Engineered Binding Microenvironments in Halogen Bonding Polymers for Enhanced Anion Sensing
Engineered Binding Microenvironments in Halogen Bonding Polymers for Enhanced Anion Sensing
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用于增强阴离子传感的卤素键合聚合物中的工程结合微环境
DOI：
10.1002/ange.202300867
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发表时间：
2023
影响因子：
--
通讯作者：
Bak K
中科院分区：
文献类型：
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作者：
Bak K
通过设计具有从主体溶剂中筛选出的结合腔的宿主来模仿自然界的聚合物蛋白质结构，是在竞争性介质中实现阴离子识别的一种很有前途的方法。然而，实现这一点可能是综合要求的。在这里，我们提出了一种合成容易处理的方法，通过直接将有效的超分子阴离子受体基序结合到聚合物支架中，通过明智地选择共聚单体来调节。用氧化还原活性、卤素键合的聚合物主体对阴离子识别和传感进行了全面的分析。值得注意的是，聚合物主体的表现一直优于它们的单体类似物，尤其是在水-有机溶剂混合物中观察到的卤化物结合增强了约50倍。这些结合增强通过低介电常数结合微环境的产生和呈现而合理化，其中存在明显的溶剂排斥。
Mimicking Nature's polymeric protein architectures by designing hosts with binding cavities screened from bulk solvent is a promising approach to achieving anion recognition in competitive media. Accomplishing this, however, can be synthetically demanding. Herein we present a synthetically tractable approach, by directly incorporating potent supramolecular anion‐receptive motifs into a polymeric scaffold, tuneable through a judicious selection of the co‐monomer. A comprehensive analysis of anion recognition and sensing is demonstrated with redox‐active, halogen bonding polymeric hosts. Notably, the polymeric hosts consistently outperform their monomeric analogues, with especially large halide binding enhancements of ca. 50‐fold observed in aqueous‐organic solvent mixtures. These binding enhancements are rationalised by the generation and presentation of low dielectric constant binding microenvironments from which there is appreciable solvent exclusion.