Self-Assembly of Poly(Janus particle)s into Unimolecular and Oligomeric Spherical Micelles

Using shape-persistent Janus particles to construct poly(Janus particle)s and studying their self-assembly behaviors are of great interest, but remain largely unexplored. In this work, we reported a type of amphiphiles constructed by the ring-opening metathesis polymerization of nonspherical molecular Janus particles (APOSS-BPOSS), called poly(Janus particle)s (poly(APOSS-BPOSS), n = 12, 17, 22, and 35, and M_n = 35-100 kg/mol). Unlike traditional bottlebrush polymers consisting of flexible side chains, these poly(Janus particles) consist of rigid hydrophilic and hydrophobic polyhedral oligomeric silsesquioxane (POSS) cages as side chains. Interestingly, instead of maintaining an expected extended chain conformation, they could also collapse and then self-assemble to form unconventional unimolecular or oligomeric spherical micelles in solutions with a feature size smaller than 7 nm. More importantly, unlike traditional amphiphilic polymer brushes that could form unimolecular micelles at a relatively high degree of polymerization by self-assembly, these poly(Janus particles)s could accomplish self-assembly at a quite low degree of polymerization because of their unique chemical structure and molecular topology. The formation of unimolecular and oligomeric micelles was also further confirmed by dissipative particle dynamics simulations. This study of introducing the POSS-based poly(Janus particle)s as a class of shape amphiphiles will provide a model system for generating unimolecular and oligomeric micellar nanostructures through solution self-assembly.