A thiocarbonate sink on the enzymatic energy landscape of aerobic CO oxidation? Answers from DFT and QM/MM models of Mo–Cu CO-dehydrogenases
(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.
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/36ea466e-f6f9-40ed-934d-2d846d5583dc
- author
- Rovaletti, Anna ; Bruschi, Maurizio ; Moro, Giorgio ; Cosentino, Ugo ; Ryde, Ulf LU and Greco, Claudio LU
- organization
- publishing date
- 2019
- 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
- 2023-04-09 07:40:14
@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}}, }