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

J Phys Chem B. 2006 Dec 7;110(48):24708-19. doi: 10.1021/jp066263i.

Abstract

A fully microscopical simulation of the rate-limiting hydrogen abstraction catalyzed by soybean lipoxygenase-1 (SLO-1) has been carried out. This enzyme exhibits the largest, and weakly temperature dependent, experimental H/D kinetic isotope effect (KIE) reported for a biological system. The theoretical model used here includes the complete enzyme with a solvation shell of water molecules, the Fe(III)-OH- cofactor, and the linoleic acid substrate. We have used a hybrid QM(PM3/d-SRP)/MM method to describe the potential energy surface of the whole system, and the ensemble-averaged variational transition-state theory with multidimensional tunneling (EA-VTST/MT) to calculate the rate constant and the primary KIE. 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. Importantly, the active site becomes more flexible in the Ile553Ala mutant reactant complex simulation (for which a markedly temperature dependent KIE has been experimentally determined), thus justifying the proposed key role of the gating promoting mode in the reaction catalyzed by SLO-1. Finally, the results indicate that the calculated KIE for the wild-type enzyme has an important dependence on the barrier width.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Binding Sites
  • Catalysis
  • Computer Simulation
  • Glycine max / enzymology*
  • Hydrogen / chemistry*
  • Iron / chemistry
  • Kinetics
  • Ligands
  • Lipoxygenase / chemistry*
  • Lipoxygenase / genetics
  • Lipoxygenase / metabolism*
  • Models, Molecular
  • Mutation / genetics
  • Protein Binding
  • Protein Structure, Tertiary
  • Substrate Specificity
  • Water

Substances

  • Ligands
  • Water
  • Hydrogen
  • Iron
  • lipoxygenase L-1
  • Lipoxygenase