Membrane stiffening in Chitosan mediated multilamellar vesicles of alkyl ether carboxylates

Abstract

Hypothesis: Membrane undulations are known to strongly affect the stability of uni- and multilamellar vesicles formed by surfactants or phospholipids. Herein, based on the same arguments, we hypothesise that the properties of polyelectrolyte mediated surfactant multilamellar vesicles, in particular the multiplicity - i.e. the number of layers forming the vesicle - depend on the dynamics of the membrane.

Experiments: Small-angle neutron scattering (SANS) and neutron spin-echo (NSE) were used to probe the structure and the dynamics of the multilayered vesicles formed in mixtures of the biopolymer chitosan and oppositely charged alkyl ether carboxylates. The neutron scattering data are complemented by static and dynamic light scattering experiments. Experiments were performed in polyelectrolyte excess conditions, and at a pH close to the pKa of the surfactant.

Findings: The structural investigation shows very clearly that multilayered surfactant/polyelectrolyte vesicles are formed in the investigated mixtures. Only 3 to 5 layers form, on average, one vesicle, as similarly found in mixtures of chitosan and phospholipid vesicles. NSE shows that the surfactant membrane becomes stiffer upon complexation with chitosan, and that the fluctuation of the layers is strongly coupled in time and space. Such strong coupling and the increase in overall stiffness is associated with a high entropic cost. Accordingly, the combined SANS and NSE study points out that the low multiplicity found in multilayered vesicles involving the rigid polysaccharide chitosan arises from the strongly coupled dynamics of the membrane layers.

Keywords: Chitosan; Membrane dynamics; Multilayered vesicles; Self-assembly; Small-angle scattering.