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镍催化的螺旋状聚(芳基异腈)的配位聚合诱导自组装

Nickel-Catalyzed Coordination Polymerization-Induced Self-Assembly of Helical Poly(aryl isocyanide)s.

作者信息

Jimaja Sètuhn, Varlas Spyridon, Xie Yujie, Foster Jeffrey C, Taton Daniel, Dove Andrew P, O'Reilly Rachel K

机构信息

Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.

School of Chemistry, University of Birmingham, Edgbaston B15 2TT, United Kingdom.

出版信息

ACS Macro Lett. 2020 Feb 18;9(2):226-232. doi: 10.1021/acsmacrolett.9b00972. Epub 2020 Jan 30.

Abstract

The interest in helix-containing nanostructures is currently growing as a consequence of their potential applications in areas such as nanomedicine, nanomaterial design, chiral recognition, and asymmetric catalysis. Herein, we present a facile and tunable one-pot methodology to achieve chiral nano-objects. The nickel-catalyzed coordination polymerization-induced self-assembly (NiCCo-PISA) of helical poly(aryl isocyanide) amphiphilic diblock copolymers was realized and allowed access to various nano-object morphologies (spheres, worm-like micelles, and polymersomes). The helicity of the core block was confirmed via circular dichroism (CD) spectroscopy for all morphologies, proving their chiral nature. Small-molecule uptake by the spherical nanoparticles was investigated by encapsulating Nile Red into the core of the spheres and subsequent transfer into aqueous media. The presence of a CD signal for the otherwise CD-inactive dye proved the chiral induction effect of the nano-objects' helical core. This demonstrates the potential of NiCCo-PISA to prepare nanoparticles for applications in nanomaterials, catalysis, and recognition.

摘要

由于含螺旋纳米结构在纳米医学、纳米材料设计、手性识别和不对称催化等领域的潜在应用,目前人们对其兴趣与日俱增。在此,我们提出一种简便且可调的一锅法来制备手性纳米物体。实现了螺旋状聚(芳基异腈)两亲性二嵌段共聚物的镍催化配位聚合诱导自组装(NiCCo-PISA),并可获得各种纳米物体形态(球体、蠕虫状胶束和聚合物囊泡)。通过圆二色性(CD)光谱证实了所有形态核心嵌段的螺旋性,证明了它们的手性本质。通过将尼罗红封装到球体核心并随后转移到水介质中,研究了球形纳米颗粒对小分子的摄取。原本无CD信号的染料出现CD信号,证明了纳米物体螺旋核心的手性诱导效应。这证明了NiCCo-PISA在制备用于纳米材料、催化和识别应用的纳米颗粒方面的潜力。

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