Cui Jie, Zhang Wenyu, Han Yuanyuan, Wang Yingying, Jiang Wei
School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, P. R. China.
School of Physics and Information Engineering, Shanxi Normal University, Taiyuan 030031, P. R. China.
Langmuir. 2023 Sep 19;39(37):13335-13344. doi: 10.1021/acs.langmuir.3c02056. Epub 2023 Sep 10.
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 (i.e., incompatibilities) 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. Noteworthy that 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. These findings can not only offer new insights into understanding of the self-assembly behavior of the TGM in solution but also provide useful guidance for simple and efficient regulation of the morphology, as well as the NP distribution and arrangement of the ordered aggregates in experiments.
通过结合自洽场理论和溶液中的密度泛函理论，研究了由单个两亲性AB二嵌段共聚物链单链连接的疏水纳米粒子（NP）构建的蝌蚪状大分子（TGM）的自组装行为。分别在大分子组分之间弱和强分子内相互作用（即不相容性）的情况下，研究了B嵌段和NP的疏水性（即溶剂性质）对TGM自组装行为的影响。除了具有被NP壳覆盖的疏水B核的传统有序聚集体（如球体、环和囊泡）外，通过在不同分子内相互作用下调节溶剂性质，还获得了几种具有新颖层次结构的聚集体，包括具有插入NP的疏水壁的囊泡、串珠状胶束和具有NP凸起的长圆柱形胶束。值得注意的是，模拟结果表明，长圆柱形胶束上NP凸起的排列可能具有一定程度的螺旋性，这意味着这些胶束可能具有一些独特的电磁特性，如圆二色性。构建了作为B嵌段和NP疏水性函数的相图，以显示这些新颖结构的形成条件。这些发现不仅可以为理解溶液中TGM的自组装行为提供新的见解，还可以为实验中有序聚集体的形态、NP分布和排列的简单有效调控提供有用的指导。
