Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO

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Título: Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO
Autor/es: Climent, Victor | Fu, Yongchun | Chumillas, Sara | Maestro, Beatriz | Li, Jian-Feng | Kuzume, Akiyoshi | Keller, Stephan | Wandlowski, Thomas
Grupo/s de investigación o GITE: Electroquímica de Superficies
Centro, Departamento o Servicio: Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica
Palabras clave: Laccase | Cysteamine | Aminothiophenol | Protein film voltammetry | Oxygen reduction | Gold electrode
Área/s de conocimiento: Química Física
Fecha de publicación: 1-jul-2014
Editor: American Chemical Society
Cita bibliográfica: The Journal of Physical Chemistry C. 2014, 118(29): 15754-15765. doi:10.1021/jp5034382
Resumen: The bioelectrocatalytic (oxygen reduction reaction, ORR) properties of the multicopper oxidase CueO immobilized on gold electrodes were investigated. Macroscopic electrochemical techniques were combined with in situ scanning tunneling microscopy (STM) and surface-enhanced Raman spectroscopy at the ensemble and at the single-molecule level. Self-assembled monolayer of mercaptopropionic acid, cysteamine, and p-aminothiophenol were chosen as redox mediators. The highest ORR activity was observed for the protein attached to amino-terminated adlayers. In situ STM experiments revealed that the presence of oxygen causes distinct structure and electronic changes in the metallic centers of the enzyme, which determine the rate of intramolecular electron transfer and, consequently, affect the rate of electron tunneling through the protein. Complementary Raman spectroscopy experiments provided access for monitoring structural changes in the redox state of the type 1 copper center of the immobilized enzyme during the CueO-catalyzed oxygen reduction cycle. These results unequivocally demonstrate the existence of a direct electronic communication between the electrode substrate and the type 1 copper center.
Patrocinador/es: Financial support from the Spanish Ministerio de Ciencia e Innovacion (CTQ2010−18570) and Generalitat Valenciana (ACOMP/2013/073) is gratefully acknowledged. The work in Bern was supported by the European Union through the FP7 BacWire Project (Contract MNP4-SL-2009-229337), the CTIProject 13696.1 PFFLR-IV, and the University of Bern through a summer fellowship to V.C.
ISSN: 1932-7447 (Print) | 1932-7455 (Online)
DOI: 10.1021/jp5034382
Idioma: eng
Tipo: info:eu-repo/semantics/article
Derechos: © 2014 American Chemical Society
Revisión científica: si
Versión del editor:
Aparece en las colecciones:INV - EQSUP - Artículos de Revistas

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