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Multimode Self-Folding Polymers via Reversible and Thermoresponsive Self-Assembly of Amphiphilic/Fluorous Random Copolymers

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Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
*E-mail [email protected] (T.T.).
*E-mail [email protected] (M.S.).
Cite this: Macromolecules 2016, 49, 12, 4534–4543
Publication Date (Web):June 10, 2016
https://doi.org/10.1021/acs.macromol.6b00998
Copyright © 2016 American Chemical Society
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Abstract

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Multimode self-folding polymers were created via the reversible and thermoresponsive self-assembly of amphiphilic/fluorous random copolymers bearing poly(ethylene glycol) (PEG) and perfluoroalkyl pendants in water, N,N-dimethylformamide (DMF), and 2H,3H-perfluoropentane (2HPFP). The random copolymers with precision primary structure were synthesized by ruthenium-catalyzed living radical copolymerization of PEG methyl ether methacrylates and perfluoroalkyl methacrylates. Owing to three distinct properties of the hydrophobic backbone, hydrophilic PEG chains, and fluorous perfluorinated pendants, the random copolymers allowed various self-assembly modes for different folded structures by changing solvents. Namely, they form self-folding polymers of fluorous and/or hydrophobic cores in water or DMF, while they in turn provide reverse self-folding polymers of hydrophilic PEG cores in 2HPFP. The reverse folding in 2HPFP was further promoted by lower critical solution temperature-type phase separation of the PEG units upon heating.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.6b00998.

  • Experimental details, characterization, NMR spectra of polymers, and cloud points of polymers in H2O (PDF)

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