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

Climent Paya, Victor Jose; Fu, Yongchun; Chumillas, Sara; Maestro, Beatriz; Li, Jianfeng; Kuzume, Akiyoshi; Keller, Stephan; Wandlowski, Thomas (2014). Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO. Journal of physical chemistry. C, 118(29), pp. 15754-15765. American Chemical Society 10.1021/jp5034382

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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.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Climent Paya, Victor Jose, Fu, Yongchun, Li, Jianfeng, Kuzume, Akiyoshi, Keller, Stephan, Wandlowski, Thomas


500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
500 Science




American Chemical Society




Beatrice Niederhauser

Date Deposited:

26 Mar 2015 10:33

Last Modified:

05 Dec 2022 14:44

Publisher DOI:





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