A Computational Comparison of Oxygen Atom Transfer Catalyzed by Dimethyl Sulfoxide Reductase with Mo and W
Li, Jilai ; Andrejic, Milica ; Mata, Ricardo A. and Ryde, Ulf LU
(2015)
In European Journal of Inorganic Chemistry
p.3580-3589
- Abstract
- A thorough computational study has been performed to investigate oxygen atom transfer (OAT) reactions catalyzed by dimethyl sulfoxide reductase (DMSOR) with a catalytic molybdenum or tungsten ion. Thirteen different density functional theory (DFT) methods have been employed to obtain structural parameters along the reaction pathway, and single-point energies were computed with local correlation coupled-cluster methods [LCCSD(T0)]. For both Mo and W, most DFT methods indicate that the enzyme follows a twostep mechanism with a stable intermediate in which a DMSO molecule coordinates to the metal ion in the +IV oxidation state, and this is also confirmed by the LCCSD(T0) energies. The W-substituted models have a 26-30 kJ/mol lower activation... (More)
- A thorough computational study has been performed to investigate oxygen atom transfer (OAT) reactions catalyzed by dimethyl sulfoxide reductase (DMSOR) with a catalytic molybdenum or tungsten ion. Thirteen different density functional theory (DFT) methods have been employed to obtain structural parameters along the reaction pathway, and single-point energies were computed with local correlation coupled-cluster methods [LCCSD(T0)]. For both Mo and W, most DFT methods indicate that the enzyme follows a twostep mechanism with a stable intermediate in which a DMSO molecule coordinates to the metal ion in the +IV oxidation state, and this is also confirmed by the LCCSD(T0) energies. The W-substituted models have a 26-30 kJ/mol lower activation barrier for the OAT reaction, and the reaction is 6370 kJ/mol more exothermic than that with Mo. Different DFT methods give widely different activation and reaction energies, which roughly depend on the amount of exact exchange in the method; these differences are also reflected in the structures, especially for the rate-limiting transition state. Consequently, there is quite a large variation in energies and various energy corrections (thermal, solvation, dispersion, and relativistic; up to 39 kJ/mol) depending on which DFT method is used to obtain the geometries. Therefore, a mechanism predicted by a single method should be viewed with caution. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/7975561
- author
- Li, Jilai
; Andrejic, Milica
; Mata, Ricardo A.
and Ryde, Ulf
LU
- organization
- publishing date
- 2015
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Density functional calculations, Molybdenum, Tungsten, Enzyme models
- in
- European Journal of Inorganic Chemistry
- issue
- 21
- pages
- 3580 - 3589
- publisher
- John Wiley & Sons Inc.
- external identifiers
-
- wos:000359297800023
- scopus:84938204657
- ISSN
- 1099-0682
- DOI
- 10.1002/ejic.201500209
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 127ec35f-6016-4f52-b621-9f8760b60a39 (old id 7975561)
- date added to LUP
- 2016-04-01 10:30:58
- date last changed
- 2023-02-20 02:34:31
@article{127ec35f-6016-4f52-b621-9f8760b60a39,
abstract = {{A thorough computational study has been performed to investigate oxygen atom transfer (OAT) reactions catalyzed by dimethyl sulfoxide reductase (DMSOR) with a catalytic molybdenum or tungsten ion. Thirteen different density functional theory (DFT) methods have been employed to obtain structural parameters along the reaction pathway, and single-point energies were computed with local correlation coupled-cluster methods [LCCSD(T0)]. For both Mo and W, most DFT methods indicate that the enzyme follows a twostep mechanism with a stable intermediate in which a DMSO molecule coordinates to the metal ion in the +IV oxidation state, and this is also confirmed by the LCCSD(T0) energies. The W-substituted models have a 26-30 kJ/mol lower activation barrier for the OAT reaction, and the reaction is 6370 kJ/mol more exothermic than that with Mo. Different DFT methods give widely different activation and reaction energies, which roughly depend on the amount of exact exchange in the method; these differences are also reflected in the structures, especially for the rate-limiting transition state. Consequently, there is quite a large variation in energies and various energy corrections (thermal, solvation, dispersion, and relativistic; up to 39 kJ/mol) depending on which DFT method is used to obtain the geometries. Therefore, a mechanism predicted by a single method should be viewed with caution.}},
author = {{Li, Jilai and Andrejic, Milica and Mata, Ricardo A. and Ryde, Ulf}},
issn = {{1099-0682}},
keywords = {{Density functional calculations; Molybdenum; Tungsten; Enzyme models}},
language = {{eng}},
number = {{21}},
pages = {{3580--3589}},
publisher = {{John Wiley & Sons Inc.}},
series = {{European Journal of Inorganic Chemistry}},
title = {{A Computational Comparison of Oxygen Atom Transfer Catalyzed by Dimethyl Sulfoxide Reductase with Mo and W}},
url = {{http://dx.doi.org/10.1002/ejic.201500209}},
doi = {{10.1002/ejic.201500209}},
year = {{2015}},
}