Bottom-up elucidation of glycosidic bond stereochemistry

Christopher J. Gray; Baptiste Schindler; Lukasz G. Migas; Martina Picmanova; Abdul R. Allouche; Anthony P. Green; Santanu Mandal; Mohammed Saddik Motawie; Raquel Sánchez Pérez; Nanna Bjarnholt; Birger Lindberg Møller; Anouk M. Rijs; Perdita E. Barran; Isabelle Compagnon; Claire E. Eyers; Sabine L. Flitsch

doi:10.1021/acs.analchem.6b04998

Bottom-up elucidation of glycosidic bond stereochemistry

Christopher J. Gray, Baptiste Schindler, Lukasz G. Migas, Martina Picmanova, Abdul R. Allouche, Anthony P. Green, Santanu Mandal, Mohammed Saddik Motawie, Raquel Sánchez Pérez, Nanna Bjarnholt, Birger Lindberg Møller, Anouk M. Rijs, Perdita E. Barran, Isabelle Compagnon, Claire E. Eyers, Sabine L. Flitsch

Plantebiokemi

40 Citationer (Scopus)

Abstract

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.

Originalsprog	Engelsk
Tidsskrift	Analytical Chemistry
Vol/bind	89
Udgave nummer	8
Sider (fra-til)	4540-4549
Antal sider	10
ISSN	0003-2700
DOI	https://doi.org/10.1021/acs.analchem.6b04998
Status	Udgivet - 18 apr. 2017

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10.1021/acs.analchem.6b04998

Citationsformater

Gray, C. J., Schindler, B., Migas, L. G., Picmanova, M., Allouche, A. R., Green, A. P., Mandal, S., Motawie, M. S., Sánchez Pérez, R., Bjarnholt, N., Møller, B. L., Rijs, A. M., Barran, P. E., Compagnon, I., Eyers, C. E., & Flitsch, S. L. (2017). Bottom-up elucidation of glycosidic bond stereochemistry. Analytical Chemistry, 89(8), 4540-4549. https://doi.org/10.1021/acs.analchem.6b04998

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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.

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Y1 - 2017/4/18

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.

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JO - Industrial And Engineering Chemistry Analytical Edition

JF - Industrial And Engineering Chemistry Analytical Edition

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Bottom-up elucidation of glycosidic bond stereochemistry

Abstract

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