Highly viscoelastic films at the water/air interface: α-Cyclodextrin with anionic surfactants.

This work showcases the remarkable viscoelasticity of films consisting of α-cyclodextrin (α-CD) and anionic surfactants (S) at the water/air interface, the magnitude of which has not been observed in similar systems. The anionic surfactants employed are sodium salts of a homologous series of n-alkylsulfates (n = 8-14) and of dodecylsulfonate. Our hypothesis was that the very high viscoelasticity can be systematically related to the bulk and interfacial properties of the system.

Complex Behavior of Aqueous α-Cyclodextrin Solutions. Interfacial Morphologies Resulting from Bulk Aggregation.

The spontaneous aggregation of α-cyclodextrin (α-CD) molecules in the bulk aqueous solution and the interactions of the resulting aggregates at the liquid/air interface have been studied at 283 K using a battery of techniques: transmission electron microscopy, dynamic light scattering, dynamic surface tensiometry, Brewster angle microscopy, neutron reflectometry, and ellipsometry. We show that α-CD molecules spontaneously form aggregates in the bulk that grow in size with time. These aggregates adsorb to the liquid/air interface with their size in the bulk determining the adsorption rate.

A small molecular size system giving unexpected surface effects: alpha-Cyclodextrin + sodium dodecyl sulfate in water.

Maximum drop volumes (MDV) and the resultant surface tension values (sigma) of alpha-cyclodextrin (alpha-CD) + sodium dodecyl sulfate (SDS) aqueous mixtures have been determined over a broad concentration range of both solutes at 283.15, 293.15, 303.

Cyclodextrin-based self-assembled nanotubes at the water/air interface.

Native alpha-cyclodextrin (alpha-CD) is found to spontaneously form films at aqueous solution/air interfaces. Shape-response measurements to volume perturbations on drops hanging from a capillary indicate that temperature and sodium dodecyl sulfate (SDS) concentration strongly modify the viscoelastic properties of such films. By using isothermal titration calorimetry (ITC), Brewster angle microscopy (BAM), atomic force microscopy (AFM), and molecular dynamics (MD) simulations, it is shown that the films consist of self-assembled nanotubes whose building blocks are cyclodextrin dimers (alpha-CD2) and alpha-CD2-SDS1 complexes.