Nucleobase-Interaction-Directed Biomimetic Supramolecular Self-Assembly.

The design and fabrication of synthetic self-assembled systems that can mimic some biological features require exquisitely sophisticated components that make use of supramolecular interactions to attain enhanced structural and functional complexity. In nature, nucleobase interactions play a key role in biological functions in living organisms, including transcription and translation processes. Inspired by nature, scientists are progressively exploring nucleobase synthons to create a diverse range of functional systems with a plethora of nanostructures by virtue of molecular-recognition-directed assembly and flexible programmability of the base-pairing interactions. To that end, nucleobase-functionalized molecules and macromolecules are attracting great attention because of their versatile structures with smart and adaptive material properties such as stimuli responsiveness, interaction with external agents, and ability to repair structural defects. In this regard, a range of nucleobase-interaction-mediated hierarchical self-assembled systems have been developed to obtain biomimetic materials with unique properties. For example, a new "grafting to" strategy utilizing complementary nucleobase interactions has been demonstrated to temporarily control the functional group display on micellar surfaces. In a different approach, complementary nucleobase interactions have been explored to enable morphological transitions in functionalized diblock copolymer assembly. It has been demonstrated that complementary nucleobase interactions can drive the morphological transformation to produce highly anisotropic nanoparticles by controlling the assembly processes at multiple length scales. Furthermore, nucleobase-functionalized bottle brush polymers have been employed to generate stimuli-responsive hierarchical assembly. Finally, such interactions have been exploited to induce biomimetic segregation in polymer self-assembly, which has been employed as a template to synthesize polymers with narrow polydispersity. It is evident from these examples that the optimal design of molecular building blocks and precise positioning of the nucleobase functionality are essential for fabrication of complex supramolecular assemblies. While a considerable amount of research remains to be explored, our studies have demonstrated the potential of nucleobase-interaction-mediated supramolecular assembly to be a promising field of research enabling the development of biomimetic materials.This Account summarizes recent examples that employ nucleobase interactions to generate functional biomaterials by judicious design of the building blocks. We begin by discussing the molecular recognition properties of different nucleobases, followed by different strategies to employ nucleobase interactions in polymeric systems in order to achieve self-assembled nanomaterials with versatile properties. Moreover, some of their prospective biological/material applications such as enhanced drug encapsulation, superior adhesion, and fast self-healing properties facilitated by complementary nucleobase interactions are emphasized. Finally, we identify issues and challenges that are faced by this class of materials and propose future directions for the exploration of functional materials with the aim of promoting the development of nucleobase-functionalized systems to design the next generation of biomaterials.