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Kanawati, B. ; von Saint Paul, V. ; Herrmann, C. ; Schäffner, A. ; Schmitt-Kopplin, P.

Mass spectrometric stereoisomeric differentiation between α- and β-ascorbic acid 2-O-glucosides. Experimental and density functional theory study.

Rapid Commun. Mass Spectrom. 25, 806-814 (2011)
DOI PMC
Open Access Green as soon as Postprint is submitted to ZB.
L-Ascorbic acid and two distinct anomers, namely the α-D-glucopyranosyl and β-D-glucopyranosyl-(1→2)-L-ascorbic acid (stereoisomers), were studied within the scope of collision-induced dissociation (CID) experiments, performed by linear ion acceleration and collision with argon atoms inside a hexapole quadrupole hexapole ion beam guide, which is coupled to an ion cyclotron resonance (ICR) cell with a 12 Tesla magnet for high-resolution measurements. Loss of C(2)H(4)O(2) neutral from the [M-H](-) anion of L-ascorbic acid was observed. Density functional theory (DFT) calculations on the 6-311+G(2d,p)//6-31+G(d) level of theory reveal a new concerted mechanism for an intramolecular gas-phase rearrangement, through which the observed ejected neutral C(2)H(4)O(2) can take place. A similar rearrangement also occurs in the case of α- and β-D-glucopyranosyl-(1→2)-L-ascorbic acid. For the α isomer, only homolytic glycoside fragmentation was observed. For the β isomer, both homolytic and heterolytic glycoside cleavages were possible. The mechanisms behind all observed fragmentation pathways were fully understood by the implementation of accurate DFT calculations. Stereoisomeric differentiation between α and β isomers of the L-ascorbic acid-2-O-glucoside could be revealed by tandem mass spectrometry (MS/MS) experiments and were explained theoretically.
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Publication type Article: Journal article
Document type Scientific Article
Corresponding Author
Keywords Cylindrical icr cell; Vitamin-C content; Gas-Phase; Fragmentation; Arabidiosis; Senescence; Transglucosylation; Optimization; Glucoside; Pathogens
ISSN (print) / ISBN 0951-4198
e-ISSN 1097-0231
Journal Rapid Communications in Mass Spectrometry
Quellenangaben Volume: 25, Issue: 6, Pages: 806-814 Article Number: , Supplement: ,
Publisher Wiley
Non-patent literature Publications
Reviewing status Peer reviewed
Institute(s) Institute of Ecological Chemistry (IOEC)
Institute of Biochemical Plant Pathology (BIOP)