Reaction intermediates in the catalytic mechanism of Escherichia coli MutY DNA glycosylase

J Biol Chem. 2004 Nov 5;279(45):46930-9. doi: 10.1074/jbc.M403944200. Epub 2004 Aug 23.

Abstract

The Escherichia coli adenine DNA glycosylase, MutY, plays an important role in the maintenance of genomic stability by catalyzing the removal of adenine opposite 8-oxo-7,8-dihydroguanine or guanine in duplex DNA. Although the x-ray crystal structure of the catalytic domain of MutY revealed a mechanism for catalysis of the glycosyl bond, it appeared that several opportunistically positioned lysine side chains could participate in a secondary beta-elimination reaction. In this investigation, it is established via site-directed mutagenesis and the determination of a 1.35-A structure of MutY in complex with adenine that the abasic site (apurinic/apyrimidinic) lyase activity is alternatively regulated by two lysines, Lys142 and Lys20. Analyses of the crystallographic structure also suggest a role for Glu161 in the apurinic/apyrimidinic lyase chemistry. The beta-elimination reaction is structurally and chemically uncoupled from the initial glycosyl bond scission, indicating that this reaction occurs as a consequence of active site plasticity and slow dissociation of the product complex. MutY with either the K142A or K20A mutation still catalyzes beta and beta-delta elimination reactions, and both mutants can be trapped as covalent enzyme-DNA intermediates by chemical reduction. The trapping was observed to occur both pre- and post-phosphodiester bond scission, establishing that both of these intermediates have significant half-lives. Thus, the final spectrum of DNA products generated reflects the outcome of a delicate balance of closely related equilibrium constants.

Publication types

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

MeSH terms

  • Adenine / chemistry
  • Aspartic Acid / chemistry
  • Binding Sites
  • Catalysis
  • Catalytic Domain
  • Crystallography, X-Ray
  • DNA / chemistry
  • DNA Glycosylases / chemistry*
  • DNA Glycosylases / metabolism
  • Dose-Response Relationship, Drug
  • Escherichia coli / enzymology*
  • Glutamic Acid / chemistry
  • Guanine / chemistry
  • Kinetics
  • Lysine / chemistry
  • Models, Chemical
  • Models, Molecular
  • Mutagenesis, Site-Directed
  • Mutation
  • Protein Conformation
  • Time Factors

Substances

  • Aspartic Acid
  • Glutamic Acid
  • Guanine
  • DNA
  • DNA Glycosylases
  • mutY adenine glycosylase
  • Adenine
  • Lysine

Associated data

  • PDB/1WEF
  • PDB/1WEG
  • PDB/1WEI