The mutation T315A in Candida albicans sterol 14alpha-demethylase causes reduced enzyme activity and fluconazole resistance through reduced affinity

J Biol Chem. 1997 Feb 28;272(9):5682-8. doi: 10.1074/jbc.272.9.5682.

Abstract

Sterol 14alpha-demethylase (P45051) is the target for azole antifungal compounds, and resistance to these drugs and agrochemicals is of significant practical importance. We undertook site-directed mutagenesis of the Candida albicans P45051 heterologously expressed in Saccharomyces cerevisiae to probe a model structure for the enzyme. The change T315A reduced enzyme activity 2-fold as predicted for the removal of the residue that formed a hydrogen bond with the 3-OH of the sterol substrate and helped to locate it in the active site. This alteration perturbed the heme environment, causing an altered reduced carbon monoxide difference spectrum with a maximum at 445 nm. The changes also reduced the affinity of the enzyme for the azole antifungals ketoconazole and fluconazole and after expression induced by galactose caused 4-5-fold azole resistance in transformants of S. cerevisiae. This is the first example of a single base change in the target enzyme conferring resistance to azoles through reduced azole affinity.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Sequence
  • Animals
  • Antifungal Agents / pharmacology*
  • Candida albicans / enzymology*
  • Cytochrome P-450 Enzyme System / genetics*
  • Cytochrome P-450 Enzyme System / metabolism
  • Drug Resistance, Microbial
  • Electron Spin Resonance Spectroscopy
  • Fluconazole / pharmacology*
  • Humans
  • Kinetics
  • Molecular Sequence Data
  • Mutagenesis
  • Oxidoreductases / genetics*
  • Oxidoreductases / metabolism
  • Rats
  • Restriction Mapping
  • Sequence Alignment
  • Sterol 14-Demethylase

Substances

  • Antifungal Agents
  • CYP51A1 protein, human
  • Fluconazole
  • Cytochrome P-450 Enzyme System
  • Oxidoreductases
  • Sterol 14-Demethylase