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Volume 271,
Number 7,
Issue of February 16, 1996 pp. 3496-3499
©1996 by The American Society for Biochemistry and Molecular Biology, Inc.
Investigation
of the Calcium-mediated Association between the Carbohydrate Head
Groups of Galactosylceramide and Galactosylceramide I Sulfate by Electrospray Ionization Mass Spectrometry
(Received for publication, August 28,
1995; and in revised form, November 20, 1995)
Kalavelil M.
Koshy
,
Joan M.
Boggs
Calcium has been shown previously to cause aggregation of
phosphatidylcholine/cholesterol liposomes containing galactosylceramide
(GalCer) with similar liposomes containing cerebroside sulfate
(galactosylceramide I sulfate) (CBS), suggesting that it
mediates a carbohydrate-carbohydrate association between these two
glycolipids. In order to determine if such an association occurs, the
noncovalent complexes formed on addition of calcium chloride to GalCer
and CBS in methanol were examined by positive and negative ion spray
mass spectrometry. Monomeric Ca complexes of both
lipids were observed. In addition, Ca also caused
oligomerization of GalCer. Oligomerization of CBS anion was not seen,
but dimers would not have been observed, as they would be neutral.
However, Ca caused heterotypic complexation of GalCer
and CBS. Although these heterotypic complexes were of low abundance in
methanol compared with the other monomeric and homotypic oligomeric
positive ions formed at low declustering potentials, the heterotypic
dimer
[GalCer CBS Ca -H] had the greatest stability of all oligomers formed and was the
only one to survive at high declustering potentials. Na did not cause oligomerization of GalCer in methanol indicating
that the complexes of GalCer with Ca are not caused
by van der Waals interactions between the lipid moieties. GalCer and
CBS are present in high concentrations in myelin. This
Ca -mediated carbohydrate-carbohydrate interaction,
which can bridge apposing bilayers, may be involved in adhesion of the
extracellular surfaces of the myelin sheath.

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Copyright © 1996 by the American Society for Biochemistry and Molecular Biology.
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