Author(s):
Barroso, Mónica 
; Arnaut, Luís G. ; Formosinho, Sebastião J.
Date: 2008
Persistent ID: http://hdl.handle.net/10316/8231
Origin: Estudo Geral - Universidade de Coimbra
Document details
A chemical understanding for the enhanced hydrogen tunnelling in hydroperoxidat...
Description
The reaction path of the Interacting-State Model (ISM) is used with the Transition-State Theory (TST) and the semiclassical correction for tunnelling (ISM/scTST) to calculate the rates of H-atom abstraction from C(11) of linoleic acid catalysed by soybean lipoxygenase-1 (SLO), as well as of an analogous uncatalysed reaction in solution. The calculated hydrogen-atom transfer rates, their temperature dependency and kinetic isotope effect (KIE) are in good agreement with the experimental data. ISM/scTST calculations reveal the hypersensitivity of the rate to protein dynamics when the hydrogen bonding to a carbon atom is present in the reaction coordinate. Copyright © 2008 John Wiley & Sons, Ltd. http://dx.doi.org/10.1002/poc.1346
The reaction path of the Interacting-State Model (ISM) is used with the Transition-State Theory (TST) and the semiclassical correction for tunnelling (ISM/scTST) to calculate the rates of H-atom abstraction from C(11) of linoleic acid catalysed by soybean lipoxygenase-1 (SLO), as well as of an analogous uncatalysed reaction in solution. The calculated hydrogen-atom transfer rates, their temperature dependency and kinetic isotope effect (KIE) are in good agreement with the experimental data. ISM/scTST calculations reveal the hypersensitivity of the rate to protein dynamics when the hydrogen bonding to a carbon atom is present in the reaction coordinate. Copyright © 2008 John Wiley & Sons, Ltd. http://dx.doi.org/10.1002/poc.1346
Document Type
Article
Language English
Language English
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