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Article Dans Une Revue Analytical and Bioanalytical Chemistry Année : 2021

Exploring the enantiomeric 13C position-specific isotope fractionation: challenges and anisotropic NMR-based analytical strategy

Résumé

Trying to answer the intriguing and fundamental question related to chiral induction/amplification at the origin of homochirality in Nature: "Is there a relationship between enantiomeric and isotopic fractionation of carbon 13 in chiral molecules?" is a difficult but stimulating challenge. Although isotropic 13C-PSIA NMR is a promising tool for determination of (13C/12C) ratios capable of providing key 13C isotopic data for understanding the reaction mechanisms of biological processes or artificial transformations, this method does not provide access to any enantiomeric 13C isotopic data unless mirror-image isomers are first physically separated. Interestingly, 13C spectral enantiodiscriminations can be potentially performed in situ in presence of enantiopure entities as chiral-europium complexes or chiral liquid crystals (CLCs). In this work, we explored for the first time the capabilities of the anisotropic 13C-{1H} NMR using PBLG-based lyotropic CLCs as enantiodiscriminating media in the context of the enantiomeric position-specific 13C isotope fractionation (EPSIF), within the requested precision of the order of the permil. As enantiomeric NMR signals are discriminated on the basis of a difference of 13C residual chemical shift anisotropy (13C-RCSA) prior to be deconvoluted, analysis of enantiomeric mixtures becomes possible. The analytical potential of this approach when using poly--benzyl-L-glutamate (PBLG) is presented, and the preliminary quantitative results on small model chiral molecules obtained at 17.5 T with a cryogenic NMR probe are reported and discussed
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Dates et versions

hal-03409628 , version 1 (29-10-2021)

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Philippe Lesot, Philippe Berdagué, Virginie Silvestre, Gérald Remaud. Exploring the enantiomeric 13C position-specific isotope fractionation: challenges and anisotropic NMR-based analytical strategy. Analytical and Bioanalytical Chemistry, 2021, 413 (25), pp.6379-6392. ⟨10.1007/s00216-021-03599-8⟩. ⟨hal-03409628⟩
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