Analysis of the two active sites of the hyaluronan synthase and the chondroitin synthase of Pasteurella multocida

Glycobiology. 2003 Oct;13(10):661-71. doi: 10.1093/glycob/cwg085. Epub 2003 Jun 10.

Abstract

Type A Pasteurella multocida produces a hyaluronan (HA) capsule to enhance infection. The 972-residue HA synthase, pmHAS, polymerizes the linear HA polysaccharide composed of alternating beta3N-acetylglucosamine (GlcNAc)-beta4glucuronic acid (GlcUA). We demonstrated previously that pmHAS possesses two independent glycosyltransferase sites. Here we further define the sites and putative motifs. Deletion of residues 1-117 does not affect HA polymerizing activity. The carboxyl-terminal boundary of the GlcUA-transferase resides within residues 686-703. Both transferase sites contain a DXD motif essential for HA synthase activity. D247N or D249N mutants possessed only GlcUA-transferase activity, whereas D527N or D529N mutants possessed only GlcNAc-transferase activity, further confirming our assignment of the two active sites within the synthase polypeptide. A potential role of the DXD motif in substrate binding was supported by experiments utilizing high UDP-sugar concentrations that partially rescued the activity of certain mutants. The WGGED sequence motif is involved in GlcNAc-transferase activity because mutants with substitutions at E369 or D370 possessed only GlcUA-transferase activity. Type F P. multocida synthesizes an unsulfated chondroitin (beta3GalNAc-beta4GlcUA) capsule. A chimeric enzyme consisting of residues 1-427 of pmHAS and residues 421-704 of pmCS, the homologous chondroitin synthase, was an active HA synthase. The converse chimeric enzyme consisting of residues 1-420 of pmCS and residues 428-703 of pmHAS was a functional chondroitin synthase. Analyses of a panel of pmHAS/pmCS chimeric enzymes identified a 44-residue region, corresponding to pmHAS residues 225-265, involved in UDP-hexosamine selectivity. Overall, these findings further support the model of two independent transferase sites within a single polypeptide.

Publication types

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

MeSH terms

  • Amino Acid Motifs
  • Amino Acid Sequence
  • Binding Sites
  • Glucuronosyltransferase
  • Hyaluronan Synthases
  • Kinetics
  • Metals / metabolism
  • Molecular Sequence Data
  • Mutagenesis, Site-Directed
  • N-Acetylgalactosaminyltransferases / chemistry*
  • N-Acetylgalactosaminyltransferases / genetics
  • N-Acetylgalactosaminyltransferases / metabolism*
  • Pasteurella multocida / enzymology*
  • Pasteurella multocida / genetics
  • Protein Structure, Tertiary
  • Sequence Deletion
  • Substrate Specificity
  • Transferases / chemistry*
  • Transferases / genetics
  • Transferases / metabolism*
  • Uridine Diphosphate / metabolism

Substances

  • Metals
  • Uridine Diphosphate
  • Transferases
  • N-Acetylgalactosaminyltransferases
  • Glucuronosyltransferase
  • chondroitin synthase
  • Hyaluronan Synthases