A combined quantum and molecular mechanical study of the O-2 reductive cleavage in the catalytic cycle of multicopper oxidases
Rulisek, Lubomir LU ; Solomon, E I and Ryde, Ulf LU
(2005)
In Inorganic Chemistry
44(16).
p.5612-5628
- Abstract
- The four-electron reduction of dioxygen to water in multicopper oxidases takes place in a trinuclear copper cluster, which is linked to a mononuclear blue copper site, where the substrates are oxidized. Recently, several intermediates in the catalytic cycle have been spectroscopically characterized, and two possible structural models have been suggested for both the peroxy and native intermediates, In this study, these spectroscopic results are complemented by hybrid quantum and molecular mechanical (QM/MM) calculations, taking advantage of recently available crystal structures with a full complement of copper ions. Thereby, we obtain optimized molecular structures for all of the Experimentally studied intermediates involved in the... (More)
- The four-electron reduction of dioxygen to water in multicopper oxidases takes place in a trinuclear copper cluster, which is linked to a mononuclear blue copper site, where the substrates are oxidized. Recently, several intermediates in the catalytic cycle have been spectroscopically characterized, and two possible structural models have been suggested for both the peroxy and native intermediates, In this study, these spectroscopic results are complemented by hybrid quantum and molecular mechanical (QM/MM) calculations, taking advantage of recently available crystal structures with a full complement of copper ions. Thereby, we obtain optimized molecular structures for all of the Experimentally studied intermediates involved in the reductive cleavage of the O-2 molecule and energy profiles for individual reaction steps, This allows identification of the experimentally observed intermediates and further insight into the reaction mechanism that is probably relevant for the whole class of multicopper oxidases, We suggest that the peroxy intermediate contains an O-2(2-) ion, in which one oxygen atom bridges the type 2 copper ion and one of the type 3 copper ions, whereas the other one coordinates to the other type 3 copper ion, One-electron reduction of this intermediate triggers the cleavage of the O-O bond, which involves the uptake of a proton, The product of this cleavage is the observed native intermediate, which we suggest to contain a O-2 ion coordinated to all three of the copper ions in the center of the cluster. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/152715
- author
- Rulisek, Lubomir
LU
; Solomon, E I
and Ryde, Ulf
LU
- organization
- publishing date
- 2005
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Inorganic Chemistry
- volume
- 44
- issue
- 16
- pages
- 5612 - 5628
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000231030900012
- pmid:16060610
- scopus:23844550273
- ISSN
- 1520-510X
- DOI
- 10.1021/ic050092z
- 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
- 5819617a-b12f-474b-bbcd-976c76e2a5d5 (old id 152715)
- date added to LUP
- 2016-04-01 11:47:36
- date last changed
- 2023-01-24 02:31:05
@article{5819617a-b12f-474b-bbcd-976c76e2a5d5,
abstract = {{The four-electron reduction of dioxygen to water in multicopper oxidases takes place in a trinuclear copper cluster, which is linked to a mononuclear blue copper site, where the substrates are oxidized. Recently, several intermediates in the catalytic cycle have been spectroscopically characterized, and two possible structural models have been suggested for both the peroxy and native intermediates, In this study, these spectroscopic results are complemented by hybrid quantum and molecular mechanical (QM/MM) calculations, taking advantage of recently available crystal structures with a full complement of copper ions. Thereby, we obtain optimized molecular structures for all of the Experimentally studied intermediates involved in the reductive cleavage of the O-2 molecule and energy profiles for individual reaction steps, This allows identification of the experimentally observed intermediates and further insight into the reaction mechanism that is probably relevant for the whole class of multicopper oxidases, We suggest that the peroxy intermediate contains an O-2(2-) ion, in which one oxygen atom bridges the type 2 copper ion and one of the type 3 copper ions, whereas the other one coordinates to the other type 3 copper ion, One-electron reduction of this intermediate triggers the cleavage of the O-O bond, which involves the uptake of a proton, The product of this cleavage is the observed native intermediate, which we suggest to contain a O-2 ion coordinated to all three of the copper ions in the center of the cluster.}},
author = {{Rulisek, Lubomir and Solomon, E I and Ryde, Ulf}},
issn = {{1520-510X}},
language = {{eng}},
number = {{16}},
pages = {{5612--5628}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Inorganic Chemistry}},
title = {{A combined quantum and molecular mechanical study of the O-2 reductive cleavage in the catalytic cycle of multicopper oxidases}},
url = {{https://lup.lub.lu.se/search/files/135493204/77_lacc.pdf}},
doi = {{10.1021/ic050092z}},
volume = {{44}},
year = {{2005}},
}