Biomimetic stimulus-responsive star diblock gelators

Novel biomimetic gelators with star diblock copolymer architectures have been synthesized by atom-transfer radical polymerization (ATRP). Two types of trifunctional ATRP initiator were used to polymerize 2-(methacryloyloxy)ethyl phosphorylcholine MPC] at 20 degrees C, followed by sequential monomer addition of various tertiary amine methacrylates or mixtures thereof. Poor living character was achieved using an amide-based trifunctional initiator, but the analogous triester initiator gave reasonably well-defined thermo-responsive and pH-responsive star diblock copolymers. The most effective thermo-responsive gelators were obtained by the statistical terpolymerization of 2-(dimethylamino)ethyl methacrylate DMA], 2-(diethylamino)ethyl methacrylate DEA], and a monomethoxy-capped poly(propylene oxide) methacrylate PPOMA], whereas pH-responsive gelators were prepared using 2-(diisopropylamino)ethyl methacrylate DPA] as the second monomer. Star diblock copolymer gelators that were both thermo-responsive and pH-responsive were obtained by the statistical copolymerization of DMA with DPA. Copolymer compositions were assessed by 1H NMR spectroscopy, and the molecular weight distributions of the three-arm star MPC homopolymer precursors were assessed by aqueous gel permeation chromatography. Static light scattering was used to obtain weight-average molecular weights of selected star diblock copolymers and rheological measurements and variable-temperature 1H NMR were used to probe the onset of gelation.