Preparation of Thermoresponsive Polymer-Modified Electrodes Having a TEMPO Moiety

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Thermoresponsive polymers having 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties were fixed on the graphite surface by using the reversible addition-fragmentation chain transfer (RAFT) graft polymerization technique. The surface of graphite has been anodically oxidized by using our original electrochemical method, and then modified with 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoyloxy groups (RAFT reagents) by esterification with the corresponding acid chlorides. From the resulting RAFT reagent-modified graphite, 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TEMPMA) and N-isopropylacrylamide (NIPAAm) monomers were copolymerized stepwise under RAFT polymerization conditions to afford the thermoresponsive block-copolymer-grafted graphite, poly(TEMPMA)-block-PNIPAAm-grafted graphite. N-Oxylation of tetramethylpiperidyl groups on the resulting graphite successfully afforded the corresponding TEMPO-containing thermoresponsive polymer-grafted graphite. Redox behavior of the resulting graphites was observed by cyclic voltammetry. The potential and intensity of the cathodic current peaks were discontinuously changed below and above the lower critical solution temperature (LCST) of the grafted thermoresponsive polymers. These results indicate that the phase transition of the thermoresponsive polymer on the graphite influences the electron transfer between the TEMPO moieties and the graphite surface.