Yu Linxiuzi, Zhang Niboqia, Zhang Ning-Ning, Gu Qianqian, Xue Yao, Wang Yu-Xi, Han Cheng-Long, Liu Kun, Sun Zhao-Yan, Qian Hu-Jun, Lu Zhong-Yuan
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130021, China.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
J Phys Chem Lett. 2021 Aug 5;12(30):7100-7105. doi: 10.1021/acs.jpclett.1c01979. Epub 2021 Jul 22.
The formation of polymer-patch nanoparticles (PNPs) involves a condensation process of grafted chains on a nanoparticle (NP) surface, which is conventionally achieved via a fine-tuning of the solvent quality. However, such a critical solvent condition differs dramatically between polymers, and the formation mechanism of different patchy structures remains under debate. In this study, we demonstrate by a combined simulation and experimental study that such a surface-patterning process can be easily achieved via a simple solvent evaporation process, which creates a natural nonsolvent condition and is, in principle, adaptable for all polymers. More importantly, we find that patchy structures are controlled by a delicate balance between enthalpic interaction and the entropy penalty of grafted chains. A small variation of cohesive energy density can lead to a dramatic change in patch structure. This work offers a robust yet easy approach for the fabrication of PNPs and provides new insights into polymer segregation on spherical surfaces.
聚合物补丁纳米颗粒（PNPs）的形成涉及纳米颗粒（NP）表面接枝链的缩合过程，传统上是通过微调溶剂质量来实现的。然而，这种关键的溶剂条件在不同聚合物之间差异很大，不同补丁结构的形成机制仍存在争议。在本研究中，我们通过模拟和实验相结合的研究表明，这种表面图案化过程可以通过简单的溶剂蒸发过程轻松实现，该过程会产生自然的非溶剂条件，并且原则上适用于所有聚合物。更重要的是，我们发现补丁结构由接枝链的焓相互作用和熵惩罚之间的微妙平衡控制。内聚能密度的微小变化会导致补丁结构发生巨大变化。这项工作为PNPs的制备提供了一种稳健且简便的方法，并为球形表面上的聚合物偏析提供了新的见解。
