Free Activation Energies and Activation Volumes for the Amide Rotation in Some Peptides Studied by High Pressure 1H-High Resolution NMR

From the pressure dependence of 1H high resolution NMR spectra of two dipeptides (glycylsarcosine and N-acetyl-ʟ-proline-NH-methylamide in the range 0.1 MPa ≤p ≤ 150 MPa the activation volumes ⊿V≠ for the amide rotation are derived. This conformational transition is characterized for glycylsarcosine by ⊿V≠ = 4 ± 1 cm3 · mol-1 and for. the proline derivative by ⊿V≠ = 7.5±1 cm3 · mol-1. From the given results the maximum contribution of proline cis ⇌ trans isomerisation to the pressure dependence of the rate of reactivation of proteins can be estimated to ~ - 30% per MPa and proline present.