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Morphology Evolution of Stimuli-Responsive Triblock Copolymer Modulated by Polyoxometalates
Junyan Tan1, Dandan Chong1, Yue Zhou1
1Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering , Peking University , Beijing 100871 , China.
Abstract:
Polyoxometalate (POM) H3PMo12O40 was coassembled with stimuli-responsive triblock copolymer poly(ethylene oxide)- block-polystyrene- block-poly(2-(dimethylamino)ethyl methacrylate) (PEO- b-PS- b-PDMAEMA) by electrostatic interactions. Depending on the POM contents, the hybrid complexes can self-assemble into a series of morphologies: micelles, rods, toroids, and vesicles. Unlike traditional morphology transition of amphiphilic block copolymer derived from a broad range of hydrophobic volume fractions, POM-induced morphology transitions just occurred in a narrow range of volume fractions. The length of rod micelles exponentially decreased with solvent compositions (tetrahydrofuran/H2O). The hybrid assemblies showed acid-base responsibility due to the PDMAEMA block. Rod micelles could further assemble and disassemble reversibly upon adding acid/base. Fluorescent polyoxometalate Na9EuW10O36 was also complexed with PEO- b-PS- b-PDMAEMA to prepare fluorescent vesicles. The vesicles showed off-on switchable fluorescence behavior accompanied with reversible vesicle-to-micelle transformation in response to pH stimuli.
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