Grate Jay W, Mo Kai-For, Daily Michael D
Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA, 99352, USA.
Angew Chem Int Ed Engl. 2016 Mar 14;55(12):3925-30. doi: 10.1002/anie.201509864. Epub 2016 Feb 10.
Sequence control in polymers, well-known in nature, encodes structure and functionality. Here we introduce a new architecture, based on the nucleophilic aromatic substitution chemistry of cyanuric chloride, that creates a new class of sequence-defined polymers dubbed TZPs. Proof of concept is demonstrated with two synthesized hexamers, having neutral and ionizable side chains. Molecular dynamics simulations show backbone-backbone interactions, including H-bonding motifs and pi-pi interactions. This architecture is arguably biomimetic while differing from sequence-defined polymers having peptide bonds. The synthetic methodology supports the structural diversity of side chains known in peptides, as well as backbone-backbone hydrogen-bonding motifs, and will thus enable new macromolecules and materials with useful functions.
聚合物中的序列控制在自然界中广为人知,它编码结构和功能。在此,我们基于三聚氯氰的亲核芳香取代化学引入了一种新架构,该架构创造了一类被称为TZPs的新型序列定义聚合物。通过两个合成的六聚体(具有中性和可电离侧链)证明了概念验证。分子动力学模拟显示了主链-主链相互作用,包括氢键基序和π-π相互作用。这种架构可以说是仿生的,同时不同于具有肽键的序列定义聚合物。该合成方法支持肽中已知的侧链结构多样性以及主链-主链氢键基序,因此将能够实现具有有用功能的新型大分子和材料。