Targeted Covalent Inhibition of Prolyl Oligopeptidase (POP): Discovery of Sulfonylfluoride Peptidomimetics

Cell Chem Biol. 2018 Aug 16;25(8):1031-1037.e4. doi: 10.1016/j.chembiol.2018.04.013. Epub 2018 May 17.

Abstract

Prolyl oligopeptidase (POP), a serine protease highly expressed in the brain, has recently emerged as an enticing therapeutic target for the treatment of cognitive and neurodegenerative disorders. However, most reported inhibitors suffer from short duration of action, poor protease selectivity, and low blood-brain barrier (BBB) permeability, which altogether limit their potential as drugs. Here, we describe the structure-based design of the first irreversible, selective, and brain-permeable POP inhibitors. At low-nanomolar concentrations, these covalent peptidomimetics produce a fast, specific, and sustained inactivation of POP, both in vitro and in human cells. More importantly, they are >1,000-fold selective against two family-related proteases (DPPIV and FAP) and display high BBB permeability, as shown in both lipid membranes and MDCK cells.

Keywords: CNS disorders; blood-brain barrier; covalent inhibitors; enzyme inhibitors; peptidomimetics.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Blood-Brain Barrier / metabolism
  • Cell Line
  • Dogs
  • Drug Discovery
  • Fluorides / chemistry*
  • Fluorides / pharmacokinetics
  • Fluorides / pharmacology*
  • Humans
  • Madin Darby Canine Kidney Cells
  • Models, Molecular
  • Peptidomimetics / chemistry*
  • Peptidomimetics / pharmacokinetics
  • Peptidomimetics / pharmacology*
  • Permeability
  • Prolyl Oligopeptidases
  • Serine Endopeptidases / metabolism*
  • Serine Proteinase Inhibitors / chemistry*
  • Serine Proteinase Inhibitors / pharmacokinetics
  • Serine Proteinase Inhibitors / pharmacology*

Substances

  • Peptidomimetics
  • Serine Proteinase Inhibitors
  • Serine Endopeptidases
  • PREPL protein, human
  • Prolyl Oligopeptidases
  • Fluorides