Kinetic analysis of an inhibitor-resistant variant of the OHIO-1 beta-lactamase, an SHV-family class A enzyme

Biochem J. 1998 Jul 15;333 ( Pt 2)(Pt 2):395-400. doi: 10.1042/bj3330395.

Abstract

The Met69-->Ile mutant of the OHIO-1 beta-lactamase, an SHV-family enzyme, is resistant to inactivation by beta-lactamase inhibitors. Analysis of purified Met69-->Ile enzyme reveals that its isoelectric point (pI 7.0) and CD spectrum are identical with those of the OHIO-1 enzyme. Levels of beta-lactamase expression in Escherichia coli as determined by immunoblotting are similar for OHIO-1 and Met69-->Ile beta-lactamase. The kinetic constants of the Met69-->Ile enzyme compared with OHIO-1 are smaller for benzylpenicillin (Km = 6 microM compared with 17 microM; kcat = 234 s-1 compared with 345 s-1 respectively) and carbenicillin (Km = 3 microM compared with 17 microM; kcat = 131 s-1 compared with 320 s-1 respectively). For the cephalosporins cephaloridine and 7-(thienyl- 2-acetamido)-3-[2-(4-N,N- dimethylaminophenylazo)pyridinium-methyl]-3-cephem-4-carboxylic acid (PADAC), a similar pattern is also seen (Km=38 microM compared with 96 microM and 6 microM compared with 75 microM respectively; kcat = 235 s-1 compared with 1023 s-1 and 9 s-1 compared with 50 s-1 respectively). Consistent with minimum inhibitory concentrations that show resistance to beta-lactam beta-lactamase inhibitors, the apparent Ki values, turnover numbers and partition ratios (kcat/kinact) for the mechanism-based inactivators clavulanate, sulbactam and tazobactam are increased. The inactivation rate constants (kinact) are decreased. The difference in activation energy, a measurement of altered affinity for the wild-type and mutant enzymes leading to acylation of the active site, reveals small energy differences of less than 8.4 kJ/mol. In total, these results suggest that the Met-->Ile substitution at position 69 in the OHIO-1 beta-lactamase alters the active site, primarily affecting the interactions with beta-lactamase inhibitors.

MeSH terms

  • Anti-Bacterial Agents / pharmacology
  • Circular Dichroism
  • Clavulanic Acid / pharmacology
  • Enzyme Inhibitors / pharmacology
  • Escherichia coli
  • Isoleucine / genetics
  • Isoleucine / metabolism
  • Kinetics
  • Methionine / genetics
  • Methionine / metabolism
  • Microbial Sensitivity Tests
  • Penicillanic Acid / analogs & derivatives
  • Penicillanic Acid / pharmacology
  • Point Mutation
  • Protein Conformation
  • Sulbactam / pharmacology
  • Tazobactam
  • beta-Lactam Resistance*
  • beta-Lactamases / biosynthesis
  • beta-Lactamases / genetics*
  • beta-Lactamases / metabolism*

Substances

  • Anti-Bacterial Agents
  • Enzyme Inhibitors
  • Isoleucine
  • Clavulanic Acid
  • Penicillanic Acid
  • Methionine
  • beta-Lactamases
  • Sulbactam
  • Tazobactam