State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , China.
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering , Sichuan University , Chengdu 610065 , China.
Langmuir. 2018 Sep 18;34(37):11034-11041. doi: 10.1021/acs.langmuir.8b01946. Epub 2018 Aug 31.
Nanoparticle morphology significantly affects the application of nanometer-scale materials. Understanding nanoparticle formation mechanisms and directing morphological control in nanoparticle self-assembly processes have received wide attention. Herein, a series of brush-like amphiphilic liquid crystalline block copolymers, PChEMA - b-POEGMA , containing cholesteryl mesogens with different hydrophobic/hydrophilic block ratios were designed and synthesized. The self-assembly behaviors of the resulting PChEMA - b-POEGMA block copolymers in different solvents (tetrahydrofuran/HO, 1,4-dioxane/HO, and N, N-dimethylformamide) were investigated in detail. Desirable micellar aggregates with well-organized architectures, including short cylindrical micelles, nanofibers, fringed platelets, and ellipsoidal vesicles with smectic micellar cores, were observed in 1,4-dioxane/HO with an increasing hydrophobic block ratio. Although both amphiphilicity and smectic order governed the self-assembly, these two factors were differently balanced in the different solvents. This unique supramolecular system provides a new strategy for the design of advanced functional nanomaterials with tunable morphologies.
纳米颗粒的形态显著影响纳米级材料的应用。理解纳米颗粒的形成机制并在纳米颗粒自组装过程中指导形态控制受到了广泛关注。本文设计并合成了一系列含有不同疏水性/亲水性嵌段比的胆甾醇介晶单元的梳状两亲性液晶嵌段共聚物 PChEMA-b-POEGMA。详细研究了所得 PChEMA-b-POEGMA 嵌段共聚物在不同溶剂（THF/H2O、1,4-二氧六环/H2O 和 DMF/H2O）中的自组装行为。在 1,4-二氧六环/H2O 中，随着疏水性嵌段比例的增加，观察到具有良好有序结构的理想胶束聚集体，包括短圆柱胶束、纳米纤维、边缘盘状胶束和具有向列相胶束核的椭圆形囊泡。尽管两亲性和向列有序性都控制着自组装，但这两个因素在不同的溶剂中得到了不同的平衡。这种独特的超分子体系为设计具有可调形态的先进功能纳米材料提供了新策略。
