Soft patchy nanoparticles from solution-phase self-assembly of binary diblock copolymers.

The fabrication of highly ordered, defect-free nanostructures is a key challenge in nanotechnology. Bottom-up fabrication approaches require nanobuilding blocks of precisely defined size and shape. In this work we propose a simple approach to obtain one type of building block--soft patchy nanoparticles--suggested by a series of coarse grain molecular dynamics simulations. A binary mixture of two different diblock copolymers with a common hydrophobic block but sufficiently dissimilar hydrophilic blocks reliably self-assembles into a "patchy" spherical micelle in water, with phase separation of the two hydrophilic blocks on the surface of the micelle core. Subsequent crosslinking of the core to solidify the patchy sphere geometry should allow further hierarchical assembly. Altering the hydrophilic versus hydrophobic composition of each polymer yields a change of morphology from "patchy spheres" to "patchy cylinders". Furthermore, by controlling the interaction strength of the blocks with solvent, the patches can be selectively placed either on the outer surface or inside the core of the micelle. The number and size of the patches are found to be largely controlled by the composition of the binary copolymer mixture.