Enhancing Crystallization of DNA-Functionalized Nanoparticles by Polymer Chains

It is a challenging task to properly realize crystal superlattices with the precise organization of individual nanoparticles (NPs) for sparely DNAfunctionalized NPs. In this contribution, taking advantage of flexible polymer chains for the delicate regulation of collective interactions, we overcome the challenge through a detailed investigation of the programmable self-assembly of bifunctionalized NPs by scale-accurate coarse-grained simulations. It is revealed that the rationally designed system of bifunctionalized NPs extremely expands the parameter space of crystalline nanostructures with various lattices in spite of a lower amount of DNA chains, originating from the strong steric hindrance of flexible polymer chains. Importantly, a geometric model is used to account for the effects of steric hindrance and unify the morphological boundaries of bifunctionalized NPs with various molecular designs of grafted chains. Furthermore, we also demonstrate that solvent responses of polymer chains can be used as a means to achieve reconfigurable self-assembly of bifunctionalized NPs. These findings not only provide fundamental insights into the programmable self-assembly of DNA-functionalized NPs but also offer design rules for the construction of crystal superlattices with elaborate architectures.