Separation of Monosaccharide Anomers on Photo-Click Cysteine-Based Stationary Phase: The α/β Interconversion Process Studied by Dynamic Hydrophilic Liquid Chromatography

In High-Performance Liquid Chromatography (HPLC), the separation of reducing sugars can typically show three possible typologies of chromatographic profiles (i.e., single peak, two resolved peaks and two peaks interconnected by a plateau) due to the rate at which the relevant α/β anomers interconver...

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Bibliographic Details
Main Authors: Andrea Calcaterra, Simone Manetto, Fabio Buonsenso, Antonio Francioso, Marco Pierini, Claudio Villani
Format: Article
Language:English
Published: MDPI AG 2022-08-01
Series:Separations
Subjects:
Online Access:https://www.mdpi.com/2297-8739/9/8/203
Description
Summary:In High-Performance Liquid Chromatography (HPLC), the separation of reducing sugars can typically show three possible typologies of chromatographic profiles (i.e., single peak, two resolved peaks and two peaks interconnected by a plateau) due to the rate at which the relevant α/β anomers interconversion (anomerization) can take place in relation to their elution-time. By analyzing these chromatographic profiles, thermodynamic and kinetic properties of anomerization phenomenon can be extrapolated. In this work we studied the anomerization of some monosaccharides by using a recently developed photo-click cysteine-based stationary phase through dynamic hydrophilic interaction liquid chromatography (D-HILIC) conditions. In the 5–25 °C temperature range, the ΔG<sup>#</sup><sub>α→β</sub> and ΔG<sup>#</sup><sub>β→α</sub> barriers were found to achieve values within the interval 21.1/22.2 kcal/mol for glucose, with differences between α→β and β→α reactions of about 0.4 kcal/mol. For xylose, in the same temperature range, the ΔG<sup>#</sup><sub>α→β</sub> and ΔG<sup>#</sup><sub>β→α</sub> barriers are between 20.7 to 21.5 kcal/mol, with differences between α→β and β→α reactions of about 0.2 kcal/mol. The experimental data are in agreement with those reported in literature, confirming the this new stationary phase using HILIC conditions is a robust platform to measure kinetic and thermodynamic properties of the isomerization reaction.
ISSN:2297-8739