Journal
MACROMOLECULES
Volume 49, Issue 12, Pages 4534-4543Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.6b00998
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Funding
- Ministry of Education, Science, Sports and Culture [A: 24245026, C: 26410134, B: 24750104]
- Sumitomo Foundation [131302]
- Research Institute for Production Development
- Japan Society for the Promotion of Sciences (JSPS) [DC1:24-6140]
- Grants-in-Aid for Scientific Research [26410134] Funding Source: KAKEN
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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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