Three-dimensional catalysis and the efficient bioelectrocatalysis beyond surface chemistry

Author(s)

Macedo, Lucyano J. A. ^[1] ; Santo, Anderson A. E. ^[2] ; Sedenho, Graziela C. ^[1] ; Hassan, Ayaz ^[1] ; Iost, Rodrigo M. ^[1] ; Feliciano, Gustavo T. ^[2] ; Crespilho, Frank N. ^[1]

Affiliation

^[1] Univ Sao Paulo, Sao Carlos Inst Chem, BR-13560970 Sao Carlos, SP - Brazil

^[2] Sao Paulo State Univ, Inst Chem, BR-14800060 Araraquara, SP - Brazil

• Document type: Journal article
• Source: JOURNAL OF CATALYSIS; v. 401, p. 200-205, SEP 2021.
• Web of Science Citations: 0

Abstract

The exceptional catalysis for the oxygen reduction reaction (ORR) of bilirubin oxidase (BOD) encouraged us to reevaluate the existing catalytic models. Experimental evidence of the electron-transfer reaction's dependence on the three-dimensional structure of BOD is demonstrated by operando X-ray absorption spectroscopy (XAS) combined with Quantum Mechanics/Molecular Mechanics (QM/MM). We suggest that if a catalytic reaction occurs in a three-dimensional environment (3D-catalysis), the energies involved in the transition states during the electron transfer cannot be explained by adsorption kinetics. In contrast, there is the formation of a three-dimensional complex (TDC). Our data suggest influence of the metallic cofactor electronic structure as well as the spatial disposition of its surrounding ligands on the electron transfer that promotes the biocatalysis. We propose that investigating enzymatic redox processes involving a dynamic three-dimensional enzymatic structure can provide further insights as how heterogeneous catalysis can work beyond single atoms and surface chemistry. (c) 2021 Elsevier Inc. All rights reserved. (AU)

• FAPESP's process: 18/22214-6 - Towards a convergence of technologies: from sensing and biosensing to information visualization and machine learning for data analysis in clinical diagnosis
• Grantee: Osvaldo Novais de Oliveira Junior
• Support Opportunities: Research Projects - Thematic Grants
• 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: 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
• 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