Identification of Asp174 and Asp175 as the key catalytic residues of human O-GlcNAcase by functional analysis of site-directed mutants

Biochemistry. 2006 Mar 21;45(11):3835-44. doi: 10.1021/bi052370b.

Abstract

O-GlcNAcase is a family 84 beta-N-acetylglucosaminidase catalyzing the hydrolytic cleavage of beta-O-linked 2-acetamido-2-deoxy-d-glycopyranose (O-GlcNAc) from serine and threonine residues of posttranslationally modified proteins. O-GlcNAcases use a double-displacement mechanism involving formation and breakdown of a transient bicyclic oxazoline intermediate. The key catalytic residues of any family 84 enzyme facilitating this reaction, however, are unknown. Two mutants of human O-GlcNAcase, D174A and D175A, were generated since these residues are highly conserved among family 84 glycoside hydrolases. Structure-reactivity studies of the D174A mutant enzyme reveals severely impaired catalytic activity across a broad range of substrates alongside a pH-activity profile consistent with deletion of a key catalytic residue. The D175A mutant enzyme shows a significant decrease in catalytic efficiency with substrates bearing poor leaving groups (up to 3000-fold), while for substates bearing good leading groups the difference is much smaller (7-fold). This mutant enzyme also cleaves thioglycosides with essentially the same catalytic efficiency as the wild-type enzyme. As well, addition of azide as an exogenous nucleophile increases the activity of this enzyme toward a substrate bearing an excellent leaving group. Together, these results allow unambiguous assignment of Asp(174) as the residue that polarizes the 2-acetamido group for attack on the anomeric center and Asp(175) as the residue that functions as the general acid/base catalyst. Therefore, the family 84 glycoside hydrolases use a DD catalytic pair to effect catalysis.

Publication types

  • Comparative Study
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetylglucosaminidase / chemistry*
  • Acetylglucosaminidase / genetics
  • Acetylglucosaminidase / isolation & purification
  • Acetylglucosaminidase / metabolism
  • Acid-Base Equilibrium
  • Amino Acid Sequence
  • Animals
  • Aspartic Acid / chemistry*
  • Aspartic Acid / genetics
  • Aspartic Acid / metabolism
  • Azides / metabolism
  • Azides / pharmacology
  • Catalysis
  • Histone Acetyltransferases / chemistry*
  • Histone Acetyltransferases / genetics
  • Histone Acetyltransferases / isolation & purification
  • Histone Acetyltransferases / metabolism
  • Humans
  • Hydrogen-Ion Concentration
  • Kinetics
  • Molecular Sequence Data
  • Multienzyme Complexes / chemistry*
  • Multienzyme Complexes / genetics
  • Multienzyme Complexes / isolation & purification
  • Multienzyme Complexes / metabolism
  • Mutagenesis, Site-Directed
  • Mutation
  • Protein Structure, Tertiary
  • Sequence Alignment
  • Thioglycosides / metabolism
  • beta-N-Acetylhexosaminidases

Substances

  • Azides
  • Multienzyme Complexes
  • Thioglycosides
  • Aspartic Acid
  • Histone Acetyltransferases
  • hexosaminidase C
  • Acetylglucosaminidase
  • beta-N-Acetylhexosaminidases