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Can Water Act as a Nucleophile in CO Oxidation Catalysed by Mo/Cu CO-Dehydrogenase? Answers from Theory

Rovaletti, Anna ; Moro, Giorgio ; Cosentino, Ugo ; Ryde, Ulf LU orcid and Greco, Claudio LU (2022) In ChemPhysChem 23(8).
Abstract

The aerobic CO dehydrogenase from Oligotropha carboxidovorans is an environmentally crucial bacterial enzyme for maintenance of subtoxic concentration of CO in the lower atmosphere, as it allows for the oxidation of CO to CO2 which takes place at its Mo−Cu heterobimetallic active site. Despite extensive experimental and theoretical efforts, significant uncertainties still concern the reaction mechanism for the CO oxidation. In this work, we used the hybrid quantum mechanical/molecular mechanical approach to evaluate whether a water molecule present in the active site might act as a nucleophile upon formation of the new C−O bond, a hypothesis recently suggested in the literature. Our study shows that activation of... (More)

The aerobic CO dehydrogenase from Oligotropha carboxidovorans is an environmentally crucial bacterial enzyme for maintenance of subtoxic concentration of CO in the lower atmosphere, as it allows for the oxidation of CO to CO2 which takes place at its Mo−Cu heterobimetallic active site. Despite extensive experimental and theoretical efforts, significant uncertainties still concern the reaction mechanism for the CO oxidation. In this work, we used the hybrid quantum mechanical/molecular mechanical approach to evaluate whether a water molecule present in the active site might act as a nucleophile upon formation of the new C−O bond, a hypothesis recently suggested in the literature. Our study shows that activation of H2O can be favoured by the presence of the Mo=Oeq group. However, overall our results suggest that mechanisms other than the nucleophilic attack by Mo=Oeq to the activated carbon of the CO substrate are not likely to constitute reactive channels for the oxidation of CO by the enzyme.

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author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
biocatalysis, CO oxidation, Mo/Cu CO dehydrogenase, nucleophilic addition, QM/MM
in
ChemPhysChem
volume
23
issue
8
publisher
John Wiley & Sons Inc.
external identifiers
  • pmid:35170169
  • scopus:85126029646
ISSN
1439-4235
DOI
10.1002/cphc.202200053
language
English
LU publication?
yes
id
983eebe5-feb1-4c5a-a1bb-b7ba7c20aa90
date added to LUP
2022-06-17 13:41:24
date last changed
2024-04-18 12:26:28
@article{983eebe5-feb1-4c5a-a1bb-b7ba7c20aa90,
  abstract     = {{<p>The aerobic CO dehydrogenase from Oligotropha carboxidovorans is an environmentally crucial bacterial enzyme for maintenance of subtoxic concentration of CO in the lower atmosphere, as it allows for the oxidation of CO to CO<sub>2</sub> which takes place at its Mo−Cu heterobimetallic active site. Despite extensive experimental and theoretical efforts, significant uncertainties still concern the reaction mechanism for the CO oxidation. In this work, we used the hybrid quantum mechanical/molecular mechanical approach to evaluate whether a water molecule present in the active site might act as a nucleophile upon formation of the new C−O bond, a hypothesis recently suggested in the literature. Our study shows that activation of H<sub>2</sub>O can be favoured by the presence of the Mo=O<sub>eq</sub> group. However, overall our results suggest that mechanisms other than the nucleophilic attack by Mo=O<sub>eq</sub> to the activated carbon of the CO substrate are not likely to constitute reactive channels for the oxidation of CO by the enzyme.</p>}},
  author       = {{Rovaletti, Anna and Moro, Giorgio and Cosentino, Ugo and Ryde, Ulf and Greco, Claudio}},
  issn         = {{1439-4235}},
  keywords     = {{biocatalysis; CO oxidation; Mo/Cu CO dehydrogenase; nucleophilic addition; QM/MM}},
  language     = {{eng}},
  month        = {{02}},
  number       = {{8}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{ChemPhysChem}},
  title        = {{Can Water Act as a Nucleophile in CO Oxidation Catalysed by Mo/Cu CO-Dehydrogenase? Answers from Theory}},
  url          = {{http://dx.doi.org/10.1002/cphc.202200053}},
  doi          = {{10.1002/cphc.202200053}},
  volume       = {{23}},
  year         = {{2022}},
}