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Lipid bilayer environments control exchange kinetics of deep cavitand hosts and enhance disfavored guest conformations†
Chemical Science ( IF 8.4 ) Pub Date : 2018-01-11 00:00:00 , DOI: 10.1039/c7sc05155g
Lizeth Perez 1 , Bethany G Caulkins 1 , Magi Mettry 1 , Leonard J Mueller 1 , Richard J Hooley 1
Affiliation  

The effects on the molecular recognition properties of water-soluble deep cavitand hosts upon embedding them in phosphocholine lipid bilayer environments have been studied by 2D NMR experiments. By employing suitable guests containing 19F or 13C nuclei that can be encapsulated inside the host, 2D EXSY NMR experiments can be used to analyze and compare the in/out guest exchange rates in aqueous solution, isotropically tumbling micelles, or magnetically ordered bicelles. These analyses show that embedding the deep cavitands in lipid bilayers slows the guest exchange rate, due to the lipids acting as a “compression sleeve” around the host, restricting guest egress. This effect also enhances guest conformations in the host that are not observed in free solution, such as axial cyclohexane conformers and ketone hydrates.

中文翻译:

脂质双层环境控制深空洞和宿主的交换动力学并增强不受欢迎的客体构象†

已经通过二维核磁共振实验研究了将水溶性深空洞和宿主嵌入磷酸胆碱脂质双层环境中对分子识别特性的影响。通过雇用包含19 F 或13的合适的客人可以封装在主体内部的 C 核,2D EXSY NMR 实验可用于分析和比较水溶液、各向同性翻滚胶束或磁性有序双胶束中的进/出客体交换率。这些分析表明,将深层空泡嵌入脂质双层会减慢客体交换率,因为脂质在宿主周围充当“压缩套筒”,限制客体出口。这种效应还增强了在游离溶液中未观察到的主体中的客体构象,例如轴向环己烷构象异构体和酮水合物。
更新日期:2018-01-11
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