Self-assembly of giant building blocks beyond conventional molecules offers tremendous opportunities for the fabrication of new-generation structural materials. This work describes the macroscopic colloidal segregation in the vesicular self-assembly of binary nanoparticle amphiphiles (NPAMs) consisting of block copolymer-grafted nanoparticles in solution. Depending on their relative size and concentration, binary NPAMs with distinctive sizes assemble into hybrid vesicles with different morphologies, namely, homogeneous vesicles, patchy vesicles, and yolk/shell vesicles. The segregation of NPAMs confined within or escaped from the vesicular membrane is driven by the conformational entropy gain of end-grafted copolymer ligands. The effect of NPAM size and concentration on the morphological transition of vesicles is mapped in a phase diagram. Moreover, a vesicular fusion/budding mechanism is proposed to illustrate the formation of uniform vesicles with yolks inside. The hybrid vesicles have potential applications in cancer imaging, biosensing, and drug delivery.

超越常规分子的巨大构件的自组装为新一代结构材料的制造提供了巨大的机会。这项工作描述了由溶液中嵌段共聚物接枝的纳米颗粒组成的二元纳米颗粒两亲物（NPAM）的囊泡自组装中的宏观胶体分离。根据它们的相对大小和浓度，具有不同大小的二元NPAM会组装成具有不同形态的杂种囊泡，即均质囊泡，斑状囊泡和卵黄/壳囊泡。端部接枝共聚物配体的构象熵增加驱动着局限在囊泡膜内或从囊泡膜逸出的NPAM分离。相位图中绘制了NPAM大小和浓度对囊泡形态转变的影响。此外，提出了一种囊泡融合/萌芽机制来说明内部具有卵黄的均匀囊泡的形成。杂种囊泡在癌症成像，生物传感和药物递送中具有潜在的应用。