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 ena...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 ofβ-cyclodextrin(β-CD),a widely used host molecule,in the hostguest chemistry by magnetic anisotropy.A rigid and chiral lanthanide binding tag was attached to theβ-CD to amplify the changes of nuclear magnetic resonance(NMR)signals in the host-guest recognition process.The installation of the paramagnetic lanthanide ion inβ-CD greatly enhances the enantiomeric discrimination up to 30-fold in comparison with the diamagneticβ-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 ofβ-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.展开更多
基金supported by the Ministry of Science and Technology of China(2021YFA1600304)the National Natural Science Foundation of China(22161142018,21991081,22174074,22374126)。
文摘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 ofβ-cyclodextrin(β-CD),a widely used host molecule,in the hostguest chemistry by magnetic anisotropy.A rigid and chiral lanthanide binding tag was attached to theβ-CD to amplify the changes of nuclear magnetic resonance(NMR)signals in the host-guest recognition process.The installation of the paramagnetic lanthanide ion inβ-CD greatly enhances the enantiomeric discrimination up to 30-fold in comparison with the diamagneticβ-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 ofβ-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.
