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Low‐energy collision‐induced dissociation of B 1 ‐type sugar ions formed from peracetylated methyl pentosides and methyl 6‐deoxyhexosides
Author(s) -
Vouros P.,
Müller D. R.,
Richter W. J.
Publication year - 1999
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199904)34:4<346::aid-jms766>3.0.co;2-q
Subject(s) - chemistry , dissociation (chemistry) , ion , tandem mass spectrometry , electron ionization , collision induced dissociation , structural isomer , mass spectrometry , mass spectrum , protonation , medicinal chemistry , tandem , computational chemistry , stereochemistry , analytical chemistry (journal) , ionization , chromatography , organic chemistry , materials science , composite material
Low‐energy collision‐induced dissociation(CID) was explored for the purpose of differentiatingbetween isomeric pertrideuteroacetylated aldopentosides,6‐deoxyaldohexosides and their respective furanosidic andpyranosidic analogues. The 1‐ O ‐methylatedderivatives were analyzed by gas chromatography/chemicalionization (CH 4 ) tandem mass spectrometry.B 1 ions (formally C(1) carbenium ions),which are expected to reflect the core structure of the parent sugarand which were produced by the elimination of methanol from theprotonated glycoside derivatives, were used as precursor ions toobtain the corresponding CID spectra. In general, strong similaritieswhich impede an unequivocal differentiation of the individualconstituents were found in the spectral patterns of the differentisomeric pairs. However, examination of the pseudo‐breakdownbehavior of the B 1 ions over the range 5–35 eVrevealed improved distinction windows which provide for a fullerdifferentiating capability between five‐andsix‐membered ring isomers including even the most problematicribose derivatives. The reliability of the analyses is enhanced bythe high reproducibility ( s <10%) of theseratios. The considerable similarity between the tandem mass spectraof certain furanosidic and pyranosidic B 1 ions is highlysuggestive of a partial loss of structural integrity, mainly due toring contraction, which occurs to different extents in the differentisomers. Copyright © 1999 John Wiley & Sons, Ltd.