Fabrication of Hierarchical Nanostructures Featuring Amplified Asymmetry Through Co‐Assembly of Liquid Crystalline Block Copolymer and Chiral Amphiphiles

The widespread presence of hierarchical asymmetric structures in nature has sparked considerable interest because of their unique functionalities. These ingenious structures across multiple scales often emerge from the transfer and amplification of asymmetry from chiral molecules under various synergistic effects. However, constructing artificial chiral asymmetric structures, particularly in developing hierarchical multicomponent structures analogous to those formed in nature through synergistic non-covalent interactions, still presents tremendous challenges. Herein, we propose a co-assembly strategy to fabricate hierarchical chiral mesostructures by combining a liquid crystalline block copolymer (LC-BCP) with a small molecular amphiphile containing chiral alanine or phenylalanine as a linker. Through a classic solvent-exchange process, chiral amphiphiles embedded within LC-BCP finely regulate the LC ordering effect and facilitate transfer and amplification of asymmetry. Consequently, various co-assembled structures with significant hierarchical chirality features are obtained through synergetic effects. Remarkably, subtle alterations to the side groups of amino acids in the amphiphiles effectively adjust the hierarchical morphology transition. Moreover, the covalent bonding sequence of amino acids in the amphiphiles emerges as a critical factor governing the formation of hierarchical nanofibers and multilayered vesicles exhibiting a superhelical sense.