RAFT-synthesized diblock and triblock copolymers: thermally-induced supramolecular assembly in aqueous media

This review highlights recent advances in the synthesis of functional, temperature-responsive, water-soluble block copolymers, including particular focus on the results obtained by employing reversible addition-fragmentation chain transfer ( RAFT) polymerization. The applicability of the RAFT process for the polymerization of functional monomers under a diverse range of experimental conditions has facilitated the synthesis of water-soluble (co) polymers that were previously inaccessible. Unprecedented control afforded by RAFT in homogeneous aqueous media allows well-defined polymeric systems to be prepared without stringent purification techniques and under increasingly ``green'' conditions while maintaining the ability to tailor many of the macromolecular characteristics ( molecular weight, chain topology, copolymer composition, functionality, etc.) that affect self-assembly in solution. Block copolymer formation and postpolymerization modification utilizing crosslinking and copper-catalyzed azide-alkyne "click'' chemistry are described, with attention being paid to their ability to control copolymer structure for subsequent self-assembly in response to changes in temperature.