Hydrogen bioelectrogeneration with pH-resilient and oxygen-tolerant cobalt apoenzyme-saccharide

Author(s)

Iost, Rodrigo M. ; Venkatkarthick, Radhakrishnan ; Nascimento, Steffane Q. ; Lima, Fabio H. B. ; Crespilho, Frank N.

• Document type: Journal article
• Source: CHEMICAL COMMUNICATIONS; v. 60, n. 18, p. 3-pg., 2024-02-01.

Abstract

Hydrogenases are enzymes that catalyze the reversible conversion of protons to hydrogen gas, using earth-abundant metals such as nickel and/or iron. This characteristic makes them promising for sustainable energy applications, particularly in clean hydrogen production. However, their widespread use faces challenges, including a limited pH range and susceptibility to oxygen. In response to these issues, SacCoMyo is introduced as an artificial enzyme. SacCoMyo is designed by replacing the native metal in the myoglobin (Myo) scaffold with a hydroxocobalamin (Co) porphyrin core and complemented by a protective heteropolysaccharide-linked (Sac) shell. This engineered protein proves to be resilient, maintaining robust functionality even in acidic environments and preventing denaturation in a pH 1 electrolyte. The cobalt porphyrin core of SacCoMyo reduces the activation overpotential for hydrogen generation. A high turnover frequency of about 2400 H2 s-1 is demonstrated in the presence of molecular oxygen, showcasing its potential in biohydrogen production and its ability to overcome the limitations associated with natural hydrogenases. SacCoMyo, an engineered artificial enzyme with a hydroxocobalamin core and protective heteropolysaccharide-linked shell, exhibits resilience in acidic electrolytes containing molecular oxygen, reducing the activation overpotential for hydrogen generation and demonstrating high turnover frequency. (AU)

• FAPESP's process: 22/09164-5 - Understanding the charge transfer mechanisms in biological and biomimetic systems using in-situ and operando techniques: from fundamental science to energy application
• Grantee: Frank Nelson Crespilho
• Support Opportunities: Regular Research Grants
• FAPESP's process: 23/10667-4 - Bioengineering of Bifunctional Metalloproteins Applied in the Production of Added Value Products
• Grantee: Rodrigo Michelin Iost
• Support Opportunities: Scholarships in Brazil - Support Program for Fixating Young Doctors
• FAPESP's process: 21/05665-7 - Development of Van der Waals surfaces for application in biodevices
• Grantee: Rafael Neri Prystaj Colombo
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• 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: 23/01529-7 - Bioengineering of bifunctional metalloproteins applied in the production of added value products
• Grantee: Frank Nelson Crespilho
• Support Opportunities: Regular Research Grants
• FAPESP's process: 20/15098-0 - Bioelectrosynthesis of value-added compounds from atmospheric nitrogen and carbon dioxide
• Grantee: Jessica Crivelaro Pacheco
• Support Opportunities: Scholarships in Brazil - Doctorate