Facile Screening of Various Micellar Morphologies by Blending Miktoarm Stars and Diblock Copolymers.

A time-saving phase-diagram screening is introduced for the self-assembly of miktoarm star polymers with different arm numbers for the insoluble part. Agreeing with theory, all conventional micellar morphologies (spherical star-like micelles, cylindrical micelles and vesicles) can be accessed by adjusting the average arm number when blending miktoarm stars with diblock copolymers (at constant arm/block lengths). Additionally, a rare clustered vesicle phase is detected. Hence, this approach permits an easy tuning of the equilibrium morphology and the size of the solvophobic domain. Such screening by scattering, ultracentrifugation, and electron microscopy techniques assists the targeted synthesis of miktoarm stars with a well-defined arm number, aimed at the morphology control of the nanostructures without blending. Specifically, we demonstrate a systematic variation of all classical micellar morphologies based on interpolyelectrolyte complexes (IPECs), consisting of a water-insoluble part formed by electrostatically coupled poly(styrenesulfonate) chains/quaternized poly(2-(dimethylamino)ethyl methacrylate) blocks, being stabilized by hydrophilic poly(ethylene oxide) blocks.