Trypanosomal nucleoside hydrolase. A novel mechanism from the structure with a transition-state inhibitor

Biochemistry. 1998 May 5;37(18):6277-85. doi: 10.1021/bi973012e.

Abstract

Nucleoside N-ribohydrolases are targets for disruption of purine salvage in the protozoan parasites. The structure of a trypanosomal N-ribohydrolase in complex with a transition-state inhibitor is reported at 2.3 A resolution. The nonspecific nucleoside hydrolase from Crithidia fasciculata cocrystallized with p-aminophenyliminoribitol reveals tightly bound Ca2+ as a catalytic site ligand. The complex with the transition-state inhibitor is characterized by (1) large protein conformational changes to create a hydrophobic leaving group site (2) C3'-exo geometry for the inhibitor, typical of a ribooxocarbenium ion (3) stabilization of the ribooxocarbenium analogue between the neighboring group 5'-hydroxyl and bidentate hydrogen bonds to Asn168; and (4) octacoordinate Ca2+ orients a catalytic site water and is liganded to two hydroxyls of the inhibitor. The mechanism is ribooxocarbenium stabilization with weak leaving group activation and is a departure from glucohydrolases which use paired carboxylates to achieve the transition state.

Publication types

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

MeSH terms

  • Amino Acid Sequence
  • Animals
  • Calcium / analysis
  • Crithidia fasciculata / enzymology*
  • Ligands
  • Models, Chemical
  • Models, Molecular
  • Molecular Sequence Data
  • N-Glycosyl Hydrolases / chemistry*
  • N-Glycosyl Hydrolases / metabolism
  • Protein Conformation
  • X-Ray Diffraction

Substances

  • Ligands
  • N-Glycosyl Hydrolases
  • inosine-uridine hydrolase
  • Calcium

Associated data

  • PDB/2MAS