Convergence of DNA nanotechnology and polymer chemistry to 'synthesize' nanopolymers with branching architectures: a...

Polymer-like superstructures termed nanopolymers from the self-assembly of atom-like nanoparticles are an emerging class of structured metamaterials with enhanced functionalities, but the controllable 'synthesis' of nanopolymers with non-linear architecture and spatially defined dimensions remains a challenge. Inspired by synthetic concepts of branched polymers, we propose a hierarchical polymerization-like protocol for the programmable coassembly of DNA-based multicomponent mixtures into non-linear nanopolymers with well-defined branching architecture and predictable spatial dimensions. By employing computational simulations, it is theoretically demonstrated that the synergy of sequence-designed DNA motifs and the proposed protocol enables the precise control over the assembly kinetics of atom-like nanoparticles and the branching architectures of nanopolymers, in agreement with the predictions of the generalized polymerization kinetics model. Furthermore, it is demonstrated that the fundamental correlations between the spatial dimension and branching architecture of nanopolymers satisfy the scaling law acquired in polymer science. These findings will facilitate the programmable coassembly of DNA supramolecules into structured metamaterials with architectural complexity observed in nature.