TY - JOUR
T1 - An electrospray-ionization tandem mass spectrometry method for determination of the anomeric configuration of glycosyl 1-phosphate derivatives
AU - Wolucka, Beata A.
AU - Rush, Jeffrey S.
AU - Waechter, Charles J.
AU - Shibaev, Vladimir N.
AU - De Hoffmann, Edmond
N1 - Funding Information:
A part of this work was supported by Grant 96-03-32473 from the Russian Foundation for Basic Research.
PY - 1998/1/15
Y1 - 1998/1/15
N2 - A rapid, simple, and sensitive method is described for the determination of the anomeric configuration of sugar 1-phosphates, sugar nucleotides, and polyisoprenyl-phospho-sugars. Negative-ion electrospray ionization of picomole amounts of glycosyl 1-phosphate derivatives produces an intense signal of the [M-H]-deprotonated molecule which, by collision-induced dissociation, decomposes in a characteristic manner depending on cis/trans configuration of the 2-hydroxyl and phosphate groups of the glycosyl residue. A distinct feature of the product ion spectra of glycosyl 1-P and polyisoprenyl-P-sugars with cis configuration is the presence of abundant ions that correspond to the [M-H2O-H]- dehydration product and the [R- PO4-(C2H3O)]- fragment arising from a cleavage across the sugar ring, where R is -H or -polyprenyl/dolichyl for glycosyl 1-P and polyisoprenyl-P- sugar, respectively. These two fragments, [M-H2O-H]- and [R-PO4- (C2H3O)]-, are absent from the product ion spectra of sugar 1-P and polyisoprenyl-P-sugars with trans configuration. For sugar nucleotides, compounds with cis configuration produce, in tandem mass spectrometry, only one abundant fragment of nucleoside monophosphate, whereas those with trans configuration give nucleoside diphosphate as a major fragment ion. Accordingly, the anomeric configuration of a glycosyl 1-phosphate derivative can be easily determined by using electrospray-ionization tandem mass spectrometry provided that the glycosyl residue of known absolute configuration has a free 2-hydroxyl group and no other charge location.
AB - A rapid, simple, and sensitive method is described for the determination of the anomeric configuration of sugar 1-phosphates, sugar nucleotides, and polyisoprenyl-phospho-sugars. Negative-ion electrospray ionization of picomole amounts of glycosyl 1-phosphate derivatives produces an intense signal of the [M-H]-deprotonated molecule which, by collision-induced dissociation, decomposes in a characteristic manner depending on cis/trans configuration of the 2-hydroxyl and phosphate groups of the glycosyl residue. A distinct feature of the product ion spectra of glycosyl 1-P and polyisoprenyl-P-sugars with cis configuration is the presence of abundant ions that correspond to the [M-H2O-H]- dehydration product and the [R- PO4-(C2H3O)]- fragment arising from a cleavage across the sugar ring, where R is -H or -polyprenyl/dolichyl for glycosyl 1-P and polyisoprenyl-P- sugar, respectively. These two fragments, [M-H2O-H]- and [R-PO4- (C2H3O)]-, are absent from the product ion spectra of sugar 1-P and polyisoprenyl-P-sugars with trans configuration. For sugar nucleotides, compounds with cis configuration produce, in tandem mass spectrometry, only one abundant fragment of nucleoside monophosphate, whereas those with trans configuration give nucleoside diphosphate as a major fragment ion. Accordingly, the anomeric configuration of a glycosyl 1-phosphate derivative can be easily determined by using electrospray-ionization tandem mass spectrometry provided that the glycosyl residue of known absolute configuration has a free 2-hydroxyl group and no other charge location.
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U2 - 10.1006/abio.1997.2421
DO - 10.1006/abio.1997.2421
M3 - Article
C2 - 9451510
AN - SCOPUS:0032518331
SN - 0003-2697
VL - 255
SP - 244
EP - 251
JO - Analytical Biochemistry
JF - Analytical Biochemistry
IS - 2
ER -