Multicomponent supramolecular materials, which comprise plural supramolecular architectures that exhibit distinct self-sorting behaviors, are receiving increasing attention because they can be implemented with sophisticated functions and hierarchical structures, e.g., living cells. Nevertheless, the application of supramolecular system design to engineer self-sorting behaviors among plural supramolecular architectures remains challenging. Herein, we show that the thermal annealing-induced one-pot assembly of multiple single-stranded DNAs and a single semi-artificial glycopeptide (GP) results in the emergent formation of integrative self-sorted supramolecular nanostructures (ssSNs) consisting of a GP supramolecular nanoribbon surrounded by DNA tile-nanotubes. Fluorescence imaging revealed the formation of each supramolecular nanostructure through orthogonal molecular assembling processes. Moreover, the fluorescence recovery after photobleaching (FRAP) disclosed the presence of reversible attractive interactions between the DNA tile, prior to the formation of the tile-nanotube, and the GP supramolecular nanostructures at the mesoscale level, which are crucial for the formation of the integrative ssSNs. Further, we revealed that the integrative ssSNs retain their biostimuli responsiveness so that each supramolecular nanostructure can be selectively degraded. Finally, we successfully constructed a complex soft nanomaterial composed of ternary supramolecular architectures (a GP supramolecular nanostructure, DNA tile-nanotube, and DNA microsphere) based on the present as well as previous findings.
Keywords: DNA nanostructures; fluorescence imaging; glycopeptides; self-assembly; self-sorting.