Colloidal Helical Inverse-Phase Assemblies Constructed by Liquid Crystal Block Copolymer with Tunable Chiral Amino Acid Spacers

Inverse-phase micelles have been extensively studied due to their high porosity, large specific surface area, and structural versatility. However, the construction of inverse-phase assemblies from anisotropic polymers driven by complex synergistic interactions has largely been underexplored. Here, we report a class of cholesterol-based block copolymers (BCPs), POEGMA_m-b-P(R)Chol_n (R = Ala, Leu, Phe), featuring chiral amino acid moieties as side-chain spacers and liquid crystalline (LC) cholesterol as mesogenic units. The integration of chirality and liquid crystallinity imparts unique anisotropic properties to these BCPs, enabling synergetic interactions between hydrogen bonding, LC ordering, and hydrophobic aggregation during self-assembly. Notably, the chirality of the amino acid spacers is preserved within the micellar structure and effectively transmitted during the self-assembly process, resulting in the formation of inverse-phase micelles with pronounced helicity. These findings highlight a versatile strategy for constructing inverse-phase nanostructures with helicity and complexity by leveraging the synergistic effects of chirality and LC order within block copolymer frameworks.