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圆柱受限条件下 ABC 三嵌段共聚物形成的可调螺旋结构。

Tunable helical structures formed by ABC triblock copolymers under cylindrical confinement.

机构信息

Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, China.

出版信息

Phys Chem Chem Phys. 2019 Dec 11;21(48):26333-26341. doi: 10.1039/c9cp04978a.

Abstract

Block copolymers confined in nanopores provide unique achiral systems for the formation of helical structures. With AB diblock copolymers, stable single and double helical structures are observed. Aiming to obtain more different helical structures, we replace the AB diblock copolymer with linear ABC triblock copolymers. We speculate that a core-shell superstructure is formed within the nanopore, which is composed of a C-core cylinder wrapped by B-helices within the A-shell. Accordingly, the pore surface is set to be most attractive to the majority A-block and a typical set of interaction parameters is chosen as χACN ≪ χABN = χBCN = 80 to generate the frustrated interfaces. Furthermore, the volume fraction of B-block is fixed as fB = 0.1 to form helical cylinders. A number of helical structures with strands ranging from 1 to 5 are predicted by self-consistent field theory, and in general, the number of strands decreases as the volume fraction of C-block fC increases in a given nanopore. More surprisingly, the variation of helical strand in the confined system has an opposite trend to that in the bulk, which mainly results from the constraint of the cylindrical confinement on the change of the curvature between the outer A-layer and the inner B/C-superdomain. Our work demonstrates a facile way to fabricate different helical superstructures.

摘要

受限在纳米孔中的嵌段共聚物为形成螺旋结构提供了独特的非手性体系。对于 AB 两嵌段共聚物,可以观察到稳定的单链和双链螺旋结构。为了获得更多不同的螺旋结构,我们用线性 ABC 三嵌段共聚物代替 AB 两嵌段共聚物。我们推测,在纳米孔内形成了一种核壳超结构,它由被 A 壳层内的 B 螺旋包裹的 C 核圆柱组成。因此,孔表面被设定为对大多数 A 嵌段最具吸引力,并选择了一组典型的相互作用参数 χACN≪χABN=χBCN=80 来产生受挫界面。此外,B 嵌段的体积分数固定为 fB=0.1 以形成螺旋圆柱。自洽场理论预测了从 1 到 5 股的许多螺旋结构,通常,在给定的纳米孔中,随着 C 嵌段 fC 的体积分数增加,股数减少。更令人惊讶的是,受限系统中螺旋股的变化与本体中的变化趋势相反,这主要是由于圆柱限制对外部 A 层和内部 B/C-超域之间曲率变化的限制所致。我们的工作展示了一种制造不同螺旋超结构的简便方法。

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