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Cooperation of Amphiphilicity and Smectic Order in Regulating the Self-Assembly of Cholesterol-Functionalized Brush-Like Block Copolymers

Li, Lishan, Zhou, Feng, Li, Yiwen, Chen, Xiaofang, Zhang, Zhengbiao, Zhou, Nianchen, Zhu, Xiulin
Langmuir 2018 v.34 no.37 pp. 11034-11041
blood platelets, composite polymers, dimethylformamide, hydrophilicity, hydrophobicity, liquids, micelles, nanofibers, nanoparticles, solvents
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, PChEMAₘ-b-POEGMAₙ, containing cholesteryl mesogens with different hydrophobic/hydrophilic block ratios were designed and synthesized. The self-assembly behaviors of the resulting PChEMAₘ-b-POEGMAₙ block copolymers in different solvents (tetrahydrofuran/H₂O, 1,4-dioxane/H₂O, 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/H₂O 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.