Supramolecular assembly of end-functionalized polymer mixtures confined in nanospheres.

Supramolecular assembly of functionalized polymers, capable of forming block copolymer-like molecular clusters, has emerged as a promising alternative for creating nanoscopically ordered structures. Here, we demonstrate that nanospheres, which have intriguing internal nanodomains and controllable surface functionality, can be fabricated by supramolecular assembly of two complementarily end-interacting species of mono-end-functionalized polymers using the self-organized precipitation (SORP) method. An exotic internal morphology, hierarchically organized structure of perforated spherical layers, was formed inside the nanosphere prepared from the stoichiometric mixture of the end-functionalized polymers, which is due to the formation of diblock-like supramolecules and their packing frustration in the spherically confined nanospace. When the mixing ratio of the two end-functionalized polymers differs from the stoichiometric ratio, the nanoparticle surface is enriched with an excess of unpaired functionalized groups, which therefore provides us with a useful way to precisely control the surface functionality of the nanoparticles.