Liquid Crystallinity and Solvophobic Interaction Drive the Differential Global Chirality in Racemic Block Copolymers

Abstract

Natural biomolecular structures possess an inherent ability to encode chiral conformations, thus the generation and regulation of chiroptical activity is crucial. While artificial polymers hold special significance in understanding life's origins, the fundamental connections between the racemic architecture and functional characteristics still need to be fully investigated. Herein, this study reports the generation and regulation of the global chirality and helical sense in racemic polymer systems, focusing on the synergistic effects of liquid crystallinity (LC) and solvophobic interaction. By systematically varying the length of alkyl spacers and the degree of polymerization (DP) of the core-forming azobenzene (Azo) blocks, the chiral communications, morphological transitions and chiroptical properties of the racemic nanoaggregates can be precisely controlled. Furthermore, the proposed “first come, first serve” (FF) and the “late-comer lives above” (LA) effect are broadly applicable and are expected to be applied to various types of racemic polymer systems. This work provides valuable insights into the design of self-assembled systems with tunable global chirality and morphology, thereby advancing the understanding of the origins of homochirality in nature.

Keywords

Chiral polymer / Helical polymer / Chiral conflict / Azobenzene / Liquid-crystalline

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2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH