Invertible vesicles and micelles formed by dually-responsive diblock random copolymers in aqueous solutions

Dually responsive diblock random copolymers poly(nPA_0.8-co- DEAEMA_0.2)-block-poly(nPA_0.8-co-EA_0.2) were made from N-n-propylacrylamide (nPA), 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-ethylacrylamide (EA) via reversible addition-fragmentation chain transfer (RAFT) polymerization. Copolymers of different block length ratios, poly(nPA₂₈-co-DEAEMA₇)-block-poly(nPA₂₉-co- EA₇) (P1) and poly(nPA₂₈-co-DEAEMA₇)-block- poly(nPA₇₀-co-EA₁₈) (P2), self-assemble into vesicles and micelles, responding to external stimuli in aqueous solutions, and both show "schizophrenic" inversion behavior when the pH and temperature are varied. The relative lengths of the two blocks are shown to affect the self-assembly of amphiphilic diblock copolymers. P1 has a similar length for both blocks and forms spherical vesicles with the first block poly(nPA ₂₉-co-EA₇) as the membrane inner layer at pH 7 and 37 °C (above the cloud point of the more hydrophobic block, CP1), while spherical micelle-like aggregates are obtained at pH 10 and 25°C (above CP1) with the second block poly(nPA₂₈-co-DEAEMA₇) as the core. In comparison, P2 has a different block length ratio (1:3, thus a much longer second block) and forms spherical micelles above CP1 at both pH 7 (the second block as the core) and pH 10 (the first block as the core). Further aggregation was observed by heating the polymer solution above the cloud point of the more hydrophilic block (CP2). The variation of the length and chemical composition of the blocks allows the tuning of the responsiveness of the block copolymers toward both pH and temperature and determines the formation of either micelles or vesicles during the aggregation.