Wang Junfeng, Zhu Bojin, Wang Yining, Hao Yujian, Zhang Jun, Li Zhen
School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China.
Soft Matter. 2021 Dec 22;18(1):97-106. doi: 10.1039/d1sm01388b.
Functional assemblies of inorganic nanoparticles (NPs) are widely studied owing to their collective electromagnetic properties and various application from nanodrugs and bioimaging. In most cases, the superstructures of NPs are prepared with the assistance of templates or external fields. Therefore, how to prepare the functional assemblies of NPs more simply remains a challenge. Here, a free-template assembly strategy for preparing the superstructures of NPs is proposed in our work. In our strategy, we design poly(glycerol monomethacrylate)--poly(2-hydroxypropyl methacrylate) (PGMA--PHPMA) coated NPs. Then, using the polymerization-induced self-assembly (PISA), hydrophobic PHPMA blocks resulted in the phase separation to form the orderly patterns, which is expected to induced NPs to self-assemble into the orderly superstructures. By DPD simulations, we find that the disk, ring, composite superstructures can be obtained by regulating the graft density, verifying that our assembly strategy of NPs is feasible. Even more interesting is that NPs are also distributed in an orderly way on the surface of aggregations to form the orderly NP patterns. Besides that, the thermodynamics, dynamics, and structure details in the self-assembly process of HINPs are shown in our work, providing a new idea and elaborate physical picture for the following preparation of the superstructure of NPs.
无机纳米粒子（NPs）的功能组装体因其集体电磁特性以及在纳米药物和生物成像等方面的各种应用而受到广泛研究。在大多数情况下，纳米粒子的超结构是在模板或外部场的辅助下制备的。因此，如何更简单地制备纳米粒子的功能组装体仍然是一个挑战。在此，我们的工作中提出了一种用于制备纳米粒子超结构的无模板组装策略。在我们的策略中，我们设计了聚（甘油单甲基丙烯酸酯）-聚（2-羟丙基甲基丙烯酸酯）（PGMA-PHPMA）包覆的纳米粒子。然后，利用聚合诱导自组装（PISA），疏水性的PHPMA嵌段导致相分离形成有序图案，有望诱导纳米粒子自组装成有序的超结构。通过耗散粒子动力学（DPD）模拟，我们发现通过调节接枝密度可以获得盘状、环状、复合超结构，验证了我们的纳米粒子组装策略是可行的。更有趣地是，纳米粒子也以有序的方式分布在聚集体表面形成有序的纳米粒子图案。除此之外，我们的工作展示了超亲水纳米粒子（HINPs）自组装过程中的热力学、动力学和结构细节，为后续纳米粒子超结构的制备提供了新的思路和详细的物理图像。
