We present a theoretical investigation providing key insights on a long-standing controversial issue that dominated the debate on carbon monoxide oxidation by Mo–Cu CO-dehydrogenases. Previous investigations gravitate around the possible occurrence of a thiocarbonate intermediate, that was repeatedly reported to behave as a thermodynamic sink on the catalytic energy landscape. By using a hierarchy of quantum mechanical and hybrid quantum/classical models of the enzyme, we show that no such energy sink is present on the catalytic energy profile. Consequent perspectives for the definition of a novel mechanistic proposal for the enzyme-catalyzed CO-oxidation are discussed in light of the recent literature.

Rovaletti, A., Bruschi, M., Moro, G., Cosentino, U., Ryde, U., & Greco, C. (2019). A thiocarbonate sink on the enzymatic energy landscape of aerobic CO oxidation? Answers from DFT and QM/MM models of Mo–Cu CO-dehydrogenases. JOURNAL OF CATALYSIS, 372, 201-205 [10.1016/j.jcat.2019.02.032].

A thiocarbonate sink on the enzymatic energy landscape of aerobic CO oxidation? Answers from DFT and QM/MM models of Mo–Cu CO-dehydrogenases

Rovaletti, A;Bruschi, M;Moro, G;Cosentino, U;Greco, C
2019

Abstract

We present a theoretical investigation providing key insights on a long-standing controversial issue that dominated the debate on carbon monoxide oxidation by Mo–Cu CO-dehydrogenases. Previous investigations gravitate around the possible occurrence of a thiocarbonate intermediate, that was repeatedly reported to behave as a thermodynamic sink on the catalytic energy landscape. By using a hierarchy of quantum mechanical and hybrid quantum/classical models of the enzyme, we show that no such energy sink is present on the catalytic energy profile. Consequent perspectives for the definition of a novel mechanistic proposal for the enzyme-catalyzed CO-oxidation are discussed in light of the recent literature.
Articolo in rivista - Articolo scientifico
Scientifica
Carbon monoxide; CO-dehydrogenase; Copper; DFT; Molybdenum; Thiocarbonate intermediate;
carbon monoxide, CO-dehydrogenase, molybdenum, copper
English
Rovaletti, A., Bruschi, M., Moro, G., Cosentino, U., Ryde, U., & Greco, C. (2019). A thiocarbonate sink on the enzymatic energy landscape of aerobic CO oxidation? Answers from DFT and QM/MM models of Mo–Cu CO-dehydrogenases. JOURNAL OF CATALYSIS, 372, 201-205 [10.1016/j.jcat.2019.02.032].
Rovaletti, A; Bruschi, M; Moro, G; Cosentino, U; Ryde, U; Greco, C
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/10281/223445
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