Long-Distance Charge Transport between Cytochrome c and Complex III is Mediated by Protons and Reactive Oxygen Species

Electron transfer (ET) between redox proteins is an essential process in the respiratory and photosynthetic transport chains. While intra-protein ET is well characterized, the experimental methods to investigate inter-protein ET are limited by the presence of the solvent and by the transient nature...

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Detalles Bibliográficos
Autores: Lagunas, Anna, Gomila, Alexandre M J, Nin-Hill, Alba, Guerra-Castellano, Alejandra, Pérez-Mejías, Gonzalo, Samitier, Josep, Rovira, Carme, Rosa, Miguel A. de la, Díaz-Moreno, Irene, Gorostiza, Pau
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/415962
Acceso en línea:http://hdl.handle.net/10261/415962
https://api.elsevier.com/content/abstract/scopus_id/105015835217
Access Level:acceso abierto
Palabra clave:Gouy‐Chapman conduit
Grotthuss (Grothuss) proton hopping conduction
Electrochemical STM
Kinetic isotope effect KIE
Mitochondria
Proton coupled electron transfer PCET
Reactive oxygen species ROS
Superoxide radical anion SOX
Descripción
Sumario:Electron transfer (ET) between redox proteins is an essential process in the respiratory and photosynthetic transport chains. While intra-protein ET is well characterized, the experimental methods to investigate inter-protein ET are limited by the presence of the solvent and by the transient nature of the protein-protein interaction and ET event, which are averaged in protein ensembles. Wiring precisely oriented redox protein partners to the nanoscale electrodes of an electrochemical scanning tunneling microscope allows recording the time- and distance-dependence of the current flowing between them. These methods have revealed that the current flowing between individual protein pairs extends beyond tunneling distances and that it is electrochemically gated. However, the corresponding mechanism and the identity of the charge carriers in aqueous solution remain to be elucidated. To determine the species involved in long-distance charge transport between the redox partner proteins Cc and Cc1 of the respiratory chain, recordings are performed as a function of pH, in heavy water solutions, and in degassed solutions. It is observed that the spatial span and electrochemical gating of long-distance currents are reduced at high pH, in heavy water, and at low oxygen concentration, showing that the currents are assisted by superoxide anions and by protons.