A qualitative quantum rate model for hydrogen transfer in soybean lipoxygenase
Journal of Chemical Physics
The hydrogen transfer reaction catalysed by soybean lipoxygenase (SLO) has been the focus of intense study following observations of a high kinetic isotope effect (KIE). Today high KIEs are generally thought to indicate departure from classical rate theory and are seen as a strong signature of tunnelling of the transferring particle, hydrogen or one of its isotopes, through the reaction energy barrier. In this paper we build a qualitative quantum rate model with few free parameters that describes the dynamics of the transferring particle when it is exposed to energetic potentials exerted by the donor and the acceptor. The enzyme’s impact on the dynamics is modelled by an additional energetic term, an oscillatory contribution known as “gating”. By varying two key parameters, the gating frequency and the mean donoracceptor separation, the model is able to reproduce well the KIE data for SLO wild-type and a variety of SLO mutants over the experimentally accessible temperature range. While SLO-specific constants have been considered here, it is possible to adapt these for other enzymes.
SJ is funded by an Imperial College London Junior Research Fellowship. SJ also acknowledges the following grants: ERC grants QFTCMPS; SIQS by the cluster of excellence EXC 201 Quantum Engineering and Space-Time Research; and EPSRC grant EP/K022512/1. JA acknowledges support by the Royal Society and EPSRC (EP/M009165/1).
This is the author accepted manuscript. The final version is available from AIP Publishing via the DOI in this record.
Vol. 147, article 114108