作者：Jie Cui, Wenyu Zhang, Yuanyuan Han, Yingying Wang, Wei Jiang
关键字：蝌蚪状巨型分子, 自组装, 纳米粒子, 自洽场理论, 密度泛函理论
论文来源：期刊
具体来源：Langmuir, 2023, 39(37), 13335-13344
发表时间：2023年

摘要：采用自洽场理论与密度泛函理论相结合，研究了由单个两亲性AB两嵌段共聚物链单端连接疏水纳米粒子（NP）构成的蝌蚪状巨型分子（TGM）在溶液中的自组装行为。分别在巨型分子组分间弱和强分子内相互作用（不相容性）情况下，考察了B嵌段和NPs疏水性（即溶剂性质）对TGMs自组装行为的影响。除具有疏水B核被NP壳覆盖的常规有序聚集体（如球、环和囊泡）外，通过在不同分子内相互作用下调节溶剂性质，还获得了多种新颖分级结构聚集体，包括NP插入疏水壁的囊泡、珠串状胶束以及带NP凸起的长圆柱胶束。值得注意的是，模拟结果表明长圆柱胶束上NP凸起的排列可能具有一定螺旋性，意味着这些胶束可能具有圆二色性等独特电磁特征。构建了以B嵌段和NPs疏水性为变量的相图，以显示这些新颖结构的形成条件。这些发现不仅为理解巨型分子自组装提供了新见解，也为设计功能杂化材料提供了指导。

Abstract：The self-assembly behavior of a tadpole-like giant molecule (TGM) constructed from a hydrophobic nanoparticle (NP) monotethered by a single amphiphilic AB diblock copolymer chain was investigated by combining self-consistent field theory and density functional theory in solution. The effects of the hydrophobicities of the B blocks and NPs (i.e., solvent properties) on the self-assembly behavior of the TGMs were investigated in the cases of weak and strong intramolecular interactions between the components of giant molecules, respectively. Besides conventional ordered aggregates (such as spheres, rings, and vesicles) with hydrophobic B-cores covered by NP shells, several aggregates with novel hierarchical structures, including vesicles with NP-inserted hydrophobic walls, bead-string-like micelles, and long cylindrical micelles with NP bumps, were obtained by tuning the solvent properties under different intramolecular interactions. Notably, the simulation results show that the arrangement of the NP bumps on the long cylindrical micelles may have a certain degree of helicity, which means that these micelles may have some unique electromagnetic features such as circular dichroism. Phase diagrams as a function of the hydrophobicities of the B blocks and NPs were constructed to show the formation conditions of these novel structures.

论文链接：https://doi.org/10.1021/acs.langmuir.3c02056