Synergetic Self‐Assembly of Liquid Crystalline Block Copolymer with Amphiphiles for Fabrication of Hierarchical Assemblies

Abstract

Novel functions and advanced structure, where each single component could not be produced individually, can exhibit from the collective and synergistic behavior of component systems. This synergetic strategy has been successfully demonstrated for co‐assembly of polymer–polymer to construct hierarchical nanomaterials. However, differences in the natures of polymer and small molecules impose challenges in the construction of sophisticated co‐assemblies with geometrical and compositional control. Herein, a synergetic self‐assembly strategy is proposed to prepare organic–organic hybrid colloidal mesostructures by blending a liquid crystalline block copolymer (LC‐BCP) with small molecular amphiphiles. Through a classic solvent‐exchange process, amphiphiles embedded with LC‐BCP realize multi‐component nucleation and hierarchical assembly driven by anisotropic interaction from the LC ordering alignment of the core‐forming block. 1D nanofibers with a periodic striped structure are formed by further LC component fusion and refinement. In addition, LC ordering effect of LC‐BCP can be regulated by selecting appropriate solvents and leads to the formation of vesicular co‐micelles. By means of the thermal‐responsive behavior of amphiphiles, hexagonal pore arrays are finally generated on the surface of those vesicles.