Hydrogen exchange-mass spectrometry measures stapled peptide conformational dynamics and predicts pharmacokinetic properties

Anal Chem. 2013 Dec 3;85(23):11185-8. doi: 10.1021/ac403173p. Epub 2013 Nov 14.

Abstract

Peptide drugs have traditionally suffered from poor pharmacokinetic properties due to their conformational flexibility and the interaction of proteases with backbone amide bonds. "Stapled Peptides" are cyclized using an all-hydrocarbon cross-linking strategy to reinforce their α-helical conformation, yielding improved protease resistance and drug-like properties. Here we demonstrate that hydrogen exchange-mass spectrometry (HX-MS) effectively probes the conformational dynamics of Stapled Peptides derived from the survivin-borealin protein-protein interface and predicts their susceptibility to proteolytic degradation. In Stapled Peptides, amide exchange was reduced by over five orders-of-magnitude versus the native peptide sequence depending on staple placement. Furthermore, deuteration kinetics correlated directly with rates of proteolysis to reveal the optimal staple placement for improved drug properties.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Sequence
  • Deuterium Exchange Measurement / methods*
  • Forecasting
  • Hydrogen / chemistry
  • Mass Spectrometry / methods*
  • Molecular Sequence Data
  • Peptide Fragments / analysis*
  • Peptide Fragments / chemistry*
  • Peptide Fragments / pharmacokinetics
  • Pharmacokinetics
  • Protein Conformation
  • Protein Structure, Tertiary

Substances

  • Peptide Fragments
  • Hydrogen