Quantitative and spatially defined functionalization of nanostructures by overcoming the strong steric hindrance through bioinspired nucleobase interactions

Polymer nanostructures with controlled and uniform sizes, tunable surface properties, and spatially defined functionalities are highly pursued by scientists. However, precise control of tailored nanostructures still represents a formidable challenge. Herein, we have successfully developed an efficient and modular route for elegantly functionalizing polymer nanostructures by harnessing robust bioinspired nucleobase interactions of polymers for overcoming the strong steric hindrance. Adenine-containing core-crosslinked nanostructures were rationally designed and fabricated with numerous pendant adenines in the hydrophobic shell layer. Although the adenine-containing hydrophobic shell layer was effectively stabilized by the hydrophilic corona layer, extraordinary multiple hydrogen bonds between bioinspired complementary nucleobase-containing polymers are capable of overcoming the strong steric hindrance for efficient binding. Bioinspired hydrogen bonding interactions of nucleobases display excellent selectivity, superior efficiency, and high association constants. Therefore, it is facile and feasible to tailor the sizes, surface properties, and functionalities of polymer nanostructures through bioinspired nucleobase interactions. Meanwhile, the modular strong interactions of complementary nucleobases enable us to achieve the quantitative core and surface functionalization of synthetic polymer nanostructures. Thus, this work provides a novel and modular strategy for fabricating well-defined nanostructures, which is promising to furnish scalable and elegant nanomaterials for various biological applications such as precise nanovaccines and nanomedicines.