Supramicellar Nanofibrils with End-to-End Coupled Uniform Cylindrical Micelle Subunits via One-Step Assembly from a Liquid Crystalline Block Copolymer

Site-specific interactions are routinely applied by nature to direct the high-level assembly of nano-objects to form hierarchical structures from monomeric nanoobjects. For most of the time, these natural processes occur spontaneously after the formation of monomeric subunits effortlessly. Herein, we present a case of one-step assembly of a liquid crystalline block copolymer to form uniform cylindrical micelles, which could further undergo spontaneous end-to-end coupling to form hierarchical supramicellar nanofibrils. Through finely adjusting the tendency of nucleation and aggregation by tuning the assembly conditions, the lengths of these monomeric cylindrical micelles could be varied within a wide range. Moreover, the resultant cylinders subsequently would undergo spontaneous end-to-end coupling to form segmented supramicellar nanofibrils, facilitated by the liquid crystalline ordering effect from the micellar core. The morphology, dimensions, and rigidity of the supramicellar fibrils could be controlled by the assembly conditions. When different monomeric cylinders were assembled, heterogeneous supramicellar nanofibrils were obtained, demonstrating the cooperative but sequential assembly mechanism.