Cryptophane-Xenon Complexes in Organic Solvents Observed through NMR Spectroscopy
Cryptophane-Xenon Complexes in Organic Solvents Observed through NMR Spectroscopy
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DOI：
10.1021/jp807425t
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发表时间：
2008-11-13
影响因子：
2.9
通讯作者：
Berthault, Patrick
中科院分区：
文献类型：
--
作者：
Huber, Gaspard;Beguin, Lwtitia;Berthault, Patrick
用热极化和超极化的核磁共振方法研究了氙气与隐形化合物的相互作用。稀有气体。本研究选取了12个具有不同立体化学结构、空腔大小以及芳环上取代基性质和数量的主体进行研究，以期为这些笼状分子衍生的Xe-129-核磁共振生物传感器的优化提供线索。研究了四个重要的性质：氙主结合常数、惰性气体的进出交换率、化学位移和笼中氙气的弛豫。这项工作旨在了解主-客相互作用的主要特征，以便为生物传感方法选择最佳候选者。此外，将氙气化学位移作为结构参数的函数进行合理化，也将有助于建立多路应用。氙气对最小的隐形原子-111具有最高的亲和力，并且具有较长的驰豫时间，有利于其超极化的守恒。然而，非常慢的输入-输出氙气交换可能会限制其未来对生物传感方法的适用性，因为无法充分利用激光偏振氙气中笼子的补充，从而能够进一步提高灵敏度。
The interaction of xenon with cryptophane derivatives is analyzed by NMR by using either thermal or hyperpolarized. noble gas. Twelve hosts differing by their stereochemistry, cavity size, and the nature and the number of the substituents on the aromatic rings have been included in the study, in the aim of extracting some clues for the optimization of Xe-129-NMR based biosensors derived from these cage molecules. Four important properties have been examined: xenon-host binding constant, in-out exchange rate of the noble gas, chemical shift, and relaxation of caged xenon. This work aims at understanding the main characteristics of the host-guest interaction in order to choose the best candidate for the biosensing approach. Moreover, rationalizing xenon chemical shift as a function of structural parameters would also help for setting up multiplexing applications. Xenon exhibits the highest affinity for the smallest cryptophane, namely cryptophane-111, and a long relaxation time inside it, convenient for conservation of its hyperpolarization. However, very slow in-out xenon exchange could represent a limitation for its future applicability for the biosensing approach, because the replenishment of the cage in laser-polarized xenon, enabling a further gain in sensitivity, cannot be fully exploited.