Allosteric Kinase Inhibitors Reshape MEK1 Kinase Activity Conformations in Cells and In Silico

Biomolecules. 2021 Mar 30;11(4):518. doi: 10.3390/biom11040518.

Abstract

Mutations at different stages of the mitogen-activated protein kinase (MAPK) signaling pathway lead to aberrant activation of the involved protein kinase entities. These oncogenic modifications alter signal propagation which converge on the gatekeeper kinases MEK1/2, transmitting the input signal to ERK1/2. Thus, targeted MEK inhibition causes qualitative alterations of carcinogenic MAPK signals. Phosphorylation of the MEK1 activation loop at the positions S218 and S222 by RAF kinases triggers the conformational alignment of MEK's catalytic pocket to enable ATP-binding and substrate phosphorylation. We have extended a kinase conformation (KinCon) biosensor platform to record MEK1 activity dynamics. In addition to MEK phosphorylation by BRAF, the integration of the phosphorylation-mimetic mutations S218D/S222D triggered opening of the kinase. Structural rearrangement may involve the flexibility of the N terminal MEK1 A-helix. Application of the allosterically acting MEK inhibitors (MEKi) trametinib, cobimentinib, refametinib, and selumetinib converted activated MEK1 KinCon reporters back into a more closed inactive conformation. We confirmed MEK1 KinCon activity dynamics upon drug engagement using the patient-derived melanoma cell line A2058, which harbors the V600E hotspot BRAF mutation. In order to confirm biosensor dynamics, we simulated structure dynamics of MEK1 kinase in the presence and absence of mutations and/or MEKi binding. We observed increased dynamics for the S218D/S222D double mutant particularly in the region of the distal A-helix and alpha-C helix. These data underline that MEK1 KinCon biosensors have the potential to be subjected to MEKi efficacy validations in an intact cell setting.

Keywords: ERK; KinCon reporter; MAPK pathway; RAF; RAS; RAS–RAF–ERK pathway; allosteric inhibitor; biosensor; cancer mutations; kinase inhibitor; personalized therapy; protein-fragment complementation assay; structure dynamics; structure simulations.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzimidazoles / pharmacology
  • Cell Line, Tumor
  • Computer Simulation
  • Drug Evaluation, Preclinical / methods*
  • HEK293 Cells
  • Humans
  • MAP Kinase Kinase 1 / antagonists & inhibitors*
  • MAP Kinase Kinase 1 / chemistry
  • MAP Kinase Kinase 1 / genetics*
  • MAP Kinase Kinase 1 / metabolism
  • Melanoma / pathology
  • Molecular Dynamics Simulation
  • Mutation
  • Phosphorylation
  • Protein Conformation
  • Protein Kinase Inhibitors / pharmacology*
  • Proto-Oncogene Proteins B-raf / genetics
  • Recombinant Proteins / genetics
  • Recombinant Proteins / metabolism

Substances

  • AZD 6244
  • Benzimidazoles
  • Protein Kinase Inhibitors
  • Recombinant Proteins
  • BRAF protein, human
  • Proto-Oncogene Proteins B-raf
  • MAP Kinase Kinase 1
  • MAP2K1 protein, human