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通过与非手性胺的非共价相互作用辅助的大分子螺旋中的手性放大以及螺旋手性的记忆

Chiral amplification in macromolecular helicity assisted by noncovalent interaction with achiral amines and memory of the helical chirality.

作者信息

Morino Kazuhide, Watase Nobuyuki, Maeda Katsuhiro, Yashima Eiji

机构信息

Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan.

出版信息

Chemistry. 2004 Oct 4;10(19):4703-7. doi: 10.1002/chem.200400381.

Abstract

Poly[(4-carboxyphenyl)acetylene] (poly-1) exhibits an intense induced circular dichroism (ICD) in the UV-visible region upon complexation with excess (R)-1-(1-naphthyl)ethylamine ((R)-2), owing to the formation of a predominantly single-handed helical conformation of the polymer backbone. In the presence of a small amount of (R)-2, poly-1 showed a very weak ICD due to the lack of a single-handed helical conformation. However, we have found that the co-addition of the excess bulky, achiral 1-naphthylmethylamine (5) with a small amount of (R)-2 caused a dramatic increase in the ICD magnitude, comparable to the full ICD induced by excess (R)-2. This indicates that an almost single-handed helix can be induced on poly-1 upon complexation with a small amount of (R)-2 assisted by achiral 5. Furthermore, the induced single-handed helical poly-1 could be successfully memorized by the replacement of (R)-2 and 5 with achiral 2-aminoethanol or n-butylamine.

摘要

聚[(4-羧基苯基)乙炔](聚-1)在与过量的(R)-1-(1-萘基)乙胺((R)-2)络合时,由于聚合物主链形成了主要为单手螺旋构象,在紫外-可见区域表现出强烈的诱导圆二色性(ICD)。在存在少量(R)-2的情况下,由于缺乏单手螺旋构象,聚-1显示出非常弱的ICD。然而,我们发现,将过量的大体积非手性1-萘基甲胺(5)与少量(R)-2共同添加会导致ICD强度显著增加,与过量(R)-2诱导的完全ICD相当。这表明在与少量(R)-2络合时,在手性5的辅助下,聚-1上可以诱导出几乎单手的螺旋结构。此外,通过用非手性2-氨基乙醇或正丁胺取代(R)-2和5,可以成功地记忆诱导的单手螺旋聚-1。

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