310-Helix stabilization and screw sense control via stereochemically configured 4-atom hydrocarbon staples

Bioorg Med Chem. 2024 Nov 15:114:117963. doi: 10.1016/j.bmc.2024.117963. Epub 2024 Oct 22.

Abstract

The 310-helix is a crucial secondary structure in proteins, playing an essential role in various protein-protein interactions, yet stabilizing it in biologically relevant peptides remains challenging. In this study, we investigated the potential of 4-atom hydrocarbon staples to stabilize 310-helices in peptides. Using ring-closing metathesis, we demonstrated that the staple's configuration is critical for both the stabilization and screw sense control of 310-helices. Circular dichroism spectroscopy revealed that the Ri,i+3S(4) staple-a 4-atom cross-link with (R)-configuration at the i position, (S)-configuration at the i + 3 position, and flanked by methyl groups-strongly induces right-handed 310-helices, especially in sequences with proteinogenic l-amino acids. Furthermore, multiple staples effectively stabilized longer peptides, underscoring the versatility of this approach for applications in peptide therapeutics and biomolecular engineering.

Keywords: 3(10)-Helix; Hydrocarbon staples; Peptide conformation; Proteinogenic peptides; Screw sense control.

MeSH terms

  • Circular Dichroism
  • Hydrocarbons* / chemistry
  • Models, Molecular
  • Molecular Structure
  • Peptides* / chemical synthesis
  • Peptides* / chemistry
  • Protein Stability
  • Protein Structure, Secondary
  • Stereoisomerism

Substances

  • Peptides
  • Hydrocarbons