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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, Anna ; Bruschi, Maurizio ; Moro, Giorgio ; Cosentino, Ugo ; Ryde, Ulf LU orcid and Greco, Claudio LU (2019) In Journal of Catalysis p.201-205
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.

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author
; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Carbon monoxide, CO-dehydrogenase, Copper, DFT, Molybdenum, Thiocarbonate intermediate
in
Journal of Catalysis
pages
5 pages
publisher
Elsevier
external identifiers
  • scopus:85062950312
ISSN
0021-9517
DOI
10.1016/j.jcat.2019.02.032
language
English
LU publication?
yes
id
36ea466e-f6f9-40ed-934d-2d846d5583dc
date added to LUP
2019-03-27 13:53:31
date last changed
2025-10-14 12:57:35
@article{36ea466e-f6f9-40ed-934d-2d846d5583dc,
  abstract     = {{<p>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.</p>}},
  author       = {{Rovaletti, Anna and Bruschi, Maurizio and Moro, Giorgio and Cosentino, Ugo and Ryde, Ulf and Greco, Claudio}},
  issn         = {{0021-9517}},
  keywords     = {{Carbon monoxide; CO-dehydrogenase; Copper; DFT; Molybdenum; Thiocarbonate intermediate}},
  language     = {{eng}},
  pages        = {{201--205}},
  publisher    = {{Elsevier}},
  series       = {{Journal of Catalysis}},
  title        = {{A thiocarbonate sink on the enzymatic energy landscape of aerobic CO oxidation? Answers from DFT and QM/MM models of Mo–Cu CO-dehydrogenases}},
  url          = {{https://lup.lub.lu.se/search/files/84187682/250_codh.pdf}},
  doi          = {{10.1016/j.jcat.2019.02.032}},
  year         = {{2019}},
}