Evidence for protein-tyrosine-phosphatase catalysis proceeding via a cysteine-phosphate intermediate

J Biol Chem. 1991 Sep 15;266(26):17026-30.

Abstract

A recombinant protein-tyrosine-phosphatase has been expressed in Escherichia coli and purified to a single band by sodium dodecyl sulfate-polyacrylamide gel electrophoresis using affinity chromatography. When the phosphatase was allowed to react with 32P-labeled substrates and then rapidly denaturated, a 32P-labeled phosphoprotein could be visualized by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Transient formation of a 32P-labeled phosphoprotein was observed, and the 32P-labeled protein disappeared as substrate was consumed. In the presence of 32P-labeled p-nitrophenyl phosphate, 0.27 mol of phosphate was incorporated per mol of protein-tyrosine-phosphatase. Site-directed mutagenesis of a catalytically essential cystine residue (position 215) in the recombinant protein resulted in an inactive enzyme, and no phosphoprotein was formed. The 32P-labeled phosphoprotein showed a maximum lability between pH 2.5 and 3.5 and was rapidly decomposed in the presence of iodine. These properties, along with additional site-directed mutations, suggest that the protein-tyrosine-phosphatase forms a covalent thiol phosphate linkage between Cys215 and phosphate.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Amino Acid Sequence
  • Animals
  • Catalysis
  • Chromatography, Gel
  • Cloning, Molecular
  • Cysteine / metabolism*
  • Electrophoresis, Polyacrylamide Gel
  • Hydrogen-Ion Concentration
  • Molecular Sequence Data
  • Mutagenesis, Site-Directed
  • Phosphoprotein Phosphatases / genetics
  • Phosphoprotein Phosphatases / metabolism*
  • Phosphoproteins / metabolism
  • Protein Tyrosine Phosphatases
  • Rats

Substances

  • Phosphoproteins
  • Phosphoprotein Phosphatases
  • Protein Tyrosine Phosphatases
  • Cysteine