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dc.contributor.author Álvarez Paggi, Damián Jorge
dc.contributor.author Meister, Wiebke
dc.contributor.author Kuhlmann, Uwe
dc.contributor.author Weidinger, Inez
dc.contributor.author Tenger, Katalin
dc.contributor.author Zimányi, Lázló
dc.contributor.author Rákhely, Gabor
dc.contributor.author Hildebrandt , Peter
dc.contributor.author Murgida, Daniel Horacio
dc.date.available 2016-11-07T14:38:10Z
dc.date.issued 2013-04-23
dc.identifier.citation Álvarez Paggi, Damián Jorge; Meister, Wiebke; Kuhlmann, Uwe; Weidinger, Inez; Tenger, Katalin; et al.; Disentangling Electron Tunneling and Protein Dynamics of Cytochrome c Through a Rationally Designed Surface Mutation; American Chemical Society; Journal Of Physical Chemistry B; 117; 20; 23-4-2013; 6061-6068
dc.identifier.issn 1089-5647
dc.identifier.uri http://hdl.handle.net/11336/8020
dc.description.abstract Non-exponential distance-dependence of the apparent electron transfer (ET) rate has been reported for a variety of redox proteins immobilized on biocompatible electrodes, thus posing a physicochemical challenge of possible physiological relevance. We have recently proposed that this behaviour may arise from the structural and dynamical complexity not only of the redox proteins, but also from their interplay with strong electric fields present in the experimental setups and in vivo (J. Am Chem. Soc 2010, 132, 5769-5778). Therefore, protein dynamics are finely controlled by the energetics of both specific contacts and the interaction between the protein?s dipole moment and the interfacial electric fields. In turn, protein dynamics may govern electron transfer kinetics through reorientation from low to high donor-acceptor electronic coupling orientations. Here we present a combined computational and experimental study of WT cytochrome c and the surface mutant K87C adsorbed on electrodes coated with self assembled monolayers (SAMs) of varying thickness (i.e., variable strength of the interfacial electric field). Replacement of the positively charged K87 by a neutral amino acid allowed us to disentangle protein dynamics and electron tunnelling from the reaction kinetics and to rationalize the anomalous distance dependence in terms of (at least) two populations of distinct average electronic couplings. Thus, it was possible to recover the exponential distance dependence expected from ET theory. These results pave the way for gaining further insight into the parameters that control protein electron transfer.
dc.format application/pdf
dc.language.iso eng
dc.publisher American Chemical Society
dc.rights info:eu-repo/semantics/restrictedAccess
dc.rights.uri https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject TRANSFERENCIA ELECTRÓNICA
dc.subject SERR
dc.subject PATHWAYS
dc.subject CITOCROMO
dc.subject.classification Físico-Química, Ciencia de los Polímeros, Electroquímica
dc.subject.classification Ciencias Químicas
dc.subject.classification CIENCIAS NATURALES Y EXACTAS
dc.title Disentangling Electron Tunneling and Protein Dynamics of Cytochrome c Through a Rationally Designed Surface Mutation
dc.type info:eu-repo/semantics/article
dc.type info:ar-repo/semantics/artículo
dc.type info:eu-repo/semantics/publishedVersion
dc.date.updated 2016-10-25T19:28:06Z
dc.journal.volume 117
dc.journal.number 20
dc.journal.pagination 6061-6068
dc.journal.pais Estados Unidos
dc.journal.ciudad Nueva York
dc.description.fil Fil: Álvarez Paggi, Damián Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
dc.description.fil Fil: Meister, Wiebke. Technishe Universitat Berlin; Alemania
dc.description.fil Fil: Kuhlmann, Uwe. Technishe Universitat Berlin; Alemania
dc.description.fil Fil: Weidinger, Inez. Technishe Universitat Berlin; Alemania
dc.description.fil Fil: Tenger, Katalin. Biological Research Center; Hungría
dc.description.fil Fil: Zimányi, Lázló. Biological Research Center; Hungría
dc.description.fil Fil: Rákhely, Gabor. University Of Szeged. Department of Biotechnology; Hungría
dc.description.fil Fil: Hildebrandt , Peter. Technishe Universitat Berlin; Alemania
dc.description.fil Fil: Murgida, Daniel Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
dc.journal.title Journal Of Physical Chemistry B
dc.relation.alternativeid info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/jp400832m
dc.relation.alternativeid info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp400832m


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info:eu-repo/semantics/restrictedAccess Excepto donde se diga explícitamente, este item se publica bajo la siguiente descripción: Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Unported (CC BY-NC-SA 2.5)