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

• Published in: Chemical communications (Cambridge, England) Vol. 6; no. 18; pp. 259 - 2511
• Main Authors: Iost, Rodrigo M, Venkatkarthick, Radhakrishnan, Nascimento, Steffane Q, Lima, Fabio H. B, Crespilho, Frank N
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 27.02.2024
• Subjects: Carbohydrates; Clean energy; Cobalt; Denaturation; Hydrogen; Hydrogen production; Hydrogen reduction; Hydrogenase; Myoglobins; Oxygen; Porphyrins
• ISSN: 1359-7345; 1364-548X; 1364-548X
• DOI: 10.1039/d3cc06185j

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 H 2 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.