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dc.contributor.author
Álvarez Paggi, Damián Jorge
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Castro, Maria Ana
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Tortora, Verónica
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Castro, Laura
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Radi, Rafael
dc.contributor.author
Murgida, Daniel Horacio
dc.date.available
2015-06-16T18:59:04Z
dc.date.issued
2013-03
dc.identifier.citation
Álvarez Paggi, Damián Jorge; Castro, Maria Ana; Tortora, Verónica; Castro, Laura; Radi, Rafael; et al.; Electrostatically Driven Second-Sphere Ligand Switch between High and Low Reorganization Energy Forms of Native Cytochrome c; Amer Chemical Soc; Journal of the American Chemical Society; 135; 3-2013; 4389-4397
dc.identifier.issn
0002-7863
dc.identifier.uri
http://hdl.handle.net/11336/757
dc.description.abstract
We have employed a combination of protein film voltammetry, time-resolved vibrational spectroelectrochemistry and molecular dynamics simulations to evaluate the electron-transfer reorganization free energy (λ) of cytochrome c (Cyt) in electrostatic complexes that mimic some basic features of protein–protein and protein–lipid interactions. The results reveal the existence of two native-like conformations of Cyt that present significantly different λ values. Conversion from the high to the low λ forms is triggered by electrostatic interactions, and involves the rupture of a weak H-bond between first- (M80) and second-sphere (Y67) ligands of the heme iron, as a distinctive feature of the conformational switch. The two flexible Ω loops operate as transducers of the electrostatic signal. This fine-tuning effect is abolished in the Y67F Cyt mutant, which presents a λ value similar to the WT protein in electrostatic complexes. We propose that interactions of Cyt with the natural redox partner proteins activate a similar mechanism to minimize the reorganization energy of interprotein electron transfer.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Amer Chemical Soc
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Cytochrome C
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Electron Transfer
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Reorganization Energy
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Electrostatic Switch
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Ciencias Naturales y Exactas
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Ciencias Químicas
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Físico-química, Ciencia de Los Polímeros, Electroquímica
dc.title
Electrostatically Driven Second-Sphere Ligand Switch between High and Low Reorganization Energy Forms of Native Cytochrome c
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2016-03-30 10:35:44.97925-03
dc.journal.volume
135
dc.journal.pagination
4389-4397
dc.journal.pais
Estados Unidos
dc.journal.ciudad
Washington
dc.description.fil
Fil: Álvarez Paggi, Damián Jorge. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Industrias; Argentina;
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Fil: Castro, Maria Ana. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Industrias; Argentina;
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Fil: Tortora, Verónica. Universidad de la República. Departamento de Bioquímica and Center for Free Radical and Biomedical Research; Uruguay;
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Fil: Castro, Laura. Universidad de la República. Departamento de Bioquímica and Center for Free Radical and Biomedical Research; Uruguay;
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Fil: Radi, Rafael. Universidad de la República. Departamento de Bioquímica and Center for Free Radical and Biomedical Research; Uruguay;
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Fil: Murgida, Daniel Horacio. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Industrias; Argentina;
dc.journal.title
Journal of the American Chemical Society
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/dx.doi.org/10.1021/ja311786b
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ja311786b
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