Sequence-Regulated Supracolloidal Copolymers via Copolymerization-Like Coassembly of Binary Mixtures of Patchy Nanoparticles.

Synthetic copolymers of molecular systems serve as an inspiration for creation of one-dimensional copolymer-like superstructures via coassembly of anisometric nanoparticles. In contrast to the covalent and molecular copolymers, the details of formation mechanisms of copolymer-like superstructures, as well as the factors determining their length and the sequences of arranged nanoparticles, are still poorly understood. Herein, we propose a joint theoretical-computational framework to probe into the coassembly mechanism and kinetics of binary mixtures of patchy nanoparticles. By applying the coarse-grained molecular dynamics simulations, it is demonstrated that the coassembly of patchy nanoparticles markedly resembles many aspects of molecular step-growth copolymerization, and the sequences of nanoparticles inside the copolymer-like superstructures can be finely regulated by the relative activity and the initial ingredient of patchy nanoparticles as well as the coassembly strategy. A quantitatively copolymerization-like model is developed to account for the coassembly kinetics of patchy nanoparticles and the sequence distribution of arranged nanoparticles, all governed by the elaborate design of lower-level building units. The jointly theoretical and simulated studies offer mechanistic insights into the copolymerization-like kinetics and the sequence prediction for the coassembly of binary mixtures of patchy nanoparticles, paving the way toward the rational design of copolymer-like superstructures with various sequences and functionalities.