Yv. Toropov et al., Molecular dynamics and spatial distribution of TOAC spin-labelled peptaibols studied in glassy liquid by echo-detected EPR spectroscopy, APPL MAGN R, 15(2), 1998, pp. 237-246
2,2,6,6-tetramethylpiperidine-1-oxyl-4-carboxylic acid (TOAC) spin-labelled
analogues of the Aib-rich peptide (peptaibol) Trichogin GA IV are investig
ated in a glassy methanol/glycerol (70/30 v/v%) system, using conventional
CW EPR and electron spin echo spectroscopy. Echo-detected (ED) EPR spectra
indicate that the labels undergo restricted orientational motion (libration
). Comparison with the small molecular spin probe Tempone shows that the dy
namics of peptide molecules is determined by their structure and not by the
surrounding medium. At the terminal positions (position 1 and 8) TOAC resi
dues were found to be more flexible than at the central 4th position. Insta
ntaneous diffusion mechanism in electron spin echo, which also contributes
to the ED EPR spectra, was employed for deriving the local concentration of
peptaibols. This approach may serve as a tool for investigation of peptide
aggregation. In the studied model glassy solution the peptaibols were foun
d to be randomly distributed.