Function of activation loop tyrosine phosphorylation in the mechanism of c-Kit auto-activation and its implication in sunitinib resistance

J Biochem. 2010 Apr;147(4):601-9. doi: 10.1093/jb/mvq015. Epub 2010 Feb 10.

Abstract

The activation of receptor tyrosine kinases (RTKs) is tightly regulated through a variety of mechanisms. Kinetic studies show that activation of c-Kit RTK occurs through an inter-molecular autophosphorylation. Phosphopeptide mapping of c-Kit reveals that 14-22 phosphates are added to each mol of wild-type (WT) c-Kit during the activation. Phosphorylation sites are found on the JM, kinase insert (KID), c-terminal domains and the activation loop (A-loop), but only the sites on the JM domain contribute to the kinase activation. The A-loop tyrosine (Y(823)) is not phosphorylated until very late in the activation (>90% completion), indicating that the A-loop phosphorylation is not required for c-Kit activation. A sunitinib-resistant mutant D816H that accelerates auto-activation by 184-fold shows no phosphorylation on the A-loop tyrosine after full activation. A loss-of-phosphorylation mutation Y823F remains fully competent in auto-activation. Similar to WT and D816H, the unactivated Y823F mutant binds sunitinib and imatinib with high affinity (K(D) = 5.9 nM). But unlike the WT and D816H where the activated enzymes lose the ability to bind the two drugs, activated Y823F binds the two inhibitors effectively. These observations suggest that the A-loop of activated Y823F remains flexible and can readily adopt unactivated conformations to accommodate DFG-out binders.

MeSH terms

  • Amino Acid Substitution
  • Antineoplastic Agents / metabolism*
  • Benzamides
  • Catalytic Domain
  • Drug Resistance, Neoplasm*
  • Enzyme Activation
  • Enzyme Inhibitors / metabolism*
  • Humans
  • Imatinib Mesylate
  • Indoles / metabolism*
  • Kinetics
  • Microchemistry / methods
  • Models, Biological
  • Mutant Proteins / chemistry
  • Mutant Proteins / isolation & purification
  • Mutant Proteins / metabolism
  • Peptide Mapping
  • Phosphorylation
  • Phosphotyrosine / physiology*
  • Piperazines / metabolism
  • Protein Binding
  • Protein Interaction Domains and Motifs / physiology*
  • Proto-Oncogene Proteins c-kit / antagonists & inhibitors
  • Proto-Oncogene Proteins c-kit / chemistry
  • Proto-Oncogene Proteins c-kit / genetics
  • Proto-Oncogene Proteins c-kit / metabolism*
  • Pyrimidines / metabolism
  • Pyrroles / metabolism*
  • Recombinant Fusion Proteins / antagonists & inhibitors
  • Recombinant Fusion Proteins / chemistry
  • Recombinant Fusion Proteins / isolation & purification
  • Recombinant Fusion Proteins / metabolism
  • Sunitinib

Substances

  • Antineoplastic Agents
  • Benzamides
  • Enzyme Inhibitors
  • Indoles
  • Mutant Proteins
  • Piperazines
  • Pyrimidines
  • Pyrroles
  • Recombinant Fusion Proteins
  • Phosphotyrosine
  • Imatinib Mesylate
  • Proto-Oncogene Proteins c-kit
  • Sunitinib