Discrimination of isomeric monosaccharide derivatives using collision-induced fingerprinting coupled to ion mobility mass spectrometry

Because of the isomeric heterogeneity that is ubiquitous in analytical science, a formidable analytical challenge is to fully discriminate multiple isomers, especially those candidate isomers with various biological functions. Ion mobility mass spectrometry (IM-MS) has gained impressive advances for gaining molecular conformations, whereas coexisting structurally similar isomers often make unambiguous discrimination impossible due to the limited IM resolution of commercially available instruments. Herein, we demonstrate an energy-resolved collision-induced fingerprint (CIF) method to fully discriminate isomeric monosaccharide derivatives that differ in terms of composition, connectivity and configuration without complex instrument modifications. By simply increasing the collisional energy in the trap cell, the full width at half maximum (FWHM) of IM peaks can be markedly narrowed by at least 2-fold. Given the excellent reproducibility of CIF measurements, the full discrimination of isomers can benefit from their unique feature values and root-mean square deviation (RMSD) in CIF spectra. Moreover, rapid discrimination of each monosaccharide derivate isomer from binary mixtures is demonstrated. This strategy will expand the horizons of IM-MS platform in the rapid differentiation of a wider range of isomers more than monosaccharide derivatives in complex systems, which facilitates the identification and evaluation of innovative isomer candidates with unexplored functions.

Automated summary

A new energy-resolved collision-induced fingerprint (CIF) method is demonstrated for fully discriminating isomeric monosaccharide derivatives without complex instrument modifications. By increasing collisional energy, the full width at half maximum (FWHM) of ion mobility (IM) peaks can be significantly narrowed, allowing for rapid discrimination of monosaccharide derivate isomers. The unique feature values and root-mean square deviation (RMSD) in CIF spectra contribute to the full discrimination of isomers, highlighting the potential of this strategy in expanding the horizons of ion mobility mass spectrometry (IM-MS) platform.