Furanose C-C-linked γ-lactones: a combined ESI FTICR MS and semi-empirical calculations study.
Sugars that incorporate the unsaturated carbonyl motif have become important synthetic targets not only as a result of their potential biological properties but also as precursors in the synthesis of many bioactive products. Moreover, little is known about the influence of the γ-lactone moiety in the fragmentation pattern of furanose rings. Therefore, two α,β-unsaturated γ-lactones (butenolides) and two β-hydroxy γ-lactones, C-C linked to a furanose ring were studied using electrospray ionization FTICR mass spectrometry. The behaviour of the protonated and sodiated forms of the compounds under study has been compared considering their structural features. Fragmentation mechanisms were established and ion structures were proposed taking into account the MS(2) and MS(3) experiments, accurate mass measurements and semi-empirical calculations. These inexpensive methods proved to be a valuable resource for proposing protonation sites and for the establishment of fragmentation pathways.
Madeira
Paulo J Amorim
PJ
Centro de Química e Bioquímica, Departamento de Química e Bioquímica da Faculdade de Ciências da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal.
Xavier
Nuno M
NM
Rauter
Amélia P
AP
Florêncio
M Helena
MH
D005663:Furans / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D007783:Lactones / Q000737:chemistry*; D008958:Models, Molecular; D010429:Pentoses / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods*
D005663:Furans; D007477:Ions; D007783:Lactones; D010429:Pentoses