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Diercks, Tammo; Infantino, Angela Simona; Unione, Luca; Jimenez-Barbero, Jesus; Oscarson, Stefan; Gabius, Hans-Joachim (2018): Fluorinated Carbohydrates as Lectin Ligands: Synthesis of OH/F-Substituted N-Glycan Core Trimannoside and Epitope Mapping by 2D STD-TOCSYreF NMR spectroscopy. In: Chemistry-A European Journal, Vol. 24, No. 59: pp. 15761-15765
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Abstract

Glycan-protein interactions play an important role in a broad range of physiological processes, raising interest to elucidate the structural interplay. Yet, their dynamic nature limits the analysis by crystallography, whereas NMR spectroscopy suffers from the low (1) H dispersion of glycans. Therefore, their sparse fluorination and NMR screening by 1D Saturation Transfer Difference with relay to (19) F (STDreF) was previously proposed to exploit the superior dispersion in (19) F NMR spectroscopy. A new 2D STD-TOCSYreF experiment is presented here that enables comprehensive epitope mapping of fluorinated glycans by combining the spectral resolution of (19) F with the spatial resolution and coverage of (1) H. For an illustration, the 2-deoxy-2-fluoro derivative of the N-glycan core trimannoside was synthesised and its recognition of Pisum sativum agglutinin by either of the two terminal mannose residues was confirmed. Going beyond the crystallographic information, the 2D STD-TOCSYreF spectrum moreover visualised collateral contacts from the branching mannose and allowed to assess the ratio of both co-existing binding modes through the alpha1,3- (67 %) and alpha1,6-linked (33 %) terminal mannose moieties.