Bottom-up elucidation of glycosidic bond stereochemistry
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Bottom-up elucidation of glycosidic bond stereochemistry. / Gray, Christopher J.; Schindler, Baptiste; Migas, Lukasz G.; Picmanova, Martina; Allouche, Abdul R.; Green, Anthony P.; Mandal, Santanu; Motawie, Mohammed Saddik; Sánchez Pérez, Raquel; Bjarnholt, Nanna; Møller, Birger Lindberg; Rijs, Anouk M.; Barran, Perdita E.; Compagnon, Isabelle; Eyers, Claire E.; Flitsch, Sabine L.
In: Analytical Chemistry, Vol. 89, No. 8, 2017, p. 4540-4549.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Bottom-up elucidation of glycosidic bond stereochemistry
AU - Gray, Christopher J.
AU - Schindler, Baptiste
AU - Migas, Lukasz G.
AU - Picmanova, Martina
AU - Allouche, Abdul R.
AU - Green, Anthony P.
AU - Mandal, Santanu
AU - Motawie, Mohammed Saddik
AU - Sánchez Pérez, Raquel
AU - Bjarnholt, Nanna
AU - Møller, Birger Lindberg
AU - Rijs, Anouk M.
AU - Barran, Perdita E.
AU - Compagnon, Isabelle
AU - Eyers, Claire E.
AU - Flitsch, Sabine L.
PY - 2017
Y1 - 2017
N2 - The lack of robust, high-throughput, and sensitive analytical strategies that can conclusively map the structure of glycans has significantly hampered progress in fundamental and applied aspects of glycoscience. Resolution of the anomeric α/β glycan linkage within oligosaccharides remains a particular challenge. Here, we show that "memory" of anomeric configuration is retained following gas-phase glycosidic bond fragmentation during tandem mass spectrometry (MS(2)). These findings allow for integration of MS(2) with ion mobility spectrometry (IM-MS(2)) and lead to a strategy to distinguish α- and β-linkages within natural underivatized carbohydrates. We have applied this fragment-based hyphenated MS technology to oligosaccharide standards and to de novo sequencing of purified plant metabolite glycoconjugates, showing that the anomeric signature is also observable in fragments derived from larger glycans. The discovery of the unexpected anomeric memory effect is further supported by IR-MS action spectroscopy and ab initio calculations. Quantum mechanical calculations provide candidate geometries for the distinct anomeric fragment ions, in turn shedding light on gas-phase dissociation mechanisms of glycosidic linkages.
AB - The lack of robust, high-throughput, and sensitive analytical strategies that can conclusively map the structure of glycans has significantly hampered progress in fundamental and applied aspects of glycoscience. Resolution of the anomeric α/β glycan linkage within oligosaccharides remains a particular challenge. Here, we show that "memory" of anomeric configuration is retained following gas-phase glycosidic bond fragmentation during tandem mass spectrometry (MS(2)). These findings allow for integration of MS(2) with ion mobility spectrometry (IM-MS(2)) and lead to a strategy to distinguish α- and β-linkages within natural underivatized carbohydrates. We have applied this fragment-based hyphenated MS technology to oligosaccharide standards and to de novo sequencing of purified plant metabolite glycoconjugates, showing that the anomeric signature is also observable in fragments derived from larger glycans. The discovery of the unexpected anomeric memory effect is further supported by IR-MS action spectroscopy and ab initio calculations. Quantum mechanical calculations provide candidate geometries for the distinct anomeric fragment ions, in turn shedding light on gas-phase dissociation mechanisms of glycosidic linkages.
KW - Journal Article
U2 - 10.1021/acs.analchem.6b04998
DO - 10.1021/acs.analchem.6b04998
M3 - Journal article
C2 - 28350444
VL - 89
SP - 4540
EP - 4549
JO - Industrial And Engineering Chemistry Analytical Edition
JF - Industrial And Engineering Chemistry Analytical Edition
SN - 0003-2700
IS - 8
ER -
ID: 180762796