Thermoinduced Crystallization-Driven Self-Assembly of Bioinspired Block Copolymers in Aqueous Solution

Zhiwei Wang (1) , Min Lin (1) , Colin Bonduelle (2, 3) , Rongye Li (1) , Zhekun Shi (1) , Chenhui Zhu (4) , Sébastien Lecommandoux (2, 3) , Zhibo Li (1) , Jing Sun (1)

1 Qingdao University of Science and Technology
2 LCPO - Laboratoire de Chimie des Polymères Organiques
3 Team 3 LCPO : Polymer Self-Assembly & Life Sciences
4 LBNL - Lawrence Berkeley National Laboratory [Berkeley]

Delicate control over architectures via crystallization-driven self-assembly (CDSA) in aqueous solution, particularly combined with external stimuli, is rare and challenging. Here, we report a stepwise CDSA process thermally initiated from amphiphilic poly(N-allylglycine)-b-poly(N-octylglycine) (PNAG-b-PNOG) conjugated with thiol-terminated triethylene glycol monomethyl ethers ((PNAG-g-EG3)-b-PNOG) in aqueous solution. The diblock copolymers show a reversible thermoresponsive behavior with nearly identical cloud points in both heating and cooling runs. In contrast, the morphology transition of the assemblies is irreversible upon a heating–cooling cycle because of the presence of a confined domain arising from crystalline PNOG, which allows for the achievement of different nanostructured assemblies by the same polymer. We demonstrated that the thermoresponsive property of PNAG-g-EG3 initiates assembly kinetically that is subsequently promoted by crystallization of PNOG thermodynamically. The irreversible morphology transition behavior provides a convenient platform for comparing the cellular uptake efficiency of nanostructured assemblies with various morphologies that are otherwise similar.

Mots clés: Morphology; Crystallization; Solution chemistry; Copolymers; Transmission electron microscopy

Domaines: Polymères; Matériaux; Matière Molle [cond-mat.soft]

Zhiwei Wang, Min Lin, Colin Bonduelle, Rongye Li, Zhekun Shi, et al.. Thermoinduced Crystallization-Driven Self-Assembly of Bioinspired Block Copolymers in Aqueous Solution. Biomacromolecules, 2020, 21 (8), pp.3411-3419. ⟨10.1021/acs.biomac.0c00844⟩. ⟨hal-02934927⟩