Thiazolidine peracetates: Novel carbohydrate derivatives that assign cis-2,3- from trans-2,3- monosaccharides by GC/MS analysis

Authors: Price, Neil; Hartman, Trina; Vermillion, Karl

Submitted to: Gordon Research Conferences
Publication Type: Abstract Only
Publication Acceptance Date: 5/15/2017
Publication Date: 6/25/2017
Citation: Price, N.P., Hartman, T.M., Vermillion, K. 2017. Thiazolidine peracetates: Novel carbohydrate derivatives that assign cis-2,3- from trans-2,3- monosaccharides by GC/MS analysis [abstract]. Gordon Research Conference on Carbohydrates: Chemical and Biochemical Approaches to Deciphering Glycan Functions, June 25-30, 2017, West Dover, NH.

Interpretive Summary:

Technical Abstract: A new type of carbohydrate derivative is described that is suitable for analysis by GC/MS. Reaction of free aldoses (pentoses or hexoses), or the component aldoses arising from acid hydrolysis of polysaccharides or oligosaccharides, with excess cysteamine hydrochloride in pyridine, results in the quantitative formation of thiazolidines, which are readily peracetylated in a one-pot reaction with acetic anhydride. Following water:ethyl acetate partitioning, the non-polar thiazolidines acetate (TPA) derivatives are analyzed by GC/EI-MS. Each aldose gives rise to two TPA geometric isomers that are readily separated by GC. The quantitative ratio of these isomers is dependent upon whether the parent monosaccharide is a cis-2,3-(Ara, Xyl, Lyx, Glc, Gul, and Gal) or a trans-2,3-aldose (Rib, All, Man, and Tal). Hence, this enables us to distinguish cis/trans-2/3 aldose isomers at low concentration. In addition, an m/z 88 EI-MS base ion is characteristic of C1-C2 bond cleavage, and is useful for isotopic labeling of the anomeric carbons of complex carbohydrates.