Photo-control of peptide conformation on a timescale of seconds with a conformationally constrained, blue-absorbing, photo-switchable linker

Org Biomol Chem. 2008 Dec 7;6(23):4323-32. doi: 10.1039/b810533b. Epub 2008 Sep 24.

Abstract

Azobenzene derivatives can be used to reversibly photo-regulate conformation and activity when introduced as intramolecular bridges in peptides and proteins. Here we report the design, synthesis, and characterization of an azobenzene derivative that absorbs between 400-450 nm in aqueous solution to produce the cis isomer, and relaxes back to the trans isomer with a half-life of a few seconds at room temperature. In the trans form, the linker can span a distance of approximately 25 A, so that it can bridge Cys residues spaced i, i + 15 in an alpha-helix. Switching of the azobenzene cross-linker from trans to cis causes a decrease in the helix content of peptides where the linker is attached via Cys residues spaced at i, i + 15 and i, i + 14 positions, no change in helix content with Cys residues spaced i, i + 11 and an increase in helix content in a peptide with Cys residues spaced at i, i + 7. In the presence of 10 mM reduced glutathione, the azobenzene cross-linker continued to photo-switch after 24 hours. This cross-linker design thus expands the possibilities for fast photo-control of peptide and protein structure in biochemical systems.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Absorption
  • Amino Acid Sequence
  • Azo Compounds / chemistry
  • Color
  • Cross-Linking Reagents / chemical synthesis
  • Cross-Linking Reagents / metabolism
  • Cross-Linking Reagents / pharmacology*
  • Drug Design
  • Glutathione / metabolism
  • Hydrogen-Ion Concentration
  • Isomerism
  • Kinetics
  • Molecular Sequence Data
  • Peptides / chemistry*
  • Peptides / metabolism
  • Photochemistry
  • Protein Conformation / drug effects
  • Solvents / chemistry
  • Spectrophotometry, Ultraviolet
  • Sulfhydryl Compounds / chemistry
  • Temperature
  • Time Factors

Substances

  • Azo Compounds
  • Cross-Linking Reagents
  • Peptides
  • Solvents
  • Sulfhydryl Compounds
  • azobenzene
  • Glutathione