Hierarchical binary colloidosomes from polymer-tethered nanocubes and nanospheres driven by entropic contribution

Binary colloidosomes with periodic cubic symmetry are fabricated from anisotropic gold nanocubes and isotropic gold nanospheres. • The spatial arrangement of AuNPs within the colloidosomes is predominantly governed by entropic effects between the two components. • This study provides a general and efficient route to precisely engineer of binary colloidosomes from geometrically distinct nanocrystals. Binary colloidosomes constructed from polymer-grafted inorganic nanocrystals have recently garnered significant attention for their potential in constructing multifunctional materials. However, the fabrication of well-defined binary colloidosomes with tailored internal architectures using geometrically distinct nanoparticles remains challenging. In this study, we demonstrate the preparation of binary colloidosomes with periodic cubic symmetry via emulsion interfacial co-assembly of polystyrene-tethered anisotropic gold nanocubes (AuNCs@PS) and isotropic gold nanospheres (AuNPs@PS). The spatial distribution of AuNPs@PS within the resulting colloidosomes is predominantly governed by entropic effects between the two components, which are quantitatively characterized using the proposed effective size ratio parameter ( λ eff ). Furthermore, by tailoring the core size of AuNPs@PS and the molecular weight of the grafted polymer, the λ eff value and the resulting configuration of the colloidosomes can be precisely controlled. This strategy provides a versatile pathway for constructing binary colloidosomes with tailored internal structures, facilitating the rational design of advanced functional materials for applications in catalysis, optoelectronics, and photothermal therapy. Well-defined binary colloidosomes with periodic cubic symmetry self-assembled from anisotropic AuNCs@PS and isotropic AuNPs@PS building blocks are constructed through emulsion interface co-assembly strategy. The spatial distribution of AuNPs@PS within the resulting colloidosomes is predominantly governed by entropic effects between the two components. Download: Download high-res image (297KB) Download: Download full-size image