The mechanism of the reaction catalyzed by ADP-beta-L-glycero-D-manno-heptose 6-epimerase

J Am Chem Soc. 2004 Jul 28;126(29):8878-9. doi: 10.1021/ja0485659.

Abstract

ADP-l-glycero-d-manno-heptose 6-epimerase (AGME, RfaD) is a bacterial enzyme that is involved in lipopolysaccharide biosynthesis and interconverts ADP-beta-l-glycero-d-manno-heptose (ADP-l,d-Hep) with ADP-beta-d-glycero-d-manno-heptose (ADP-d,d-Hep). AGME is known to require a tightly bound NADP+ cofactor for activity and presumably employs a mechanism involving transient oxidation of the substrate. Four mechanistic possibilities are considered that involve transient oxidation at either C-7' ', C-6' ', or C-4' ' of the heptose nucleotide. In this contribution, the use of solvent isotope incorporation studies and alternate substrates provides strong evidence for a mechanism involving nonstereospecific oxidation/reduction directly at C-6' '. It was found that the epimerization proceeds without any detectable incorporation of solvent-derived deuterium or 18O-isotope into the product. This argues against mechanisms involving either proton transfers at carbon or dehydration/rehydration events. In addition, the deoxygenated analogues, 7' '-deoxy-ADP-l,d-Hep and 4' '-deoxy-ADP-l,d-Hep, were both found to serve as substrates for the enzyme, indicating that oxidation at either C-7' ' or C-4' ' is not required for catalysis.

Publication types

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

MeSH terms

  • Carbohydrate Epimerases / chemistry*
  • Carbohydrate Epimerases / metabolism*
  • Escherichia coli / enzymology
  • Escherichia coli / genetics
  • Heptoses / chemistry
  • Heptoses / metabolism
  • Nuclear Magnetic Resonance, Biomolecular
  • Oxidation-Reduction
  • Recombinant Proteins / chemistry
  • Recombinant Proteins / metabolism

Substances

  • Heptoses
  • Recombinant Proteins
  • glycero-alpha-manno-heptopyranose
  • ADP-L-glycero-D-mannoheptose-6-epimerase
  • Carbohydrate Epimerases