Lee Seunghyun, Shin Aram, Park Jinwoo, Yun Sowon, Kim Minseong, Lee Dong Woog, Kim Byeong-Su
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of Korea.
Department of Chemistry, Yonsei University, Seoul 03722, Republic of Korea.
Proc Natl Acad Sci U S A. 2025 Feb 11;122(6):e2419404122. doi: 10.1073/pnas.2419404122. Epub 2025 Feb 5.
Anion-π interactions are crucial in various biological processes, such as enzyme catalysis and ion transport. Despite their significance, the exploitation of anion-π interactions in synthetic polymer systems remains underexplored. This study investigates anion-π interactions using chemically well-defined peptidomimetics guided by the composition of mussel foot proteins. Specifically, polyether-based polymers were designed utilizing two functional epoxide monomers-catechol acetonide glycidyl ether and 4,4-dimethyl-2-oxazoline glycidyl ether-to mimic the key amino acids 3,4-dihydroxyphenylalanine and aspartic acid, respectively. A surface forces apparatus was employed to study the anion-π interaction between the polymers, considering the effects of relative monomer composition and pH conditions. The maximum cohesion energy of 15.0 mJ/m was observed at an equimolar monomer composition at pH 7. Incorporating a phenyl group instead of the catechol group and introducing competing anions confirmed the dominant role of anion-π interactions. This study highlights the significance of anion-π interactions, posing a high potential in the design and synthesis of functional materials.
阴离子-π相互作用在各种生物过程中至关重要，如酶催化和离子运输。尽管其具有重要意义，但在合成聚合物体系中对阴离子-π相互作用的开发仍未得到充分探索。本研究以贻贝足蛋白的组成为指导，利用化学结构明确的拟肽来研究阴离子-π相互作用。具体而言，基于聚醚的聚合物是利用两种功能性环氧化合物单体——儿茶酚丙酮缩甘油醚和4,4-二甲基-2-恶唑啉缩水甘油醚——分别模拟关键氨基酸3,4-二羟基苯丙氨酸和天冬氨酸设计而成的。考虑到相对单体组成和pH条件的影响，采用表面力仪研究了聚合物之间的阴离子-π相互作用。在pH 7的等摩尔单体组成下，观察到最大内聚能为15.0 mJ/m²。用苯基取代儿茶酚基团并引入竞争性阴离子证实了阴离子-π相互作用的主导作用。本研究突出了阴离子-π相互作用的重要性，在功能材料的设计与合成方面具有很高的潜力。
