Stereocomplex-Driven Morphological Transition of Coil–Rod–Coil Poly(lactic acid)-Based Cylindrical Nanoparticles

[Image: see text] The stereocomplexation of poly(lactic acid) (PLA) enantiomers opens up an avenue for the formation of new materials with enhanced performance, specifically regarding their mechanical and thermal resistance and resistance to hydrolysis. Despite these useful features, the study of the stereocomplexation between block copolymers based on PLA in solution is limited, and a comprehensive understanding of this phenomenon is urgently needed. Herein, triblock copolymers of poly(N-hydroxyethyl acrylamide) and PL(or D)LA in which PLA was midblock (PHEAAm(y)-b-PL(D)LA(x)-b-PHEAAm(y)) were synthesized and assembled into cylindrical micelles via crystallization-driven self-assembly . The stereocomplexation between enantiomeric micelles facilitates the morphological transition, and the transformation process was investigated in detail by varying the aging temperature, block composition, and solvent. It was found that the solubility of the copolymers played a vital role in determining the occurrence and the speed of the chain exchange between the micelles and the unimers, which thereafter has a significant impact on the shape transition. These results lead to a deeper understanding of the stereocomplex-driven morphological transition process and provide valuable guidance for further optimization of the transition under physiological conditions as a new category of stimuli-responsive systems for biomedical applications.