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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 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
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
2019-04-23 04:47:25
@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},
  keyword      = {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          = {http://dx.doi.org/10.1016/j.jcat.2019.02.032},
  year         = {2019},
}