Abstract

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Well defined redox responsive amphiphilic block copolymers of ethylene oxide, EO, and 2- methacryloyloxyethyl ferrocenecarboxylate, MAEFc were prepared by atom transfer radical polymerization (ATRP). The synthetic procedure was monitored by size exclusion chromatography (SEC) and the block copolymers were characterized using ¹H NMR spectroscopy. The self-assembly behavior of these amphiphilic copolymers was studied in aqueous solutions and in acetonitrile, both selective solvents for the PEO block. The formation of supramolecular structures (micelles and micellar aggregates) was revealed by Dynamic Light Scattering (DLS) using the CONTIN algorithm. The thermal properties of the block copolymers were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Cyclic voltammetry of PEO-b-PMAEFc copolymers in CHCl₃ solutions revealed a single redox process, a quasireversible oxidation wave with very slow kinetics, attributed to the Fe^II  Fe^III oxidation of the ferrocenyl units. The oxidation of the copolymers became more difficult and that the kinetic reversibility of the redox process was diminished as the PEO/PMAEFc ratio in the polymer chain increased.

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