Artículo
Alternative ground states enable pathway switching in biological electron transfer
Abriata, Luciano Andres
; Álvarez Paggi, Damián Jorge
; Ledesma, Gabriela Nanci
; Blackburn, Ninian J.; Vila, Alejandro Jose
; Murgida, Daniel Horacio
Fecha de publicación:
10/2012
Editorial:
National Academy of Sciences
Revista:
Proceedings of the National Academy of Sciences of The United States of America
ISSN:
0027-8424
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Electron transfer is the simplest chemical reaction and constitutes the basis of a large variety of biological processes, such as photosynthesis and cellular respiration. Nature has evolved specific proteins and cofactors for these functions. The mechanisms optimizing biological electron transfer have been matter of intense debate, such as the role of the protein milieu between donor and acceptor sites. Here we propose a mechanism regulating long-range electron transfer in proteins. Specifically, we report a spectroscopic, electrochemical, and theoretical study on WT and single-mutant CuA redox centers from Thermus thermophilus, which shows that thermal fluctuations may populate two alternative ground-state electronic wave functions optimized for electron entry and exit, respectively, through two different and nearly perpendicular pathways. These findings suggest a unique role for alternative or "invisible" electronic ground states in directional electron transfer. Moreover, it is shown that this energy gap and, therefore, the equilibrium between ground states can be fine-tuned by minor perturbations, suggesting alternative ways through which protein-protein interactions and membrane potential may optimize and regulate electron-proton energy transduction.
Palabras clave:
Cytochrome Oxidase
,
Invisible States
,
Nmr
,
Paramagnetic Proteins
,
Spectroscopy
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Articulos(IBR)
Articulos de INST.DE BIOLOGIA MOLECULAR Y CELULAR DE ROSARIO
Articulos de INST.DE BIOLOGIA MOLECULAR Y CELULAR DE ROSARIO
Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos(IQUIR)
Articulos de INST.DE QUIMICA ROSARIO
Articulos de INST.DE QUIMICA ROSARIO
Citación
Abriata, Luciano Andres; Álvarez Paggi, Damián Jorge; Ledesma, Gabriela Nanci; Blackburn, Ninian J.; Vila, Alejandro Jose; et al.; Alternative ground states enable pathway switching in biological electron transfer; National Academy of Sciences; Proceedings of the National Academy of Sciences of The United States of America; 109; 43; 10-2012; 17348-17353
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