Structural insights into the catalytic mechanism of phosphate ester hydrolysis by dUTPase

J Biol Chem. 2004 Oct 8;279(41):42907-15. doi: 10.1074/jbc.M406135200. Epub 2004 Jun 17.

Abstract

dUTPase is essential to keep uracil out of DNA. Crystal structures of substrate (dUTP and alpha,beta-imino-dUTP) and product complexes of wild type and mutant dUTPases were determined to reveal how an enzyme responsible for DNA integrity functions. A kinetic analysis of wild type and mutant dUTPases was performed to obtain relevant mechanistic information in solution. Substrate hydrolysis is shown to be initiated via in-line nucleophile attack of a water molecule oriented by an activating conserved aspartate residue. Substrate binding in a catalytically competent conformation is achieved by (i) multiple interactions of the triphosphate moiety with catalysis-assisting Mg2+, (ii) a concerted motion of residues from three conserved enzyme motifs as compared with the apoenzyme, and (iii) an intricate hydrogen-bonding network that includes several water molecules in the active site. Results provide an understanding for the catalytic role of conserved residues in dUTPases.

MeSH terms

  • Amino Acid Motifs
  • Amino Acid Sequence
  • Binding Sites
  • Catalysis
  • Catalytic Domain
  • Crystallography, X-Ray
  • DNA / chemistry
  • Electrons
  • Escherichia coli / enzymology*
  • Esters / chemistry*
  • Hydrogen Bonding
  • Hydrolysis
  • Kinetics
  • Ligands
  • Magnesium / chemistry
  • Models, Chemical
  • Models, Molecular
  • Molecular Sequence Data
  • Mutation
  • Phosphates / chemistry*
  • Protein Binding
  • Pyrophosphatases / chemistry*
  • Sequence Homology, Amino Acid
  • Uracil / chemistry
  • Water / chemistry

Substances

  • Esters
  • Ligands
  • Phosphates
  • Water
  • Uracil
  • DNA
  • Pyrophosphatases
  • dUTP pyrophosphatase
  • Magnesium