A chemical understanding for the enhanced hydrogen tunnelling in hydroperoxidation of linoleic acid catalysed by soybean lipoxygenase-1

Abstract

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.