DNA Hierarchical Superstructures from Micellar Units: Stiff Hydrogels and Anisotropic Nanofibers

Abstract Supramolecular materials have been assembled using a wide range of interactions, including the hydrophobic effect, DNA base‐pairing, and hydrogen bonding. Specifically, DNA amphiphiles with a hydrophobic building block self‐assemble into diverse morphologies depending on the length and composition of both blocks. Herein, we take advantage of the orthogonality of different supramolecular interactions – the hydrophobic effect, Watson‐Crick‐Franklin base pairing and RNA kissing loops – to create hierarchical self‐assemblies with controlled morphologies on both the nanometer and the micrometer scales. Assembly through base‐pairing leads to the formation of hybrid, multi‐phasic hydrogels with high stiffness and self‐healing properties. Assembly via hydrophobic core interactions gives anisotropic, discrete assemblies, where DNA fibers with one sequence are terminated with DNA spheres bearing different sequences. This work opens new avenues for the bottom‐up construction of DNA‐based materials, with promising applications in drug delivery, tissue engineering, and the creation of complex DNA structures from a minimum array of components.