The direct synthesis of sulfobetaine-containing amphiphilic block copolymers and their self-assembly behavior

Diblock copolymers containing the thermo-responsive sulfobetaine, [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (DMAPS), were synthesized by the aqueous RAFT polymerization of DMAPS, followed by direct chain extension in hexafluoroisopropanol (HFIP) with methyl methacrylate (MMA). This was shown to give lower dispersity polymers than RAFT emulsion polymerization. The diblock copolymers self-assembled in water to form micelles, as analyzed by light scattering (LS) and transmission electron microscopy (TEM). Micelles formed from diblocks bearing a long PDMAPS block were shown to swell with temperature, rather than display a traditional UCST cloud point. This was due to the polymers retaining hydrophilicity, even at temperatures well below the UCST for the corresponding PDMAPS homopolymer, as shown by variable temperature NMR. This swelling behavior was utilized in the release of a hydrophobic dye in response to temperature. This approach has great potential for applications in controlled release whilst maintaining the structure of the carrier nanoparticles.