Glycobiology Advance Access published online on September 26, 2003
Glycobiology, doi:10.1093/glycob/cwh003
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© 2003 Oxford University Press
ORIGINAL ARTICLES
1 Institute of Medical Biochemistry, Göteborg University, Box 440, SE 405 30, Sweden Glycoconjugates of the gastrointestinal tract are important for microbial interactions. The expression of histo-blood group glycosyltransferases both governs the expression of blood group determinants and in part the structure and size of the glycoconjugates. Using neutral glycolipids isolated from the small intestine of a rare blood group O Le(a-b-) ABH secretor-negative (nonsecretor) individual we were able to map the "default" pathway of the individual lacking ABO, Lewis and secretor glycosyltransferases. Structures were deduced with combined analysis of mass spectrometry (MALDI-TOF and ESI-MS/MS), and 1H nuclear magnetic resonance spectroscopy (500 and 600 MHz 1H NMR). All structures present at a level >5% were structurally resolved and included two extended structures: Gal The first, a novel component, is based on a type 2 chain and bears the Lex glycotopes on both its branches. The second, a major component, is based on a type 1 chain which bears a 3-linked type 1 precursor (Lec) glycotope and a 6-linked Lex glycotope on its branches. This latter structure is identical to that previously isolated from plasma and characterized by MS and GC-MS but not by NMR. Structural resolution of these structures was supported by reanalysis of the blood group H-active decaosylceramides previously isolated from rat small intestine. Other minor linear monofucosylated penta-, hepta- and difucosylated octaosylceramides, some bearing blood group determinants, were also identified. The cumulative data was used to define a default biosynthesis pathway where it can be seen that carbohydrate chain extension, in the absence of blood group glycosyltransferases, is controlled and regulated by non-blood group fucosylation and branching with type 2 Gal
Revised on August 31, 2003
Accepted on September 3, 2003
Default biosynthesis pathway for blood-group related glycolipids in human small intestine as defined by structural identification of linear and branched glycosylceramides in a group O Le(a-b-) nonsecretor
2 Swegene Proteomics Center, Göteborg University, Sweden
3 Glycoscience Research Centre, Auckland University of Technology, Private Bag 92006, Auckland 1020, New Zealand; Kiwi Ingenuity Limited, PO Box 39373, Howick, New Zealand
4(Fuc
3)GlcNAc3(Gal4[Fuc3]GlcNAc6)Gal4GlcNAc3Gal4Glc1Cer and Gal3GlcNAc3(Gal4[Fuc3]GlcNAc6)Gal3GlcNAc3Gal4Glc1Cer.4GlcNAc branches.
Glycosyltransferase, ABO, Lewis, Secretor, histo-blood group antigen
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