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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Assessing electron transfer reactions and catalysis in multicopper oxidases with operando X-ray absorption spectroscopy

Full text
Author(s):
Macedo, Lucyano J. A. [1] ; Hassan, Ayaz [1] ; Sedenho, Graziela C. [1] ; Crespilho, Frank N. [1]
Total Authors: 4
Affiliation:
[1] Univ Sao Paulo, Sao Carlos Inst Chem, BR-13560970 Sao Paulo - Brazil
Total Affiliations: 1
Document type: Journal article
Source: NATURE COMMUNICATIONS; v. 11, n. 1 JAN 16 2020.
Web of Science Citations: 0
Abstract

Here we propose an experimental setup based on operando X-ray absorption spectroscopy (XAS) to understand why copper-containing oxidoreductase enzymes show exceptional performance as catalysts for the oxygen reduction reaction (ORR). An electrode based on carbon nanoparticles organized in mesoporous structures with bilirubin oxidase (BOD) was developed to be used in a home-made operando XAS electrochemical cell, and we probed the electron transfer under ORR regime. In the presence of molecular oxygen, the BOD cofactor containing 4 copper ions require an overpotential about 150 mV to be reduced as compared to that in the absence of oxygen. A second electron transfer step, which occurs faster than the cofactor reduction, suggests that the cooper ions act as a tridimensional redox active electronic bridges for the electron transfer reaction. (AU)

FAPESP's process: 17/20493-2 - Study of metalloenzymes through electrochemistry coupled to vibrational spectroscopy
Grantee:Lucyano Jefferson Alves de Macêdo
Support Opportunities: Scholarships in Brazil - Doctorate
FAPESP's process: 19/15333-1 - Bio-photo-electrochemical hybrid cells for solar energy conversion
Grantee:Frank Nelson Crespilho
Support Opportunities: Regular Research Grants
FAPESP's process: 16/25806-6 - Interaction between biomolecules and nanostructures: electrochemistry, interfaces and surfaces
Grantee:Ayaz Hassan
Support Opportunities: Scholarships in Brazil - Post-Doctoral
FAPESP's process: 19/12053-8 - High performance electrodes applied in organic batteries and in biofuel cell
Grantee:Frank Nelson Crespilho
Support Opportunities: Regular Research Grants
FAPESP's process: 15/22973-6 - Development of Microbial Fuel Biocells for Bioproduction and Oxidation of Ethanol
Grantee:Graziela Cristina Sedenho
Support Opportunities: Scholarships in Brazil - Doctorate