Order–Order Morphological Transitions for DualStimulus Responsive Diblock Copolymer Vesicles
A seriesof non-ionic poly(glycerol monomethacrylate)–poly(2-hydroxypropylmethacrylate) (PGMA–PHPMA) diblock copolymer vesicles has beenprepared by reversible addition–fragmentation chain transfer(RAFT) aqueous dispersion polymerization of HPMA at 70 °C atlow pH using a carboxylic acid-based chain transfer agent. The degreeof polymerization (DP) of the PGMA block was fixed at 43, and theDP of the PHPMA block was systematically varied from 175 to 250 inorder to target vesicle phase space. Based on our recent work describingthe analogous PGMA–PHPMA diblock copolymer worms [LovettJ. R.; Angew. Chem.2015, 54, 1279−128325418214], such diblock copolymer vesicles were expectedto undergo an order–order morphological transition via ionizationof the carboxylic acid end-group on switching the solution pH. Indeed,irreversible vesicle-to-sphere and vesicle-to-worm transitions wereobserved for PHPMA DPs of 175 and 200, respectively, as judged byturbidimetry, transmission electron microscopy (TEM), and dynamiclight scattering (DLS) studies. However, such morphological transitionsare surprisingly slow, with relatively long time scales (hours) beingrequired at 20 °C. Moreover, no order–order morphologicaltransitions were observed for vesicles comprising longer membrane-formingblocks (e.g., PGMA43–PHPMA225–250) on raising the pH from pH 3.5 to pH 6.0. However, in such casesthe application of a dual stimulus comprising the same pH switch immediatelyfollowed by cooling from 20 to 5 °C, induces an irreversiblevesicle-to-sphere transition. Finally, TEM and DLS studies conductedin the presence of 100 mM KCl demonstrated that the pH-responsivebehavior arising from end-group ionization could be suppressed inthe presence of added electrolyte. This is because charge screeningsuppresses the subtle change in the packing parameter required todrive the morphological transition.
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