Primary structure of human milk octa-, dodeca- and tridecasaccharides determined by a combination of 1H-NMR spectroscopy and fast-atom-bombardment mass spectrometry. Evidence for a new core structure, the para-lacto-N-octaose.

Two octasaccharides, two dodecasaccharides and a tridecasaccharide have been isolated from human milk by a combination of paper chromatography, high-performance liquid chromatography and high-performance anion-exchange chromatography. Their structural analysis investigated by 400-MHz 1H- and 13C-NMR spectroscopy and by mass spectrometry led to the following structures. [formula: see text] The two octasaccharides have been previously characterized in human milk; the complete assignment of the 1H and 13C spectra is reported here. One of the dodecasaccharides is a tetrafucosyl derivative with a new core: typeI-(beta 1-3)-typeII-(beta 1-3)-typeII-(beta 1-3)-Gal((beta 1-4)Glc, where typeI = Gal(beta 1-3)GlcNAc and typeII = Gal(beta 1-4)GlcNAc. These oligosaccharides display simultaneously Lewis(b) and Lewis(x) determinants or Lewis(a), Lewis(b) and Lewis(x) determinants.