Kinetics of the aspartyl transpeptidation of daptomycin, a novel lipopeptide antibiotic

Pharm Res. 1989 May;6(5):387-93. doi: 10.1023/a:1015927330908.

Abstract

Two degradation products of the lipopeptide antibiotic, daptomycin, were identified and the reaction pathway and kinetics were delineated in aqueous solution at 60 degrees C, pH range 3 to 8 and ionic strength 0.01. The degradation products were 1) a succinimido intermediate (anhydro-daptomycin) formed by attack of side-chain carbonyl on the peptide-bond nitrogen in the asp-gly sequence and 2) a beta-asp daptomycin isomer formed by rehydration of the anhydrodaptomycin succinimide. This aspartyl transpeptidation pathway was found to be reversible. Formation of the anhydrodaptomycin from either daptomycin or beta-asp daptomycin was pH dependent but the pH-rate profiles for anhydrodaptomycin formation were not mechanistically interpretable. The pH-rate profiles for the formation of daptomycin or beta-asp daptomycin from the anhydrodaptomycin were linear with slopes = 1, which is consistent with nucleophilic hydroxide ion attack of the succinimido intermediate at either the alpha-carbonyl, giving rise to the beta-asp daptomycin, or the beta-carbonyl, giving rise to daptomycin.

MeSH terms

  • Aspartic Acid / metabolism*
  • Biotransformation
  • Carboxylic Acids / metabolism
  • Chromatography, High Pressure Liquid
  • Daptomycin
  • Hydrogen-Ion Concentration
  • Hydrolysis
  • Peptides / metabolism
  • Peptides / pharmacokinetics
  • Spectrophotometry, Ultraviolet
  • Time Factors

Substances

  • Carboxylic Acids
  • Peptides
  • Aspartic Acid
  • Daptomycin