitz S.) > (2010-2014) > Electronic Structur...
Electronic Structural Flexibility of Heterobimetallic Mn/Fe Cofactors : R2lox and R2c Proteins
-
- Shafaat, Hannah S. (författare)
- Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34-36, Mülheim an der Ruhr D-45470, Germany
-
- Griese, Julia J. (författare)
- Stockholms universitet,Institutionen för biokemi och biofysik,Department of Biochemistry and Biophysics, Stockholm University, Stockholm SE-106 91, Sweden
-
- Pantazis, Dimitrios A. (författare)
- Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34-36, Mülheim an der Ruhr D-45470, Germany
- visa fler...
- visa färre...
- (creator_code:org_t)
- 2014-09-15
- 2014
- Engelska.
- Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 136:38, s. 13399-13409
- Tidskriftsartikel (refereegranskat)
Abstract
Ämnesord
Stäng
- The electronic structure of the Mn/Fe cofactor identified in a new class of oxidases (R2lox) described by Andersson and Hogbom [Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 5633] is reported. The R2lox protein is homologous to the small subunit of class Ic ribonucleotide reductase (R2c) but has a completely different in vivo function. Using multifrequency EPR and related pulse techniques, it is shown that the cofactor of R2lox represents an antiferromagnetically coupled Mn-III/Fe-III dimer linked by a mu-hydroxo/bis-mu-carboxylato bridging network. The Mn-III ion is coordinated by a single water ligand. The R2lox cofactor is photoactive, converting into a second form (R2lox(photo)) upon visible illumination at cryogenic temperatures (77 K) that completely decays upon warming. This second, unstable form of the cofactor more closely resembles the Mn-III/Fe-III cofactor seen in R2c. It is shown that the two forms of the R2lox cofactor differ primarily in terms of the local site geometry and electronic state of the Mn-III ion, as best evidenced by a reorientation of its unique Mn-55 hyperfine axis. Analysis of the metal hyperfine tensors in combination with density functional theory (DFT) calculations suggests that this change is triggered by deprotonation of the mu-hydroxo bridge. These results have important consequences for the mixed-metal R2c cofactor and the divergent chemistry R2lox and R2c perform.
Ämnesord
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
Hitta via bibliotek
- Journal of the American Chemical Society (Sök värdpublikationen i LIBRIS)
Till lärosätets databas
Hitta mer i SwePub
- Av författaren/redakt...
- Shafaat, Hannah ...
- Griese, Julia J.
- Pantazis, Dimitr ...
- Roos, Katarina
- Andersson, Charl ...
- Popovic-Bijelic, ...
- visa fler...
- Gräslund, Astrid
- Siegbahn, Per E. ...
- Neese, Frank
- Lubitz, Wolfgang
- Högbom, Martin
- Cox, Nicholas
- visa färre...
- Om ämnet
-
- NATURVETENSKAP
- NATURVETENSKAP
- och Kemi
- Artiklar i publikationen
- Journal of the A ...
- Av lärosätet
- Stockholms universitet
- Uppsala universitet
Sök utanför SwePub
- Sök vidare i:
- Google Book Search
- Google Scholar
Kungliga biblioteket hanterar dina personuppgifter i enlighet med EU:s dataskyddsförordning (2018), GDPR. Läs mer om hur det funkar här.
Så här hanterar KB dina uppgifter vid användning av denna tjänst.
- Copyright © LIBRIS - Nationella bibliotekssystem
- LIBRIS.kb.se
