Expanding the Toolbox of DNA Supramolecular Polymerization for Hyperbranched Nanopolymers

With the unique combination of polymer-like functionality and biologically inspired dynamics, supramolecular DNA nanopolymers have become a highly promising platform for engineering next-generation smart soft materials. Realizing their full functional potential requires expanding the architectural diversity of DNA nanopolymers in a manner akin to that of classical polymers. In this contribution, we present a remarkable advancement in the introduction of trivalent DNA nanostars with carefully designed sequences of sticky ends. Through the coarse-grained molecular dynamics simulations, it is revealed that the trivalent DNA nanostars have the capability to yield the hyperbranched nanopolymers with a tunable branching degree under one-pot programmable self-assembly. Importantly, extending the classical model of polymerization kinetics enables the quantitative prediction of the growth kinetics and branching degree of hyperbranched DNA nanopolymers, which can be tailored through the designed elements of trivalent DNA nanostars. Furthermore, the terminations of hyperbranched DNA nanopolymers are used as active sites to ligate the DNA-functionalized nanoparticles and yield the hierarchical coassemblies of branched nanoarchitectures, a previously unreported topology. We envision that the polymerization-like self-assembly of DNA nanostars will serve as a versatile platform for diversifying the topological architectures of supramolecular nanostructures, thereby advancing the broad applicability of DNA-based functional materials.