Spherical Glycopolymer Architectures using RAFT: From Stars with a beta-Cyclodextrin Core to Thermoresponsive Core-Shell Particles

Glycopolymers with a seven-arm star architectures based on a beta-cyclodextrin core (beta-CD-RAFT) were successfully prepared using reversible addition-fragmentation chain transfer (RAFT) polymerization. A bimodal molecular weight distribution was observed in the early stages of the polymerization. At monomer conversions of N-acryloyl glucose (AGA) above 10% the polymerization proceeded according to a living behaviour and molecular weights of more than 200000 g mol(-1) were obtained. However, the resulting star polymers did not undergo well-controlled chain extension with N-isopropyl acrylamide (NIPAAm) and the formation of block structures in each arm was prevented. Alternatively, the arm-first technique was employed. Block copolymers based on AGA and PNIPAAm were self-assembled into micelles at a solution temperature above the lower critical solution temperature. Subsequent core-crosslinking with hexan-1,6-diol diacrylate resulted in unimolecular micelles with thermoresponsive properties. Dynamic light scattering studies, surface tensiometry, and transmission electron microscopy confirmed the formation of core-shell particles.