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Temperature-driven changeover in the electron-transfer mechanism of a thermophilic plastocyanin

 

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Opened Access Temperature-driven changeover in the electron-transfer mechanism of a thermophilic plastocyanin
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Author: Olloqui Sariego, José Luis
Moreno Beltrán, José Blas
Díaz Quintana, Antonio Jesús
Rosa Acosta, Miguel Ángel de la
Calvente Pacheco, Juan José
Andreu Fondacabe, Rafael Jesús
Department: Universidad de Sevilla. Departamento de Bioquímica Vegetal y Biología Molecular
Universidad de Sevilla. Departamento de Química Física
Date: 2014
Published in: Journal of Physical Chemistry Letters, 5 (5), 910-914.
Document type: Article
Abstract: Electron-transfer kinetics of the thermophilic protein Plastocyanin fromPhormidium laminosumadsorbed on 1,ω-alkanedithiol self-assembled monolayers (SAMs)deposited on gold have been investigated. The standard electron-transfer rate constant hasbeen determined as a function of electrode−protein distance and solution viscosity over abroad temperature range (0−90°C). For either thin or thick SAMs, the electron-transferregime remains invariant with temperature, whereas for the 1,11-undecanethiol SAM ofintermediate chain length, a kinetic regime changeover from a gated or friction-controlledmechanism at low temperature (0−30°C) to a nonadiabatic mechanism above 40°Cisobserved. To the best of our knowledge, this is thefirst time a thermal-induced transitionbetween these two kinetic regimes is reported for a metalloprotein.
Cite: Olloqui Sariego, J.L., Moreno Beltrán, J.B., Díaz Quintana, A.J., Rosa Acosta, M.Á.d.l., Calvente Pacheco, J.J. y Andreu Fondacabe, R.J. (2014). Temperature-driven changeover in the electron-transfer mechanism of a thermophilic plastocyanin. Journal of Physical Chemistry Letters, 5 (5), 910-914.
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URI: https://hdl.handle.net/11441/84985

DOI: 10.1021/jz500150y

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