Anomerization of Acrylated Glucose During Traveling Wave Ion Mobility Spectrometry

Abstract

Abstract. Anomerization of simple sugars in the liquid phase is known as an acidand base-catalyzed process, which highly depends on solvent polarity. This reaction is reported here to occur in the gas phase, during traveling wave ion mobility spectrometry (TWIMS) experiments aimed at separating α-and β-anomers of penta-acrylated glucose generated as ammonium adducts in electrospray ionization. This compound was available in two samples prepared from glucose dissolved in solvents of different polarity, namely tetrahydrofuran (THF) and N,Ndimethylacetamide (DMAC), and analyzed by electrospray tandem mass spectrometry (ESI-MS/MS) as well as traveling wave ion mobility (ESI-TWIMS-MS). In MS/MS, an anchimerically-assisted process was found to be unique to the electrosprayed α-anomer, and was only observed for the THF sample. In ESI-TWIMS-MS, a signal was measured at the drift time expected for the α-anomer for both the THF and DMAC samples, in apparent contradiction to the MS/MS results, which indicated that the α-anomer was not present in the DMAC sample. However, MS/MS experiments performed after TWIMS separation revealed that ammonium adducts of the α-anomer produced from each sample, although exhibiting the same collision cross section, were clearly different. Indeed, while the α-anomer actually present in the THF sample was electrosprayed with the ammonium adducted at the C2 acrylate, its homologue only observed when the DMAC sample was subjected to TWIMS hold the adducted ammonium at the C1 acrylate. These findings were explained by a β/α inter-conversion upon injection in the TWIMS cell, as supported by theoretical calculation and dynamic molecular modeling.

Smart IM-MS and NMR study of natural diastereomers: the study case of the essential oil from Senecio transiens

“…The theoretical estimation of the CCS values for the two diastereomers A and B was obtained by adapting the computational protocols based on atomistic molecular dynamics (MD) simulations described in details in our previous works [15,16]. In brief, the two molecules were built and optimized in AMBER 20 [17] using the Generalized Amber Force Field (GAFF) [18].…”

An experimental and theoretical study on stereocontrolled glycosylations by a “one-pot” procedure

“…Furthermore, the formation of 1,2- cis -products can be achieved if glycosidation gives the β-anomer first and anomerization occurs subsequently (glycosidation–anomerization). 13…”