CO2-responsive polyacrylamide copolymer vesicles with acid-sensitive morpholine moieties and large hydrophobic RAFT end-group
Chalmers, Benjamin A.
Cheung, David L.
Zetterlund, Per B.
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Chalmers, Benjamin A., Magee, Christopher, Cheung, David L., Zetterlund, Per B., & Aldabbagh, Fawaz. (2017). CO2-responsive polyacrylamide copolymer vesicles with acid-sensitive morpholine moieties and large hydrophobic RAFT end-group. European Polymer Journal, 97(Supplement C), 129-137. doi: https://doi.org/10.1016/j.eurpolymj.2017.10.004
Sequential Reversible Addition Fragmentation Chain Transfer (RAFT) polymerizations using 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044) and 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) were used to give amphiphilic polyacrylamide block copolymers containing N-(2-morpholin-4-ylethyl)acrylamide (MEA), where the morpholine moieties are CO2-responsive. The order in which monomers were polymerized determined the placement of the large hydrophobic RAFT end group with more complex ABA′ type self-assembly (e.g. patterned and large worm-like vesicles, large compound micelles) obtained when the dodecyl trithiocarbonate end-group was attached to the hydrophilic poly(MEA) block. Cleaving the hydrophobic end group reverts self-assembly to simpler spherical vesicles observed in the triblock of the same chemical composition, but with the RAFT end group attached to the hydrophobic poly(tert-butyl acrylamide) block. Ionization of the hydrophilic poly(MEA) block through flushing with CO2 irreversibly shifts self-assembly towards lower order morphologies with spherical micelles being more favoured than vesicles.