Influence of Tacticity on the Self-Assembly of Poly(ethylene glycol)-b-poly(lactic acid) Block Copolymers

Lactide, possessing two stereocenters and thus three distinct configurations (DD, DL, and LL), serves as a captivating building block for polymers and self-assembly. Notably, polylactide (PLA) exhibits stereocomplexation, displaying heightened interactions between different configurations compared with interactions within the same configuration. This characteristic renders PLA an intriguing subject for investigating self-assembly behavior. In this study, 22 PEG-b-PLA polymers were synthesized and self-assembled, with analysis conducted through NMR and cryo-TEM techniques. A range of morphologies, including vesicles, diamond-shaped lamellae, and branched networks, were achieved by manipulating the tacticities. Enhanced comprehension of self-assembly interactions holds promise for advancing molecular recognition, self-replication, and asymmetric catalysis.