Secondary Structure in Enzyme-Inspired Polymer Catalysts Impacts Water Oxidation Efficiency

Author(s)

Sedenho, Graziela C. ; Nascimento, Steffane Q. ; Zamani, Marjon ; Crespilho, Frank N. ; Furst, Ariel L.

• Document type: Journal article
• Source: ADVANCED SCIENCE; v. 11, n. 25, p. 6-pg., 2024-04-17.

Abstract

Protein structure plays an essential role on their stability, functionality, and catalytic activity. In this work, the interplay between the beta-sheet structure and its catalytic implications to the design of enzyme-inspired materials is investigated. Here, inspiration is drawn from the active sites and beta-sheet rich structure of the highly efficient multicopper oxidase (MCO) to engineer a bio-inspired electrocatalyst for water oxidation utilizing the abundant metal, copper. Copper ions are coordinated to poly-histidine (polyCuHis), as they are in MCO active sites. The resultant polyCuHis material effectively promotes water oxidation with low overpotentials (0.15 V) in alkaline systems. This activity is due to the 3D structure of the poly-histidine backbone. By increasing the prevalence of beta-sheet structure and decreasing the random coil nature of the polyCuHis secondary structures, this study is able to modulates the electrocatalytic activity of this material is modulated, shifting it toward water oxidation. These results highlight the crucial role of the local environment at catalytic sites for efficient, energy-relevant transformations. Moreover, this work highlights the importance of conformational structure in the design of scaffolds for high-performance electrocatalysts. Conformational changes mimicking protein secondary structural changes impact the catalytic activity of the water oxidation reaction using a bio-inspired poly-histidine/Cu(II) catalyst. image (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: 20/04796-8 - In situ and operando studies of metaloenzymes for energy conversion and fuel bioelectrosynthesis
• Grantee: Graziela Cristina Sedenho
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 21/10307-2 - Engineering enzyme-displayed microbial cell surfaces and electrode surfaces for energy conversion and bioelectrosynthesis
• Grantee: Graziela Cristina Sedenho
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor