Thiazolidine Peracetates: Carbohydrate Derivatives that Readily Assign cis‑,trans-2,3-Monosaccharides by Gas Chromatography–Mass Spectrometry Analysis

A novel group of carbohydrate derivatives is described that uniquely assign cis/trans-2,3-aldose stereoisomers at low nanomolar concentrations. Aldopentoses, aldohexoses, or component aldoses from hydrolysis of polysaccharides or oligosaccharides react with cysteamine in pyridine to give quantitativ...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2018-07, Vol.90 (13), p.8044-8050
Main Authors: Price, Neil. P. J, Hartman, Trina M, Vermillion, Karl E
Format: Article
Language:English
Subjects:
Aldolase
Analytical chemistry
Carbohydrates
Chemistry
Chromatography
Cysteamine
Derivatives
Gas chromatography
Isomers
Mass spectrometry
Microorganisms
Monosaccharides
Oligosaccharides
Organic chemicals
Polymers
Polysaccharides
Spectroscopy
Sugar
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Summary:A novel group of carbohydrate derivatives is described that uniquely assign cis/trans-2,3-aldose stereoisomers at low nanomolar concentrations. Aldopentoses, aldohexoses, or component aldoses from hydrolysis of polysaccharides or oligosaccharides react with cysteamine in pyridine to give quantitative formation of thiazolidines, which are subsequently peracetylated in a one-pot reaction. The nonpolar thiazolidines peracetate (TPA) derivatives are analyzed by gas chromatography and electron impact mass spectrometry (GC/EI-MS), each aldose giving rise to two TPA geometric isomers. The quantitative ratio of these diastereomers is dependent upon whether the parent monosaccharide is cis-2,3-(Rib, Lyx, Man, All, Gul, and Tal), or trans-2,3-aldose (Xyl, Ara, Glc, Gal, Ido, and Alt). TPAs generate observed EI-MS fragment ions characteristic of C1–C2 and C3–C4 bond cleavage of the parent sugars. This has been used to estimate the extent of metabolic labeling of microbial cell-wall carbohydrates, especially into the defining anomeric carbons and during aldolase / ketolase -catalyzed rearrangements.
ISSN:0003-2700
1520-6882
DOI:10.1021/acs.analchem.8b00976