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Prior studies of the solution conformation of the Lewis (Le) trisaccharide, αFuc-(1→3)[βGal-(1→4)]-βGlcNAc, suggest that nonclassical inter-residue C-H···O hydrogen bonding in aqueous solution contributes to the stabilization of its 3D structure and affects its biological properties. Experimental evidence for this hydrogen bond in aqueous solution has been reported in the form of a NMR spin-coupling constant between C5'Fuc and H1″Gal measured by 2D NMR methods in unlabeled samples. A methyl glycoside of Le (MeβLe) was prepared containing selective C-labeling at C5'Fuc, and the H1″Gal signal was examined in high-field H NMR spectra for evidence of splitting or line-broadening caused by the C at C5'Fuc.

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An emerging NMR method, analysis, has been applied to investigate context effects on the conformational properties of several human milk oligosaccharides (HMOs). The model of the β-(1→4) linkage in the disaccharide, methyl β-lactoside (MeL), was compared to those obtained for the same linkage in the HMO trisaccharides, methyl 2'-fucosyllactoside (Me2'FL) and methyl 3-fucosyllactoside (Me3FL), and in the tetrasaccharide, methyl 2',3-difucosyllactoside (Me2',3DFL). analysis revealed significant context effects on the mean values and circular standard deviations (CSDs) of the psi (ψ) torsion angles in these linkages.

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Bioinformatics-aided function exploration of GH29 fucosidases from human gut Parabacteroides.

Glycobiology

December 2024

Guangdong Engineering Technology Research Centre of Enzyme and Biocatalysis, Institute of Biological and Medical Engineering, Guangdong Academy of Sciences, No. 10 Shiliugang Road, Haizhu District, Guangzhou, Guangdong 510316, P. R. China.

Gut microbes produce α-l-fucosidases critical for utilizing human milk oligosaccharides, mucosal and dietary glycans. Although gut Parabacteroides have garnered attention for their impact on host health and disease, their CAZymes remain poorly studied. CAZome analysis of eleven gut Parabacteroides type strains revealed their capacity to degrade mucin O-glycans.

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Gas-Phase Structures of Fucosylated Oligosaccharides: Alkali Metal and Halogen Influences.

J Phys Chem B

September 2024

Department of Chemistry and Biochemistry and Biomolecular Sciences Institute, Florida International University, 11200 SW Eighth Street, Miami, Florida 33199, United States.

Fucosylated carbohydrate antigens play critical roles in physiology and pathology with function linked to their structural details. However, the separation and structural characterization of isomeric fucosylated epitopes remain challenging analytically. Here, we report for the first time the influence of alkali metal cations (Li, Na, K, Rb, and Cs) and halogen anions (Cl, Br, and I) on the gas-phase conformational landscapes of common fucosylated trisaccharides (Lewis A, X, and H types 1 and 2) and tetrasaccharides (Lewis B and Y) using trapped ion mobility spectrometry coupled to mass spectrometry and theoretical calculations.

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Article Synopsis
  • Protonated fucose-containing oligosaccharides often rearrange during mass spectrometry, creating complex fragments that complicate analysis.
  • This study utilizes density functional theory to analyze IR spectra of specific trisaccharides, concluding that they do not undergo rearrangement in the gas phase.
  • Key factors for rearrangement include the presence of a mobile proton and the stability differences between the parent ions and their rearranged forms.
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