UCST-Type Thermosensitive Hairy Nanogels Synthesized by RAFT Polymerization-Induced Self-Assembly

While lower critical solution temperature (LCST)-type thermosensitive nanogels have been intensively studied, the upper critical solution temperature (UCST)-type versions are much less explored. This communication reports a method for the synthesis of zwitterionic UCST nanogels by reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly in water-organic solvent mixtures. The nanogels were prepared by RAFT polymerization of 3-dimethyl(methacryloyloxyethyl)ammonium propanesulfonate, whose polymer is known to exhibit UCST behavior in water, conducted in ethanol-water mixtures at 70 °C using poly(poly(ethylene glycol) methyl ether methacrylate) as a macro-chain transfer agent (CTA) and a difunctional monomer as cross-linker. At a sufficiently high ethanol content in reaction media, spherical hairy nanogels with a single size distribution were obtained. These nanogels exhibited reversible heating-induced swelling and cooling-induced shrinking, consistent with the expected UCST behavior. The hydrodynamic size, volume changing ratio, and transition temperature of nanogels can be tuned by varying ethanol content in solvent mixtures, molar ratio of monomer-to-macro-CTA, and amount of cross-linker. Hairy nanogels were also successfully synthesized using a water-THF mixture as medium. The use of water-organic solvent mixtures as reaction media allowed for facile incorporation of a hydrophobic fluorescent monomer to make functional UCST nanogels.