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Multigeometry nanoparticles with high complexity in composition and structure have attracted significant attention for enhanced functionality. We assess a simple but versatile strategy to construct hybrid nanoparticles with subdivided geometries through the cooperative assembly of diblock copolymer blends with asymmetric architectures. We report the formation of multicompartmental, vesicular, cylindrical, and spherical structures from pure AB systems. Then, we explore the assemblies of binary AB/AC blends, where the two incompatible, hydrophobic diblock copolymers subdivide into self-assembled local geometries, and the complexity of the obtained morphologies increases. We expand the strategy to ternary AB/AC/AD systems by tuning the effect of phase separation of different hydrophobic domains on the surface or internal region of the nanoparticle. The kinetic control of the coassembly in the initial stage is crucial for controlling the final morphology. The interactions of copolymers with different block lengths and chemistries enable the stabilization of interfaces, rims and ends of subdomains in the hybrid multigeometry nanoparticles. With further exploration of size and shape, the dependence of local geometry on the volume fraction is discussed. We show an efficient approach for controllable multigeometry nanoparticle construction that will be useful for multifunctional and hierarchical nanomaterials.

Controllable Multigeometry Nanoparticles via Cooperative Assembly of Amphiphilic Diblock Copolymer Blends with Asymmetric Architectures