Hierarchical self-assembly of miktoarm star copolymers with pathway complexity,Polymer Chemistry

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Hierarchical self-assembly of miktoarm star copolymers with pathway complexity
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-12-9 , DOI: 10.1039/d0py01170c
Jie Xiao _{1,

2,

3,

4,

5} , Qun He _{1,

2,

3,

4,

5} , Minjun Yang _{1,

2,

3,

4,

5} , Haoquan Li _{1,

2,

3,

4,

5} , Xiandeng Qiu _{1,

2,

3,

4,

5} , Binghua Wang _{6,

7,

8,

9} , Bin Zhang _{6,

7,

8,

9} , Weifeng Bu _{1,

2,

3,

4,

5}

Affiliation

The hierarchical self-assembly of molecular building blocks provides promising opportunities toward the exploration of functional soft materials with structural programmability. Here, we report the hierarchical self-assembly behaviors of amphiphilic miktoarm star copolymers with pathway complexity. In our experiments, supramolecular miktoarm star copolymers with a cluster core of [α-SiW₁₂O₄₀]⁴⁻ and four polystyrene-block-poly(ethylene glycol) cations (PS_n-b⁺-PEG_m, n = 17, 26, 39, 57, 81; m = 45, SEW-1–5) are used as a model of amphiphilic miktoarm stars. When dispersed in the selective THF/methanol and toluene/methanol mixture solvents, the miktoarm stars of SEW-2–5 self-assemble to form bundled fibers, sheet-like assemblies, and hollow spheres. These complex structures are packed by reverse cylindrical or spherical micelles having [α-SiW₁₂O₄₀]⁴⁻/PEG₄₅ cores and PS_n coronas, wherein the micelle building blocks are originally formed by SEW-2–5 in the nonselective solvents THF and toluene. These hierarchically self-assembled structures do not resemble micelle-like nano-objects formed by amphiphilic copolymers in selective solvents. The mechanism behind such unconventional aggregates is presumably due to intra- and inter-micelle van der Waals attractions occurring under poor solvent conditions for the PS_n coronas. The difference is that SEW-3–5 self-assemble into normal vesicles with a PS_n core and a [α-SiW₁₂O₄₀]⁴⁻/PEG₄₅ corona in the chloroform/methanol mixture solvent. The reverse cylinders, rices, and spheres originally fabricated from SEW-3–5 in chloroform experience molecular reorganization for such normal vesicles in the present selective solvents. Moreover, SEW-1 forms normal lamellae in all the methanol based mixture solvents. The results presented herein not only enable us to reconsider the self-assembly behaviors of amphiphilic miktoarm stars in solution, but also provide opportunities for constructing advanced functional materials with high-level structural hierarchy.

中文翻译：

具有路径复杂性的miktoarm星形共聚物的分层自组装

分子构件的分层自组装为探索具有结构可编程性的功能性软材料提供了广阔的机遇。在这里，我们报告具有路径复杂性的两亲miktoarm星型共聚物的分层自组装行为。在我们的实验中，超分子具有的簇核[α-硅钨酸杂臂星形共聚物₁₂ ö ₄₀ ] ^4-和四个聚苯乙烯-嵌段-聚（乙二醇）阳离子（PS _ñ - b ⁺ -PEG_米，Ñ = 17，26 ，39，57，81; m = 45，SEW-1–5）用作两亲米克星的模型。当分散在选择性的THF /甲醇和甲苯/甲醇混合物溶剂中时，SEW-2-5的拟臂星会自组装成束纤维，片状组件和空心球。这些复杂的结构通过反向圆柱形或球形胶束具有填充[α-硅钨酸₁₂ ö ₄₀ ] ^4- / PEG ₄₅芯和PS _Ñ电晕，其中所述胶束构建块最初是由形成SEW-2-5在非选择性溶剂THF和甲苯中。这些分层的自组装结构与由两亲性共聚物在选择性溶剂中形成的胶束状纳米物体不同。这种非常规聚集体背后的机理可能是由于在PS _n电晕的不良溶剂条件下发生了胶束内和胶束间范德华吸引力。不同的是，SEW-3-5自组装成具有正常囊泡PS _Ñ芯和[α-硅钨酸₁₂ ö ₄₀ ] ^4- / PEG ₄₅电晕在氯仿/甲醇混合溶剂。反向圆柱，大米和球体最初由SEW-3-5制成在本发明的选择性溶剂中，对于氯仿中的正常囊泡，在氯仿中的分子经历分子重组。此外，SEW-1在所有基于甲醇的混合溶剂中均形成正常的薄片。本文介绍的结果不仅使我们能够重新考虑溶液中两亲米克星的自组装行为，而且还为构建具有高级结构层次的高级功能材料提供了机会。

更新日期：2020-12-18

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