Bromo-substituted indirubins for inhibition of protein kinase-mediated signalling involved in inflammatory mediator release in human monocytes

Bioorg Chem. 2024 Aug:149:107470. doi: 10.1016/j.bioorg.2024.107470. Epub 2024 May 23.

Abstract

Targeting protein kinases that regulate signalling pathways in inflammation is an effective pharmacological approach to alleviate uncontrolled inflammatory diseases. In this context, the natural product indirubin and its 6-bromo-substituted analogue 6-bromoindirubin-3 -glycerol-oxime ether (6BIGOE; 1) were identified as potent inhibitors of glycogen synthase kinase-3β (GSK-3β). These inhibitors suppress the release of pro-inflammatory cytokines and prostaglandins (PG) from human monocytes. However, indirubin derivatives target several protein kinases such as cyclin-dependent kinases (CDKs) which has been a major concern for their application in inflammation therapy. Here, we report on a library of 13 5-bromo-substituted indirubin derivatives that have been designed to improve potency and target selectivity. Side-by-side comparison of reference compound 1 (6BIGOE) with 5-bromo derivatives revealed its isomer 2 (5BIGOE), as the most potent derivative able to supress pro-inflammatory cytokine and PG release in lipopolysaccharide-stimulated human monocytes. Analysis of protein kinase inhibition in intact monocytes, supported by our in silico findings, proposed higher selectivity of 1 for GSK-3β inhibition with lesser potency against CDKs 8 and 9. In contrast, 2 supressed the activity of these CDKs with higher effectiveness than GSK-3β, representing additional targets of indirubins within the inflammatory response. Encapsulation of 1 and 2 into polymer-based nanoparticles (NP) improved their pharmacological potential. In conclusion, the 5- and 6-brominated indirubins 1 and 2 as dual GSK-3β and CDK8/9 inhibitors represent a novel concept for intervention with inflammatory disorders.

Keywords: Bromoindirubins; Cyclin-dependent kinases; Cytokines; Glycogen synthase kinase-3β; Inflammation; Monocytes; Polymer-based nanoparticles; Prostaglandins.

MeSH terms

  • Cytokines / antagonists & inhibitors
  • Cytokines / metabolism
  • Dose-Response Relationship, Drug
  • Humans
  • Indoles* / chemistry
  • Indoles* / pharmacology
  • Inflammation Mediators / antagonists & inhibitors
  • Inflammation Mediators / metabolism
  • Lipopolysaccharides / antagonists & inhibitors
  • Lipopolysaccharides / pharmacology
  • Molecular Docking Simulation
  • Molecular Structure
  • Monocytes* / drug effects
  • Monocytes* / metabolism
  • Protein Kinase Inhibitors* / chemical synthesis
  • Protein Kinase Inhibitors* / chemistry
  • Protein Kinase Inhibitors* / pharmacology
  • Signal Transduction* / drug effects
  • Structure-Activity Relationship

Substances

  • Indoles
  • Protein Kinase Inhibitors
  • indirubin
  • Inflammation Mediators
  • Lipopolysaccharides
  • Cytokines