Dielectric and Mechanic Relaxation in Polyelectrolyte-Supported Bilayer Stacks: A Model for the Dynamics of Membranes?

The dielectric and mechanical relaxation of two different polyelectrolyte−lipid complexes with a stack-of-bilayer morphology is characterized by broad band dielectric spectroscopy in the frequency range between 10 -2 and 10 7 Hz and by dynamic shear relaxation experiments. With these experiments, we compare a synthetic model system consisting of polyacrylic acid and didodecyldimethylammonium counterions (PAA−C 12 2 ) with the complex of a fraction of soybean lecithine and a cationic polyelectrolyte (PDADMAC−Lec). The lamellar morphologies consisting of stacks of bilayers are characterized by quantitative small angle X-ray scattering measurements. PAA−C 12 2 shows in the mechanical experiment two β-relaxation processes and exhibits at room temperature a storage modulus of G‘ ≈ 200 MPa which is considering the observed good deformability very high. The whole behavior is similar to high-performance loaded rubbers and reflects the extraordinary mechanical response of the lamellar superstructure. For PDADMAC−Lec, a less structured relaxation behavior and lower moduli are found. Above the glass transition, a transition zone is observed which is followed by a rubbery plateau with G‘ being still on the order of 1 MPa. Considering the very high deformability of this material, the natural polyelectrolyte lipid complex turned out to be an excellent rubbery material. In the dielectric relaxation experiment, both systems show a very similar behavior which is regarded to be typical for a stack-of-bilayer order. At low temperatures, localized β-relaxations are described which are tentatively assigned to lipid motions. In addition, both systems exhibit a transition from a nonohmic to an ohmic conductivity which occurs close to the softening point of the polyelectrolyte layers.