Combined X-ray, NMR, and kinetic analyses reveal uncommon binding characteristics of the hepatitis C virus NS3-NS4A protease inhibitor BI 201335

J Biol Chem. 2011 Apr 1;286(13):11434-43. doi: 10.1074/jbc.M110.211417. Epub 2011 Jan 26.

Abstract

Hepatitis C virus infection, a major cause of liver disease worldwide, is curable, but currently approved therapies have suboptimal efficacy. Supplementing these therapies with direct-acting antiviral agents has the potential to considerably improve treatment prospects for hepatitis C virus-infected patients. The critical role played by the viral NS3 protease makes it an attractive target, and despite its shallow, solvent-exposed active site, several potent NS3 protease inhibitors are currently in the clinic. BI 201335, which is progressing through Phase IIb trials, contains a unique C-terminal carboxylic acid that binds noncovalently to the active site and a bromo-quinoline substitution on its proline residue that provides significant potency. In this work we have used stopped flow kinetics, x-ray crystallography, and NMR to characterize these distinctive features. Key findings include: slow association and dissociation rates within a single-step binding mechanism; the critical involvement of water molecules in acid binding; and protein side chain rearrangements, a bromine-oxygen halogen bond, and profound pK(a) changes within the catalytic triad associated with binding of the bromo-quinoline moiety.

MeSH terms

  • Aminoisobutyric Acids
  • Carrier Proteins / antagonists & inhibitors*
  • Carrier Proteins / chemistry*
  • Catalytic Domain
  • Clinical Trials, Phase I as Topic
  • Crystallography, X-Ray
  • Hepacivirus / enzymology*
  • Hepatitis C / drug therapy
  • Hepatitis C / enzymology
  • Humans
  • Intracellular Signaling Peptides and Proteins
  • Leucine / analogs & derivatives
  • Nuclear Magnetic Resonance, Biomolecular
  • Oligopeptides / chemistry*
  • Oligopeptides / therapeutic use
  • Proline / analogs & derivatives
  • Protease Inhibitors / chemistry*
  • Protease Inhibitors / therapeutic use
  • Protein Binding
  • Quinolines
  • Thiazoles / chemistry*
  • Thiazoles / therapeutic use
  • Viral Nonstructural Proteins / antagonists & inhibitors*
  • Viral Nonstructural Proteins / chemistry*

Substances

  • Aminoisobutyric Acids
  • Carrier Proteins
  • Intracellular Signaling Peptides and Proteins
  • NS3 protein, hepatitis C virus
  • NS4A cofactor peptide, Hepatitis C virus
  • Oligopeptides
  • Protease Inhibitors
  • Quinolines
  • Thiazoles
  • Viral Nonstructural Proteins
  • faldaprevir
  • Proline
  • Leucine

Associated data

  • PDB/3P8N
  • PDB/3P8O