Nitrobenzoxadiazole-based GSTP1-1 inhibitors containing the full peptidyl moiety of (pseudo)glutathione

J Enzyme Inhib Med Chem. 2016 Dec;31(6):924-30. doi: 10.3109/14756366.2015.1070845. Epub 2015 Sep 2.

Abstract

Context: The inhibition of glutathione S-transferase P1-1 (GSTP1-1) is a sound strategy to overcome drug resistance in oncology practice.

Objective: The nitrobenzoxadiazolyl (NBD) S-conjugate of glutathione and the corresponding γ-oxa-glutamyl isostere (compounds 1 and 5, respectively) have been disclosed as GST inhibitors. The rationale of their design is discussed in juxtaposition to non-peptide NBD thioethers.

Materials and methods: Synthesis of derivatives 1 and 5 and in vitro evaluation on human GSTP1-1 and M2-2 are reported.

Results: Conjugates 1 and 5 were found to be low micromolar inhibitors of both isoforms. Furthermore, they display a threefold reduction in selectivity for GSTM2-2 over the P1-1 isozyme in comparison with the potent non-peptide inhibitor nitrobenzoxadiazolyl-thiohexanol (NBDHEX).

Discussion and conclusions: Spectroscopic data are congruent with the formation of a stable sigma-complex between GSH and the inhibitors in the protein active site. Conjugate 5 is suitable for in vivo modulation of GST activity in cancer treatment.

Keywords: Glutathione S-conjugates; glutathione S-transferases; nitrobenzoxadiazole S-derivatives; pseudopeptide; urethane bond.

MeSH terms

  • 4-Chloro-7-nitrobenzofurazan / chemical synthesis
  • 4-Chloro-7-nitrobenzofurazan / chemistry
  • 4-Chloro-7-nitrobenzofurazan / pharmacology*
  • Dose-Response Relationship, Drug
  • Enzyme Inhibitors / chemical synthesis
  • Enzyme Inhibitors / chemistry*
  • Enzyme Inhibitors / pharmacology*
  • Glutathione / chemistry
  • Glutathione / pharmacology*
  • Glutathione S-Transferase pi / antagonists & inhibitors*
  • Glutathione S-Transferase pi / metabolism
  • Glutathione Transferase / antagonists & inhibitors*
  • Glutathione Transferase / metabolism
  • Humans
  • Molecular Structure
  • Structure-Activity Relationship

Substances

  • Enzyme Inhibitors
  • Glutathione S-Transferase pi
  • Glutathione Transferase
  • glutathione S-transferase Mu 2
  • 4-Chloro-7-nitrobenzofurazan
  • Glutathione