Reversible ketomethylene-based inhibitors of human neutrophil proteinase 3

J Med Chem. 2014 Nov 26;57(22):9396-408. doi: 10.1021/jm500782s. Epub 2014 Nov 12.

Abstract

Neutrophil serine proteases, proteinase 3 (PR3) and human neutrophil elastase (HNE), are considered as targets for chronic inflammatory diseases. Despite sharing high sequence similarity, the two enzymes have different substrate specificities and functions. While a plethora of HNE inhibitors exist, PR3 specific inhibitors are still in their infancy. We have designed ketomethylene-based inhibitors for PR3 that show low micromolar IC50 values. Their synthesis was made possible by amending a previously reported synthesis of ketomethylene dipeptide isosteres to allow for the preparation of derivatives suitable for solid phase peptide synthesis. The best inhibitor (Abz-VADnV[Ψ](COCH2)ADYQ-EDDnp) was found to be selective for PR3 over HNE and to display a competitive and reversible inhibition mechanism. Molecular dynamics simulations show that the interactions between enzyme and ketomethylene-containing inhibitors are similar to those with the corresponding substrates. We also confirm that N- and C-terminal FRET groups are important for securing high inhibitory potency toward PR3.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Binding, Competitive
  • Catalytic Domain
  • Chemistry, Pharmaceutical / methods
  • Dipeptides / chemistry
  • Drug Design
  • Enzyme Inhibitors / chemistry*
  • Fluorescence Resonance Energy Transfer / methods
  • Humans
  • Inflammation
  • Inhibitory Concentration 50
  • Ketones / chemistry
  • Models, Molecular
  • Molecular Dynamics Simulation
  • Myeloblastin / antagonists & inhibitors*
  • Myeloblastin / chemistry*
  • Peptides / chemistry
  • Substrate Specificity

Substances

  • Dipeptides
  • Enzyme Inhibitors
  • Ketones
  • Peptides
  • Myeloblastin