  Following up a recent paper on grafted sliding polymer layers (Macromolecules
2005, 38, 1434-1441), we investigated the influence of the sliding degree of
freedom on the self-assembly of sliding polymeric surfactants that can be
obtained by complexation of polymers with cyclodextrins. In contrast to the
micelles of quenched block copolymer surfactants, the free energy of micelles
of sliding surfactants can have two minima: the first corresponding to small
micelles with symmetric arm lengths, and the second corresponding to large
micelles with asymmetric arm lengths. The relative sizes and concentrations of
small and large micelles in the solution depend on the molecular parameters of
the system. The appearance of small micelles drastically reduces the kinetic
barrier signifying the fast formation of equilibrium micelles.
