Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
J Am Chem Soc. 2014 Feb 12;136(6):2602-10. doi: 10.1021/ja412172f. Epub 2014 Jan 30.
Although an analogy has been drawn between them, organic molecular amphiphiles (MAMs) and inorganic nanoparticle (NP) amphiphiles (NPAMs) are significantly different in dimension, geometry, and composition as well as their assembly behavior. Their concurrent assembly can synergetically combine the inherent properties of both building blocks, thus leading to new hybrid materials with increasing complexity and functionality. Here we present a new strategy to fabricate hybrid vesicles with well-defined shape, morphology, and surface pattern by coassembling MAMs of block copolymers (BCPs) and NPAMs comprising inorganic NPs tethered with amphiphilic BCPs. The assembly of binary mixtures generated unique hybrid Janus-like vesicles with different shapes, patchy vesicles, and heterogeneous vesicles. Our experimental and computational studies indicate that the different nanostructures arise from the delicate interplay between the dimension mismatch of the two types of amphiphiles, the entanglement of polymer chains, and the mobility of NPAMs. In addition, the entropic attraction between NPAMs plays a dominant role in controlling the lateral phase separation of the two types of amphiphiles in the membranes. The ability to utilize multiple distinct amphiphiles to construct discrete assemblies represents a promising step in the self-assembly of structurally complex functional materials.
尽管已经对它们进行了类比，但有机分子两亲体（MAMs）和无机纳米粒子（NP）两亲体（NPAMs）在尺寸、几何形状和组成以及它们的组装行为方面存在显著差异。它们的并发组装可以协同结合两个构建块的固有性质，从而导致具有越来越复杂和多功能的新型杂化材料。在这里，我们提出了一种新策略，通过组装由与两亲性嵌段共聚物（BCP）连接的无机 NP 组成的 NPAMs 和嵌段共聚物（BCP）的 MAMs，来制备具有明确定义形状、形态和表面图案的混合囊泡。二元混合物的组装产生了具有不同形状、斑驳囊泡和异质囊泡的独特混合类 Janus 囊泡。我们的实验和计算研究表明，不同的纳米结构源于两种两亲体的尺寸不匹配、聚合物链缠结和 NPAMs 的迁移性之间的微妙相互作用。此外，NPAMs 之间的熵吸引力在控制膜中两种两亲体的横向相分离方面起着主导作用。利用多种不同两亲体来构建离散组装的能力代表了在结构复杂功能材料的自组装方面迈出的有希望的一步。
