Crystal Structures of Trimethoprim-Resistant DfrA1 Rationalize Potent Inhibition by Propargyl-Linked Antifolates

ACS Infect Dis. 2016 Feb 12;2(2):149-56. doi: 10.1021/acsinfecdis.5b00129. Epub 2016 Jan 4.

Abstract

Multidrug-resistant Enterobacteriaceae, notably Escherichia coli and Klebsiella pneumoniae, have become major health concerns worldwide. Resistance to effective therapeutics is often carried by class I and II integrons that can confer insensitivity to carbapenems, extended spectrum β-lactamases, the antifolate trimethoprim, fluoroquinolones, and aminoglycosides. Specifically of interest to the study here, a prevalent gene (dfrA1) coding for an insensitive dihydrofolate reductase (DHFR) confers 190- or 1000-fold resistance to trimethoprim for K. pneumoniae and E. coli, respectively. Attaining inhibition of both the wild-type and resistant forms of the enzyme is critical for new antifolates. For several years, we have been developing the propargyl-linked antifolates (PLAs) as effective inhibitors against trimethoprim-resistant DHFR enzymes. Here, we show that the PLAs are active against both the wild-type and DfrA1 DHFR proteins. We report two high-resolution crystal structures of DfrA1 bound to potent PLAs. The structure-activity relationships and crystal structures will be critical in driving the design of broadly active inhibitors against wild-type and resistant DHFR.

Keywords: DfrA1; Enterobacteriaceae; antifolate; resistance; trimethoprim.

MeSH terms

  • Anti-Bacterial Agents / chemistry*
  • Anti-Bacterial Agents / pharmacology*
  • Bacterial Proteins / chemistry
  • Crystallography, X-Ray
  • Escherichia coli / enzymology
  • Folic Acid Antagonists / chemistry*
  • Folic Acid Antagonists / pharmacology*
  • Humans
  • Integrons
  • Klebsiella pneumoniae / enzymology
  • Structure-Activity Relationship
  • Tetrahydrofolate Dehydrogenase / chemistry*
  • Trimethoprim / pharmacology*
  • Trimethoprim Resistance / drug effects*
  • beta-Lactamases / metabolism

Substances

  • Anti-Bacterial Agents
  • Bacterial Proteins
  • Folic Acid Antagonists
  • Trimethoprim
  • Tetrahydrofolate Dehydrogenase
  • beta-Lactamases