Ditopic Ion Transport Systems: Anion-p Interactions and Halogen Bonds at Work
Ditopic Ion Transport Systems: Anion-p Interactions and Halogen Bonds at Work
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DOI：
10.1002/anie.201104966
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发表时间：
2011-01-01
影响因子：
16.6
通讯作者：
Matile, Stefan
中科院分区：
文献类型：
--
作者：
Jentzsch, Andreas Vargas;Emery, Daniel;Matile, Stefan
在脂质双层膜中运行的离子运输系统[1 - 3]正在成为一种有吸引力的工具，用于探测弱相互作用的功能相关性，否则很难观察到这种方法建立在这样一个概念之上，即与结合研究中检测所需的相互作用相比，传输和催化在弱相互作用下运行得最好。早期在理论和体膜上的重要工作已经证实了传输效率遵循“金发姑娘原则”，即更强的粘合剂不是最好的传输体在此，我们引入了单原子突变系列和一个新的双主题离子传输系统，以证明阴离子-π相互作用的一般功能相关性，并首次实现了阴离子与卤素键的传输。与氢键的频率相比，功能卤素键的稀缺性[5-10]让人想起阴离子-π相互作用[11]与无处不在的阳离子-π相互作用的情况。卤素键的强度随卤素原子极化率的增加而增加，在碘取代基上卤素键的效率最高。[5,6]它们强烈依赖于环境，包括溶剂化/脱溶作用，并且在非竞争性疏水溶剂中最强卤素键在固态晶体工程中得到了广泛的研究虽然存在合理药物设计和溶液中阴离子与卤素键结合的开创性例子，但它们在催化方面的应用，特别是在运输方面的应用，基本上还没有被探索过。杯状[4]芳烃1-6被设计用来分析卤素键、氢键和阴离子-π的单独贡献
Ion transport systems that operate in lipid bilayer membranes [1–3] are emerging as attractive tools to probe the functional relevance of weak interactions that are otherwise difficult to observe.[1] This approach builds on the notion that transport and catalysis operate best with weaker interactions than the ones that are required for detection in binding studies. Earlier important work in theory and in bulk membranes has confirmed that transport efficiency follows “Goldilocks principle”, with the stronger binders not being the best transporter.[4] Herein, we introduce single-atom mutation series with a new ditopic ion transport system to demonstrate the general functional relevance of anion–π interactions and to achieve, for the first time, anion transport with halogen bonds.The rarity of functional halogen bonds [5–10] compared to the frequency of hydrogen bonds is reminiscent of the situation with anion–π interactions [11] compared to the ubiquitous cation–π interactions. Increasing in strength with halogen atom polarizability, halogen bonds are most efficient with iodine substituents.[5, 6] They strongly depend on the environment, including contributions from solvation/desolvation, and are strongest in noncompetitive hydrophobic solvents.[7] Halogen bonds have been studied extensively in solid-state crystal engineering.[5] Whereas pioneering examples for rational drug design [8] and anion binding with halogen bonds in solution exist,[9] their application to catalysis [10] and particularly to transport is essentially unexplored. Calix [4] arenes 1–6 were designed to dissect the individual contributions of halogen bonds, hydrogen bonds, and anion–π