Knotting matters: orderly molecular entanglements.

Knotting matters: orderly molecular entanglements.
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打结问题:有序的分子纠缠。

DOI:
10.1039/d2cs00323f
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发表时间:
2022-09-20
影响因子:
46.2
通讯作者:
Zhang, Liang
Zhang, Liang
中科院分区:
化学1区
文献类型:
--
作者:
Ashbridge, Zoe;Fielden, Stephen D. P.;Leigh, David A.;Pirvu, Lucian;Schaufelberger, Fredrik;Zhang, Liang

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以有序的方式缠结线可以产生有用的效果,从鞋带和渔网到用绳子绑起来的棕色纸包。在纳米级,具有足够长度和柔性的非结晶聚合物链随机形成缠结的混合物,其中包含不同大小、形状和复杂性的开结。然而,也可以通过控制链交叉的数量、序列和立体化学来获得精确拓扑结构的离散分子结:有序的分子缠结。在过去的十年中,在新生领域的分子纳米拓扑学已经取得了实质性的进展,与一般的合成策略和新的打结图案的介绍,沿着洞察有序缠结序列的属性和功能。通过打结赋予的构象限制可以诱导变构、强的和选择性的阴离子结合、催化活性,导致跨长度尺度的有效手性表达、对药物递送有效的构象中的结合模式,并且促进分子水平的机械功能。随着复杂的分子拓扑结构变得越来越容易合成,它们有可能在分子和材料设计策略中发挥重要作用。我们突出分子结的特殊例子来说明为什么这些是我们最喜欢的东西。本文综述了有序分子缠结化学的最新进展。随着复杂的纳米拓扑结构变得越来越容易,它们可能在分子设计中发挥重要作用。
Entangling strands in a well-ordered manner can produce useful effects, from shoelaces and fishing nets to brown paper packages tied up with strings. At the nanoscale, non-crystalline polymer chains of sufficient length and flexibility randomly form tangled mixtures containing open knots of different sizes, shapes and complexity. However, discrete molecular knots of precise topology can also be obtained by controlling the number, sequence and stereochemistry of strand crossings: orderly molecular entanglements. During the last decade, substantial progress in the nascent field of molecular nanotopology has been made, with general synthetic strategies and new knotting motifs introduced, along with insights into the properties and functions of ordered tangle sequences. Conformational restrictions imparted by knotting can induce allostery, strong and selective anion binding, catalytic activity, lead to effective chiral expression across length scales, binding modes in conformations efficacious for drug delivery, and facilitate mechanical function at the molecular level. As complex molecular topologies become increasingly synthetically accessible they have the potential to play a significant role in molecular and materials design strategies. We highlight particular examples of molecular knots to illustrate why these are a few of our favourite things. We review recent progress in molecular knotting, the chemistry of orderly molecular entanglements. As complex nanotopologies become increasingly accessible they may play significant roles in molecular design.
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