Temperature and pH-sensitive ABC triblock polymers were prepared to form hydrogel membranes capable of changing their structure in response to environmental stimuli, allowing drug release, from a micro implantable device, in short and repetitive pulses. We have previously investigated the capacity of hydrogels to sustain open loop oscillatory behavior, with application in rhythmic hormone release. This novel oscillator is mediated by feedback instability between swelling/shrinking of the hydrogel and an enzyme reaction, whose product modifies pH in the hydrogel. The objective of this work was to prepare and characterize triblock polymer-based hydrogels, to overcome limitations of conventional hydrogels. Our strategy involves reversible arrangement of A and C thermosensitive domains within a strong network, whereas B block is also pH-sensitive. The triblock was mainly based on the use of NIPAAm (N, isopropylacrylamide) and AA (acrylic acid) monomers. Polymers were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. Polymers molecular weight (Mn) and polydispersity index (PDI) were determined by matrix-assisted laser desorption ionization/mass spectrometry (MALDI). Monomers conversion was assessed by NMR and copolymers composition by NMR and pH-titration. Temperature and pH responsiveness was studied by turbidity and light scattering experiments. ABC triblock presented Mn close to 40,000 Da and was nearly monodisperse (PDI<1.1). The monomers conversion was 92%, 97% and 39% for A, B and C blocks, respectively. The opposing effects of hydrophobicity and ionization on the aggregation behavior of the diblock have been highlighted through the turbidity and light scattering data. AB diblock cloud points were 32, 34, 35.5 and 37.5°C for 3, 5, 10 and 20% of AA, respectively. Micelles or aggegrates were observed depending on pH and temperature. ABC triblock polymers with controlled architecture and Mn distribution were synthesized and fully characterized. The results suggest that these block polymers are promising materials for stimuli-responsive hydrogel membranes applied to medical devices. Work supported by the Swiss National Fund for Scientific Research and an NSF-funded MRSEC (DMR#0819885) at the University of Minnesota.

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