Temperature-induced structure switch in thermo-responsive micellar interpolyelectrolyte complexes: toward core-shell-corona and worm-like morphologies

The spontaneous formation and thermo-responsiveness of a colloidally-stable interpolyelectrolyte complex (IPEC) based on a linear temperature-sensitive diblock copolymer poly(vinyl sulfonate)(31)-b-poly(N-isopropyl acrylamide)(27) (PVS31-b-PNIPAM(27)) and a star-shaped quaternized miktoarm polymer poly(ethylene oxide)(114)-(poly(2-(dimethylamino)ethyl methacrylate)(17))(4) (PEO114-(qPDMAEMA(17))(4)) was investigated in aqueous media at 0.3 M NaCl by means of dynamic light scattering (DLS), small angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryo-TEM). The micellar macromolecular co-assemblies show a temperature-dependent size and morphology, which result from the lower critical solution temperature (LCST) behavior of the PNIPAM-blocks. Hence, the micellar co-assemblies grow upon heating. At 60 degrees C, spherical core-shell-corona co-assemblies are proposed with a hydrophobic PNIPAM core, a water-insoluble IPEC shell, and a hydrophilic PEO corona. These constructs develop into a rod-like structure upon extended equilibration. In turn, PEO-arms and PNIPAM-blocks within a hydrophilic mixed two-component corona surround the water-insoluble IPEC domain at 20 degrees C, thereby forming spherical core-corona co-assemblies. Reversibility of the structural changes is suggested by the scattering data. This contribution addresses the use of a combination of oppositely charged thermo-responsive and bis-hydrophilic star-shaped polymeric components toward IPECs of diverse morphological types.