Hierarchical Self‐Assembly in Liquid‐Crystalline Block Copolymers Enabled by Chirality Transfer

Abstract

Helical topological structures are often found in chiral biological systems, but seldom in synthesized polymers. Now, controllable microphase separation of amphiphilic liquid‐crystalline block copolymers (LCBCs) consisting of hydrophilic poly(ethylene oxide) and hydrophobic azobenzene‐containing poly(methylacrylate) is combined with chirality transfer to fabricate helical nanostructures by doping with chiral additives (enantiopure tartaric acid). Through hydrogen‐bonding interactions, chirality is transferred from the dopant to the aggregation, which directs the hierarchical self‐assembly in the composite system. Upon optimized annealing condition, helical structures in film are fabricated by the induced aggregation chirality. The photoresponsive azobenzene mesogens in the LCBC assist photoregulation of the self‐assembled helical morphologies. This allows the construction and non‐contact manipulation of complicated nanostructures.

Bioinspired light-driven chloride pump with helical porphyrin channels

“…The stacking frustration could reduce the ion conductivity of the porphyrin channels. To mitigate stacking frustration, free porphyrins are introduced into the BCP system, which acts as a repairing agent 26 , and bridges the adjacent porphyrin core in p -BCP 27 , 28 . Different TPP contents are doped into the p -BCP system, defined as p -BCP@ n TPP, where n is the TPP doping number per p -BCP (Supplementary Fig.…”

Formation of Size‐Controllable Tetragonal Nanoprisms by Crystallization‐Directed Ionic Self‐Assembly of Anionic Porphyrin and PEO‐Containing Triblock Cationic Copolymer

“…Molecular self-assembly represents one of the most promising bottom-up methodologies to build well-defined to fabricate and regulate anisotropic nanostructures, especially in the condensed state of matter. [27][28][29] Besides, some recent works reveal that small organic molecules also display controllable anisotropic morphologies and length distribution by rationally designing the directional noncovalent interactions, such as hydrogen bonding and π-π stacking, [30][31][32][33][34][35] which provided a broader insight into the design of controllable selfassembly and supramolecular materials. However, so far, it remains challenging to create size-controllable anisotropic nanostructures via ionic self-assembly (ISA), because the electrostatic interactions are isotropic, which greatly impedes directional growth.…”