Thermoresponsive and Redox Behaviors of Poly(N-isopropylacrylamide)-Based Block Copolymers Having TEMPO Groups as Their Side Chains

Thermoresponsive and redox-active block copolymers having 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties have been synthesized by using the reversible addition-fragmentation chain transfer (RAFT) polymerization technique. N-Isopropylacrylamide (NIPAAm) and 2,2,6,6-tetramethylpiperidyl methacrylate (TEMPMA) monomers were copolymerized step-wise under RAFT polymerization conditions to afford the thermoresponsive block copolymers, PNIPAAm-block-PTEMPMA and PNIPAAm-block-PTEMPMA-block-PNIPAAm. Oxidation of tetramethylpiperidine groups in the copolymers successfully afforded the corresponding TEMPO-containing block copolymers. The resulting triblock copolymer was found to be thermoresponsive showing lower critical solution temperature (LCST) at 34 degrees C in its aqueous solution. Redox behavior of the resulting copolymer was observed by cyclic voltammetry. The potential of anodic current peak changed below and above the LCST of the block copolymer. These results indicate that the phase transition of thermoresponsive polymer influences the redox potential of TEMPO moieties.