Multigeometry Nanoparticles from the Orthogonal Self-Assembly of Block Alternating Copolymers via Simulation.

Multigeometry nanoparticles (MGNs) have a high level of complexity both in composition and structure, and they are prevailing in nature and have shown great potential for multifunctional nanomaterials and hierarchy self-assembly. Polymer self-assembly is a common way to construct MGNs. However, up to now, the self-assembly strategy and the polymer category to fabricate MGNs are quite limited, and it is still a big challenge to get MGNs in a controlled way. Herein, by employing dissipative particle dynamics simulation, we provide a new "covalent-bonding-forced orthogonal self-assembly" strategy for the preparation of MGNs through the self-assembly of block alternating copolymers. Without any additional cautious control, block alternating copolymers can directly self-assemble into various MGNs, except for two basic requirements: the critical molecular weight of each block and the incompatibility of different blocks. Any different simple geometries, like vesicles, cylinders, and spheres, can be combined at will to construct arbitrary customized MGNs by changing the blocks. We further explore the effect of polymer concentration and the volume ratio of different blocks, through which the sizes, components, and structures of the MGNs can be regulated simply. In addition, we extend this strategy to ternary systems to fabricate much more complicated nanoparticles with triple geometries. We believe the present work has provided a promising and simple strategy to efficiently construct MGNs with precisely controllable geometries.