New 4-O-substituted xylosyl units in the xyloglucan from leaves of Hymenaea courbaril

A homogeneous fucogalactoxyloglucan, isolated from the leaves of Hymenaea courbaril, was analysed by methylation-GC-MS. These procedures involved derived partially O-methylated alditol acetates and acetylated aldononitriles, which demonstrated the presence of both 2-O- and 4-O-substituted Xylp units in the side-chains. The presence of the unusual, latter structure was confirmed by 2D NMR spectroscopy with a correlated HMQC C-4/H-4 signal at δ 77.8/3.73. A similar 4-O-substituted xylosyl structure was present in a decasaccharide Glc4Xyl3Gal2Fuc obtained via endo-glucanase treatment of the polysaccharide, which gave rise to a molecular ion with m/z 1555 (ESI-MS, Na+ form).