Primary structure of neutral oligosaccharides derived from respiratory‐mucus glycoproteins of a patient suffering from bronchiectasis, determined by combination of 500‐MHz ¹H‐NMR spectroscopy and quantitative sugar analysis

Abstract

Carbohydrate chains of respiratory‐mucus glycopeptides from a patient (blood group O) suffering from bronchiectasis with a Kartagener's syndrome have been released by alkaline borohydride treatment. Application of high‐performance liquid chromatography using subsequently two silica columns, one bonded with aminopropyl groups and the other with octadecyl groups, afforded 39 neutral fractions; 35 oligosaccharide‐alditol structures have been characterized by employing 500‐MHz 1H‐NMR spectroscopy in conjunction with sugar analysis. Here, 16 oligosaccharide structures, possessing a core consisting of Galβ(1→3)GalNAc‐ol with or without branching through a GlcNAc residue linked β(1→6) to the GalNAc residue (core type 2 or core type 1, respectively), are described. Ten oligosaccharide‐alditols with these types of cores (2, 3, 10a, 14, 7, 11a, 15a, 16a, 12 and 16c) have been identified previously in human bronchial mucins of patients suffering from cystic fibrosis [Lamblin, G., Boersma, A., Lhermitte, M., Roussel, P., Mutsaers, J. H. G. M., Van Halbeek, H. and Vliegenthart, J. F. G. (1984) Eur. J. Biochem. 143, 227–236]. Of the remaining six compounds, one is a partial structure of oligosaccharides previously described: The structures 17a and 20 contain the Y determinant, i.e., Fucα(1→2)Galβ(1→4)[Fucα(1→3)]GlcNAcβ(1→). High‐resolution 1H‐NMR spectroscopy is able to distinguish whether the Y determinant is β(1→3) or β(1→6) linked in such oligosaccharide‐alditols.

Six fucose‐α(1–2) sugars and α‐fucose assigned in the human brain using in vivo two‐dimensional MRS

“…They have reported that the MR spectral characteristics, in particular the chemical shift, alter according to the type of oligosaccharide in which the fucose is incorporated . They have also described how the chemical shifts of these fucose entities can alter with changes to the microenvironment , such as pH. The spectral characteristics are consistent with several of those assigned in the cell models.…”

1H‐MRS can detect aberrant glycosylation in tumour cells: a study of the HeLa cell line

“…It cannot be invoked for the fucose in b conformation as this molecule is only present in mammals in GDP-fucose and/or in free fucose and not in fucose bound to other residues. Either the presence of free fucose or a restricted On the other hand, the intensity of the fucose signal at 4.28 ppm, corresponding to a fucose bound to Gal (54,55,57), increases after the Golgi pH increase by NH 4 Cl treatment (Table 3). Distribution of fucosyltransferase has been the object of studies in relation to Lewis antigen synthesis by concluding that its alteration is mainly attributable to Golgi subcompartments (63).…”

“…According to current literature (54)(55)(56)(57)(58)(59), the chemical shift of the H5 proton points to fucose moiety differently bound in an oligosaccharide chain. The rather low-field resonance of aFuc2 and aFuc3 reported in Table 2 …”

“…residues bound to Gal (54)(55)(56)(57)(58)(59). Two fucose residues with these bonding are, actually, present in the antigen sialyl Lewis Y, and are released in blood (9) while the sialyl Lewis X contains only one Fuc bound to GlcNAc that actually resonates at 4.83 ppm (56).…”

The role of airway mucus in pulmonary toxicology.

“…Mucin glycans can be classified into three groups of increasing acidity: neutral, sialylated, and sulfated (22,(36)(37)(38). To date, over 100 mucin oligosaccharides have been identified, including 81 from one subject alone (22,37,(39)(40)(41).…”