Reactivity of asparagine residue at the active site of the D105N mutant of fluoroacetate dehalogenase from Moraxella sp. B

Biochim Biophys Acta. 2004 Apr 8;1698(1):27-36. doi: 10.1016/j.bbapap.2003.10.002.

Abstract

Fluoroacetate dehalogenase from Moraxella sp. B (FAc-DEX) catalyzes cleavage of the carbon-fluorine bond of fluoroacetate, whose dissociation energy is among the highest found in natural products. Asp105 functions as the catalytic nucleophile that attacks the alpha-carbon atom of the substrate to displace the fluorine atom. In spite of the essential role of Asp105, we found that site-directed mutagenesis to replace Asp105 by Asn does not result in total inactivation of the enzyme. The activity of the mutant enzyme increased in a time- and temperature-dependent manner. We analyzed the enzyme by ion-spray mass spectrometry and found that the reactivation was caused by the hydrolytic deamidation of Asn105 to generate the wild-type enzyme. Unlike Asn10 of the l-2-haloacid dehalogenase (L-DEX YL) D10N mutant, Asn105 of the fluoroacetate dehalogenase D105N mutant did not function as a nucleophile to catalyze the dehalogenation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Substitution
  • Asparagine / genetics
  • Asparagine / metabolism*
  • Fluoroacetates / metabolism
  • Hydrolases / genetics
  • Hydrolases / metabolism*
  • Mass Spectrometry
  • Moraxella / enzymology*
  • Moraxella / genetics
  • Mutation*
  • Protein Renaturation

Substances

  • Fluoroacetates
  • Asparagine
  • fluoroacetic acid
  • Hydrolases
  • haloacetate dehalogenase