Abstract
The thermodynamic stability and structural inversion process of polymeric micelles is explored that are formed by the purely pH‐responsive poly(methacrylic acid)‐b‐poly((2‐diethylamino)ethyl methacrylate) (PMAA‐b‐PDEA) diblock copolymer in aqueous environment with different pH (from pH 2 to 12) employing dissipative particle dynamics (DPD) simulations and coarse‐grained models. In acid environments, thermodynamically stable micelles can be generated with well‐defined micellar structures of a PMAA‐core and PDEA‐corona by protonation of the amine groups of PDEA segments. In stark contrast, in alkaline environments, the polymeric micelles invert their micellar structure (PDEA‐core and PMAA‐corona) by ionization of the carboxylic acid groups of PMAA segments. The mesoscopic simulations, which agree with experimental outcomes, reveal an isoelectric point at pH 7.2 and a wide pH interval where the polymeric micelles lose their thermodynamic stability and tend to precipitate. The structural inversion process triggered by the pH effect is characterized by a simultaneous immersion and ascent of polymeric segments.
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