Nano-patterned structures in cylindrical polyelectrolyte brushes assembled with oppositely charged polyions

We demonstrate that the electrostatically driven association of cylindrical polyelectrolyte brushes (CPBs) with oppositely charged linear polyelectrolytes (PEs) in dilute aqueous solution gives rise to well-defined and colloidaly stable (not undergoing secondary aggregation with time) polymeric nano-assemblies representing novel water-soluble interpolyelectrolyte complexes (IPECs). Each complex particle comprises a single "host'' CPB whose charge is undercompensated by the "guest'' PE chains. Molecular dynamics (MD) simulations were used to probe the structural organization of these nano-assemblies. We find that they spontaneously adopt the shape of a necklace of complex coacervate pearls which comprise charged monomer units of CPB and those of the guest PEs in approximately stoichiometric (1 : 1) ratio. Each complex coacervate pearl is decorated by a star-like PE corona formed by the branches of the CPB not involved in the interpolyelectrolyte complexation. Repulsive interactions between these coronas stabilize the periodic intra-molecular structure and assure aggregative stability of the IPEC derived from the single CPB. AFM images of the complex particles deposited on mica unambiguously support their pearl-necklace structural organization. Our work theoretically predicts and experimentally confirms a possibility to tune the periodicity of one-dimensional intramolecular nano-patterned structures at will by a variation of the base-molar ratio between the oppositely charged macromolecular building blocks incorporated in the polymeric nano-assembly, that is, by a variation of the stoichiometry of the IPECs.