Tuning thermoresponsive behavior of diblock copolymers and their gold core hybrids. Part 2. How properties change depending on block attachment to gold nanoparticles.

Thermoresponsive diblock copolymers of di(ethylene glycol) methyl ether methacrylate (DEGMA) and oligo(ethylene glycol) methyl ether acrylate (OEGA) were synthesized by reversible addition-fragmentation chain transfer polymerization, allowing us to prepare diblocks with a thiol group at the desired chain end, and bond that block to a ~20 nm gold nanoparticle core. The cloud point and coil-globule transition window were measured by UV-vis spectroscopy. The gold core lowered the cloud point and narrowed the coil-globule transition window of all the diblock hybrids, but raised the cloud point of statistical copolymer hybrids that had similar cloud points. The extent of the change in the thermo-response properties of the hybrid diblock copolymers was more significant when the gold was bonded to the DEGMA block than the OEGA block. This block is less hydrophilic and sterically hindered than OEGA and may adsorb more effectively to the gold so that the hydration of the outer OEGA block is relatively unaffected by the Au core. This work indicates that diblock copolymers allow factors such as steric bulk and the effects on arrangement around a metal core to be effective tools for manipulating thermo-responsive properties that are not as significant with statistical copolymers.