Nonlinear electrical and rheological spectroscopies identify structural and supramolecular relaxations in a model peptide.

Abstract

Supercooled liquid secondary amides display an electrical absorption peak characterized by an almost Debye-like shape, indicative of a close-to-exponential polarization response. This response, believed to be supramolecular in nature, is so enormously intense that the amide's structural process, contributing only a few percent to the total relaxation strength, is hard to resolve reliably using standard dielectric spectroscopy. To overcome this issue, nonlinear dielectric spectroscopy involving field-induced structural recovery and temperature-induced physical aging, was applied near the calorimetric glass transition of a mixture of N-methylformamide and N-ethylacetamide. Without the need to rely on cumbersome deconvolution procedures, it is thus demonstrated that the supramolecular response is by a factor of 6 slower than the structural relaxation. Conversely, in linear rheological experiments only the structural relaxation could be resolved, but not the supramolecular one. However, medium-amplitude oscillatory shear experiments carried out at 160 K do reveal the supramolecular process. Hence, the combination of linear and nonlinear mechanical measurements corroborates the dielectrically uncovered spectral separation of the two processes.