INQUIMAE   12526
INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
artículos
Título:
Reversible Switching of Redox-Active Molecular Orbitals and Electron Transfer Pathways in CuA Sites of Cytochrome c Oxidase
Autor/es:
ZITARE U.; ALVAREZ PAGGI, D.; MORGADA M.; ABRIATA, L.A.; VILA, A.J.; MURGIDA, D.H.
Revista:
Angewandte Chemie
Editorial:
WILEY-V C H VERLAG GMBH
Referencias:
Lugar: Weinheim; Año: 2015 vol. 54 p. 9555 - 9555
ISSN:
1433-7851
Resumen:
The CuA site of cytochrome c oxidase is a redox hubthat participates in rapid electron transfer at low driving forceswith two redox cofactors in nearly perpendicular orientations.Spectroscopic and electrochemical characterizations performedon first and second-sphere mutants have allowed usto experimentally detect the reversible switching between twoalternative electronic states that confer different directionalitiesto the redox reaction. Specifically, the M160H variant ofa native CuA shows a reversible pH transition that allows tofunctionally probe both states in the same protein species.Alternation between states exerts a dramatic impact on thekinetic redox parameters, thereby suggesting this effect as themechanism underlying the efficiency and directionality of CuAelectron transfer in vivo. These findings may also prove usefulfor the development of molecular electronics.