Photoswitchable elements within a peptide backbone-ultrafast spectroscopy of thioxylated amides

J Phys Chem B. 2005 Mar 17;109(10):4770-5. doi: 10.1021/jp045151t.

Abstract

A series of thioxo compounds, thioacetamide, N-methylthioacetamide, a cyclic thioxoamide [(S)-5-thioxopyrrolidine-2-carboxylic acid ethyl ester], two thioxylated dipeptides (Ala-Psi[CS-NH]-Ala and Phe-Psi[CS-NH]-Ala) and a thioxylated dodecapeptide (Lys-Glu-Thr-Ala-Ala-Ala-Lys-Phe-Glu-Arg-Gln-His-Psi[CS-NH]-Nle-Asp-Ser-Ser-Thr-Ser-Ala-Ala, or [thioxo-His(12)]-S-peptide; Nle = norleucine) are investigated by ultrafast spectroscopy in the visible and near UV. The different molecules show very similar absorption dynamics featuring a rise of a strong visible absorption band on the subpicosecond and picosecond time scale. The decay of the visible absorption occurs within 150-600 ps. The observations are interpreted by the ultrafast formation of triplet states and their decay on the subnanosecond time scale. Comparison with published IR experiments on N-methylthioacetamide indicates that the cis-trans isomerization around the thioxopeptide bond is terminated within less than 1 ns.

MeSH terms

  • Amides / chemistry*
  • Data Interpretation, Statistical
  • Peptides / chemistry*
  • Photochemistry
  • Spectrophotometry, Ultraviolet
  • Sulfhydryl Compounds / chemistry*
  • Thioacetamide / analogs & derivatives
  • Thioacetamide / chemistry

Substances

  • Amides
  • N-methylthioacetamide
  • Peptides
  • Sulfhydryl Compounds
  • Thioacetamide