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Increase of chiral sensing ability in host-guest chemistry by magnetic anisotropy
Science China Chemistry ( IF 10.4 ) Pub Date : 2024-06-19 , DOI: 10.1007/s11426-024-1989-y
Jia-Liang Chen , Bin Li , Feng Yang , Tiesheng Shi , Xun-Cheng Su

Enantiomeric molecules generally play distinct functions in chemistry, biology, and pharmacology. Similar physical and chemical properties of chiral analytes lay difficulty in discrimination and quantification of the enantiomers. We report herein an efficient approach of increasing the chiral sensing ability of β-cyclodextrin (β-CD), a widely used host molecule, in the host-guest chemistry by magnetic anisotropy. A rigid and chiral lanthanide binding tag was attached to the β-CD to amplify the changes of nuclear magnetic resonance (NMR) signals in the host-guest recognition process. The installation of the paramagnetic lanthanide ion in β-CD greatly enhances the enantiomeric discrimination up to 30-fold in comparison with the diamagnetic β-CD reference. In addition, the magnitude of the paramagnetic effects is tunable according to the diverse range of paramagnetic strength of the lanthanide series. The reported method significantly increases the chiral sensing ability of β-CD, which can be applied to other host molecules. The transferred paramagnetic effects, pseudocontact shifts (PCSs) and paramagnetic relaxation enhancements (PREs), from the host to the guest molecules, are valuable structural restraints to determine the absolute stereochemistry of the chiral analytes. The strategy does not need modification of the analytes and is complementary to the reported analytical methods that rely on the functionalization of the chiral analytes.



中文翻译:


通过磁各向异性提高主客体化学中的手性传感能力



对映体分子通常在化学、生物学和药理学中发挥不同的功能。手性分析物相似的物理和化学性质给对映体的区分和定量带来了困难。我们在此报告了一种通过磁各向异性提高主客体化学中广泛使用的主体分子β-环糊精(β-CD)手性传感能力的有效方法。将刚性手性镧系元素结合标签附着在β-CD上,以放大主客体识别过程中核磁共振(NMR)信号的变化。与反磁性 β-CD 参考相比,在 β-CD 中安装顺磁性镧系元素离子大大增强了对映体辨别能力,高达 30 倍。此外,顺磁效应的大小可以根据镧系元素顺磁强度的不同范围进行调节。该方法显着提高了β-CD的手性传感能力,可应用于其他主体分子。从主体分子到客体分子的转移顺磁效应、赝接触位移(PCS)和顺磁弛豫增强(PRE)是确定手性分析物的绝对立体化学的有价值的结构限制。该策略不需要对分析物进行修改,并且是对依赖于手性分析物功能化的报道的分析方法的补充。

更新日期:2024-06-22
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