Kinetic and mechanistic analysis of Trypanosoma cruzi trans-sialidase reveals a classical ping-pong mechanism with acid/base catalysis

Biochemistry. 2008 Mar 18;47(11):3507-12. doi: 10.1021/bi7024832. Epub 2008 Feb 20.

Abstract

The trans-sialidase from Trypanosoma cruzi catalyzes the transfer of a sialic acid moiety from sialylated donor substrates to the terminal galactose moiety of lactose and lactoside acceptors to yield alpha-(2,3)-sialyllactose or its derivatives with net retention of anomeric configuration. Through kinetic analyses in which the concentrations of two different donor aryl alpha-sialoside substrates and the acceptor substrate lactose were independently varied, we have demonstrated that this enzyme follows a ping-pong bi-bi kinetic mechanism. This is supported for both the native enzyme and a mutant (D59A) in which the putative acid/base catalyst has been replaced by the demonstration of the half-reaction in which a sialyl-enzyme intermediate is formed. Mass spectrometric analysis of the protein directly demonstrates the formation of a covalent intermediate, while the observation of release of a full equivalent of p-nitrophenol by the mutant in a pre-steady state burst provides further support. The active site nucleophile is confirmed to be Tyr342 by trapping of the sialyl-enzyme intermediate using the D59A mutant and sequencing of the purified peptic peptide. The role of D59 as the acid/base catalyst is confirmed by chemical rescue studies in which activity is restored to the D59A mutant by azide and a sialyl azide product is formed.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alanine / genetics
  • Animals
  • Aspartic Acid / genetics
  • Azides / chemistry
  • Catalysis
  • Glycoproteins / chemistry*
  • Glycoproteins / genetics
  • Glycoproteins / metabolism*
  • Hydrogen-Ion Concentration
  • Hydrolysis
  • Kinetics
  • N-Acetylneuraminic Acid / chemistry
  • Neuraminidase / chemistry*
  • Neuraminidase / genetics
  • Neuraminidase / metabolism*
  • Nitrophenols / chemistry
  • Substrate Specificity / genetics
  • Trypanosoma cruzi / enzymology*
  • Trypanosoma cruzi / genetics
  • Tyrosine / chemistry

Substances

  • Azides
  • Glycoproteins
  • Nitrophenols
  • Aspartic Acid
  • Tyrosine
  • trans-sialidase
  • Neuraminidase
  • N-Acetylneuraminic Acid
  • Alanine
  • 4-nitrophenol