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Open AccessArticle

Expanding the Reaction Space of Linkage-Specific Sialic Acid Derivatization

Center for Proteomics and Metabolomics, Leiden University Medical Center, 2333ZA Leiden, The Netherlands
Author to whom correspondence should be addressed.
Molecules 2019, 24(19), 3617;
Received: 5 September 2019 / Revised: 4 October 2019 / Accepted: 6 October 2019 / Published: 8 October 2019
(This article belongs to the Special Issue Oligosaccharides and Glyco-Conjugates II)
The human glycome is characterized by a high degree of sialylation, affecting, amongst others, cell–cell interactions and protein half-life. An established method for the linkage isomer-specific characterization of N-glycan sialylation is based on the linkage-specific derivatization of sialylated glycoconjugates, inducing ethyl esterification of α2,6-linked sialic acids and lactonization of α2,3-linked sialic acids. While the carboxylic acid activator and nucleophile used in this reaction received extensive investigation, the role of the catalyst was never thoroughly explored. A frequently used catalyst for the linkage-specific esterification of sialic acids is 1-hydroxybenzotriazole (HOBt). Here, a systematic evaluation was performed of five HOBt alternatives in combination with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) in ethanol for the linkage-specific derivatization of sialic acids. Derivatized glycans were analyzed by MALDI-TOF-MS and the catalyst performance was evaluated based on the completeness of the reactions and the linkage-specificity obtained. The use of both 6-Cl-HOBt and 6-CF3-HOBt resulted in high linkage-specificity and minimal byproduct formation, similar to the benchmark method using HOBt. Performing the reaction with these catalysts at neutral or acidic pH showed comparable efficiencies on both sialyllactose and complex-type N-glycans. The reported investigations resulted in an expansion of the reaction space for linkage-specific sialic acid derivatization. View Full-Text
Keywords: glycosylation; sialic acids; derivatization; isomer-specificity; catalysts; mass spectrometry; glycomics glycosylation; sialic acids; derivatization; isomer-specificity; catalysts; mass spectrometry; glycomics
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Pongracz, T.; Wuhrer, M.; de Haan, N. Expanding the Reaction Space of Linkage-Specific Sialic Acid Derivatization. Molecules 2019, 24, 3617.

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