不对称聚合诱导结晶驱动的螺旋、棒状线圈聚（芳基异氰化物）嵌段共聚物的自组装,Journal of the American Chemical Society

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不对称聚合诱导结晶驱动的螺旋、棒状线圈聚（芳基异氰化物）嵌段共聚物的自组装
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-03-13 , DOI: 10.1021/jacs.2c13354
Randall A Scanga ₁ , Ali Shahrokhinia ₁ , Jake Borges ₁ , Sean H Sarault ₁ , Michael B Ross ₁ , James F Reuther ₁

Affiliation

聚合诱导结晶驱动自组装 (PI-CDSA) 首次与螺旋棒线圈嵌段共聚物 (BCP) 自组装相结合，可实现可扩展和可控的原位合成可变形状的手性纳米结构、大小和维数。在此，我们报告了新开发的非对称PI-CDSA ( A- PI-CDSA) 合成和原位方法由聚（芳基异氰化物）（PAIC）刚性棒和聚（乙二醇）（PEG）随机线圈组分组成的手性棒线圈 BCP 的自组装。使用基于 PEG 的镍 (II) 大分子引发剂，可在 5.0–10 wt% 的固含量范围内构建具有可变手性形态的 PAIC-BCP 纳米结构。在 PAIC-BCP 的核心与电晕比率较低的情况下，我们通过“活的” A- PI-CDSA展示了手性一维 (1D) 纳米纤维的可扩展形成，其轮廓长度可以通过改变单聚体到一维来调整种子颗粒比。在高铁芯与电晕比下，A-PI-CDSA 用于通过涡流搅拌辅助的自发成核和生长快速制造分子薄、均匀的六角形纳米片。对二维种子、活性A- PI-CDSA 的研究揭示了 CDSA 背景下的全新范例，其中分层手性、M螺旋螺旋形形态（即六角螺旋体）在三个维度（即高度和面积）上进行了尺寸调整通过改变单聚体与种子的比例。这些独特的纳米结构是原位形成的通过以对映选择性方式围绕螺型位错缺陷位点快速结晶，固体含量高达 10 wt%。PAIC 块的液晶性质决定了这些 BCP 的分层组装，手性在长度尺度和多个维度上进行了翻译，从而提供了手性光学活性的大幅放大，螺旋角纳米结构的 g 因子达到-0.030 。

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Asymmetric Polymerization-Induced Crystallization-Driven Self-Assembly of Helical, Rod-Coil Poly(aryl isocyanide) Block Copolymers

Polymerization-induced crystallization-driven self-assembly (PI-CDSA) is combined, for the first time, with helical, rod-coil block copolymer (BCP) self-assembly to enable scalable and controllable in situ synthesis of chiral nanostructures of variable shape, size, and dimensionality. Herein, we report newly developed asymmetric PI-CDSA (A-PI-CDSA) methodologies in the synthesis and in situ self-assembly of chiral, rod-coil BCPs composed of poly(aryl isocyanide) (PAIC) rigid-rod and poly(ethylene glycol) (PEG) random-coil components. Using PEG-based nickel(II) macroinitiators, the construction of PAIC-BCP nanostructures with variable chiral morphologies is accomplished at solids contents ranging 5.0–10 wt %. At low core-to-corona ratios for PAIC-BCPs, we demonstrate the scalable formation of chiral one-dimensional (1D) nanofibers via “living” A-PI-CDSA whose contour lengths can be tuned through alterations to unimer-to-1D seed particle ratio. At high core-to-corona ratios, A-PI-CDSA was implemented for the rapid fabrication of molecularly thin, uniform hexagonal nanosheets via spontaneous nucleation and growth aided by vortex agitation. Investigations into 2D seeded, living A-PI-CDSA revealed a brand-new paradigm in the context of CDSA where hierarchically chiral, M helical spirangle morphologies (i.e., hexagonal helicoids) are size-tuned in three dimensions (i.e., heights and areas) via alterations to unimer-to-seed ratio. These unique nanostructures are formed in situ at scalable solids contents up to 10 wt % via rapid crystallization about screw dislocation defect sites in an enantioselective fashion. The liquid crystalline nature of PAIC blocks dictates the hierarchical assembly of these BCPs, with chirality translated across length scales and in multiple dimensions affording large amplifications in chiroptical activity with g-factors reaching −0.030 for spirangle nanostructures.

更新日期：2023-03-13

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