A qualitative quantum rate model for hydrogen transfer in soybean lipoxygenase.

@article{Jevtic2017AQQ,
  title={A qualitative quantum rate model for hydrogen transfer in soybean lipoxygenase.},
  author={Srdjan Jevtic and Jennifer Anders},
  journal={The Journal of chemical physics},
  year={2017},
  volume={147 11},
  pages={
          114108
        }
}
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… 

Figures and Tables from this paper

Experimental and Theoretical Examination of the Kinetic Isotope Effect in Cytochrome P450 Decarboxylase OleT.

A more fundamental understanding of the OleT reaction coordinate contributes to the development of biomimetic catalysts for controlled C─H bond activation, an outstanding current challenge for (bio)synthetic chemistry.

Proton tunnelling in hydrogen bonds and its implications in an induced-fit model of enzyme catalysis

The role of proton tunnelling in biological catalysis is investigated here within the frameworks of quantum information theory and thermodynamics and it is found that in this scenario the enzyme lowers the activation energy so much that there is no energy barrier left in the tautomerization, even if the quantum correlations quickly decay.

Modeling the Ligand Effect on the Structure of CYP 450 Within the Density Functional Theory.

An improved understanding of the P450 structure is relevant to the development of biomimetic catalysts and inhibitors for controlled CH-bond activation, an outstanding challenge of synthetic

Cavity-altered thermal isomerization rates and dynamical resonant localization in vibro-polaritonic chemistry.

It has been experimentally demonstrated that reaction rates for molecules embedded in microfluidic optical cavities are altered when compared to rates observed under "ordinary" reaction conditions.

Parameter Reliability and Understanding Enzyme Function

This review considers the evaluation of published literature data on Michaelis–Menten parameters with particular emphasis on the assessment of its fitness for purpose.

References

SHOWING 1-10 OF 40 REFERENCES

Enzyme dynamics and tunneling enhanced by compression in the hydrogen abstraction catalyzed by soybean lipoxygenase-1.

The computational results show that the compression of the wild-type active site enzyme results in the huge contribution of tunneling (99%) to the rate of the hydrogen abstraction, thus justifying the proposed key role of the gating promoting mode in the reaction catalyzed by SLO-1.

Proton-coupled electron transfer in soybean lipoxygenase.

The proton donor-acceptor vibrational motion plays a vital role in decreasing the dominant donor- acceptor distance relative to its equilibrium value to facilitate the proton-coupled electron transfer reaction.

Proton-coupled electron transfer in soybean lipoxygenase: dynamical behavior and temperature dependence of kinetic isotope effects.

The dynamical behavior and the temperature dependence of the kinetic isotope effects (KIEs) are examined for the proton-coupled electron transfer reaction catalyzed by the enzyme soybean lipoxygenase without fitting any parameters directly to the experimental kinetic data.

Temperature-dependent isotope effects in soybean lipoxygenase-1: correlating hydrogen tunneling with protein dynamics.

WT-SLO has an active site structure that is well organized to support hydrogen Tunneling and that mutations perturb structural elements that support hydrogen tunneling, which allows the detection and characterization of a protein-gating mode in catalysis.

Enhanced Rigidification within a Double Mutant of Soybean Lipoxygenase Provides Experimental Support for Vibronically Nonadiabatic Proton-Coupled Electron Transfer Models

A nearly temperature-independent kinetic isotope effect (KIE) with an average KIE value of 661 ± 27 for a double mutant of SLO at six temperatures is reported, providing strong experimental support for the model of hydrogen tunneling in SLO.

Proton-coupled electron transfer reactions: analytical rate constants and case study of kinetic isotope effects in lipoxygenase.

The application of this theory to PCET in the enzyme soybean lipoxygenase illustrates the regimes of validity for the various rate constant expressions and elucidates the fundamental physical principles dictating PCET reactions.

Probing Nonadiabaticity in the Proton-Coupled Electron Transfer Reaction Catalyzed by Soybean Lipoxygenase

Quantitative diagnostics have been devised to characterize the vibronic nonadiabaticity between the electron–proton quantum subsystem and the classical nuclei, as well as the electrons and proton(s) within the quantum subsystem, which will be useful for theoretical modeling of a broad range of PCET processes.

Temperature dependence of kinetic isotope effects for enzymatic carbon-hydrogen bond cleavage

An analysis is reported of the anomalously weak temperature dependence of large kinetic isotope effects (KIEs) observed for enzymes that catalyze carbon-hydrogen bond cleavage. After a critical

Quantum variational transition state theory for hydrogen tunneling in enzyme catalysis.

  • E. Pollak
  • Biology
    The journal of physical chemistry. B
  • 2012
It is suggested that variational transition state theory as applied to dissipative systems, above the crossover temperature between deep tunneling and thermal activation, may be used as a paradigm for understanding the dynamics of these reactions.

Extremely Elevated Room-Temperature Kinetic Isotope Effects Quantify the Critical Role of Barrier Width in Enzymatic C–H Activation

These findings show the compelling property of room-temperature hydrogen tunneling within a biological context and demonstrate the very high sensitivity of such tunneling to barrier width.