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Reorganization Energy for Internal Electron Transfer in Multicopper Oxidases.

Hu, LiHong LU ; Farrokhnia, Maryam LU ; Heimdal, Jimmy LU ; Shleev, Sergey LU ; Rulisek, Lubomir LU and Ryde, Ulf LU (2011) In The Journal of Physical Chemistry Part B 115(Online September 28, 2011). p.13111-13126
Abstract
We have calculated the reorganization energy for the intramolecular electron transfer between the reduced type 1 copper site and the peroxy intermediate of the trinuclear cluster in the multicopper oxidase CueO. The calculations are performed at the combined quantum mechanics and molecular mechanics (QM/MM) level, based on molecular dynamics simulations with tailored potentials for the two copper sites. We obtain a reorganization energy of 91-133 kJ/mol, depending on the theoretical treatment. The two Cu sites contribute by 12 and 22 kJ/mol to this energy, whereas the solvent contribution is 34 kJ/mol. The rest comes from the protein, involving small contributions from many residues. We have also estimated the energy difference between the... (More)
We have calculated the reorganization energy for the intramolecular electron transfer between the reduced type 1 copper site and the peroxy intermediate of the trinuclear cluster in the multicopper oxidase CueO. The calculations are performed at the combined quantum mechanics and molecular mechanics (QM/MM) level, based on molecular dynamics simulations with tailored potentials for the two copper sites. We obtain a reorganization energy of 91-133 kJ/mol, depending on the theoretical treatment. The two Cu sites contribute by 12 and 22 kJ/mol to this energy, whereas the solvent contribution is 34 kJ/mol. The rest comes from the protein, involving small contributions from many residues. We have also estimated the energy difference between the two electron-transfer states and show that the reduction of the peroxy intermediate is exergonic by 43-87 kJ/mol, depending on the theoretical method. Both the solvent and the protein contribute to this energy difference, especially charged residues close to the two Cu sites. We compare these estimates with energies obtained from QM/MM optimizations and QM calculations in a vacuum and discuss differences between the results obtained at various levels of theory. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
115
issue
Online September 28, 2011
pages
13111 - 13126
publisher
The American Chemical Society
external identifiers
  • wos:000296686000001
  • pmid:21955325
  • scopus:80855128956
ISSN
1520-5207
DOI
10.1021/jp205897z
language
English
LU publication?
yes
id
3603b768-7243-44f0-8097-5c9c53f7bafe (old id 2201084)
date added to LUP
2011-11-09 11:36:50
date last changed
2017-11-12 03:34:33
@article{3603b768-7243-44f0-8097-5c9c53f7bafe,
  abstract     = {We have calculated the reorganization energy for the intramolecular electron transfer between the reduced type 1 copper site and the peroxy intermediate of the trinuclear cluster in the multicopper oxidase CueO. The calculations are performed at the combined quantum mechanics and molecular mechanics (QM/MM) level, based on molecular dynamics simulations with tailored potentials for the two copper sites. We obtain a reorganization energy of 91-133 kJ/mol, depending on the theoretical treatment. The two Cu sites contribute by 12 and 22 kJ/mol to this energy, whereas the solvent contribution is 34 kJ/mol. The rest comes from the protein, involving small contributions from many residues. We have also estimated the energy difference between the two electron-transfer states and show that the reduction of the peroxy intermediate is exergonic by 43-87 kJ/mol, depending on the theoretical method. Both the solvent and the protein contribute to this energy difference, especially charged residues close to the two Cu sites. We compare these estimates with energies obtained from QM/MM optimizations and QM calculations in a vacuum and discuss differences between the results obtained at various levels of theory.},
  author       = {Hu, LiHong and Farrokhnia, Maryam and Heimdal, Jimmy and Shleev, Sergey and Rulisek, Lubomir and Ryde, Ulf},
  issn         = {1520-5207},
  language     = {eng},
  number       = {Online September 28, 2011},
  pages        = {13111--13126},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Reorganization Energy for Internal Electron Transfer in Multicopper Oxidases.},
  url          = {http://dx.doi.org/10.1021/jp205897z},
  volume       = {115},
  year         = {2011},
}