| A New Approach to the Characterization of Sulfated and Sialyl Lewis-Type Glycosphingolipids Using Positive-Ion FABMS, ESIMS, and CID-MS/MS |
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*a) Glycobiology Research, Frontier Research Program, The Institute of Physical and Chemical Research (RIKEN) (Wako-shi, Saitama 351-01, Japan) b) Research and Development Laboratories, Soda Aromatic Co., Ltd. (Noda-shi, Chiba 270-02, Japan) c) Laboratory of Synthetic Cellular Chemistry, The Institute of Physical and Chemical Research (RIKEN) (Wako-shi, Saitama 351-01, Japan) d) Faculty of Agriculture, University of Tokyo (Yayoi, Bunkyo-ku, Tokyo 113, Japan) |
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| Positive-ion fast atom bombardment (FAB) and electrospray ionization (ESI) mass spectrometry have been used in the structural characterization of sulfated and sialyl Lewis (Le)-type glycosphingolipids. Both FAB and ESI collision-induced dissociation tandem mass spectrometry (CID-MS/MS) of acidic glycosphingolipids allowed identification of the sulfated and sialyl sugars, and provided information on the sugar chain sequences. The positive-ion tandem FABMS of sulfated Le-type glycosphingolipids gave the daughter ions produced by the elimination of (fucose-H2O) unit from the fragment ions containing the non-reducing end. On the other hand, the CID-MS/MS of sialyl analogs showed the characteristic ions derived from the loss of (N-acetylneuraminic acid-H2O) unit, in addition to the elimination of (fucose-H2O) unit. The ESI CID-MS/MS of multiple-charged ions provided even more detailed structural information, and some of the daughter ions useful for structural studies appeared in the higher mass region than the precursor owing to a lower charge-state. These methodologies can be applied to the structural analyses of glycoconjugates with much larger molecular masses and higher polarity, such as the poly-sulfated and sialyl analogs. | ||
| Key words: Sulfated Lewisa, Sulfated Lewisx, Sialyl Lewisa, Sialyl Lewisx, Glycosphingolipid, Fast atom bombardment mass spectrometry, Electrospray ionization mass spectrometry, Collision-induced dissociation tandem mass spectrometry | ||
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