Characteristic fragmentation patterns of trimethylsilyl and trimethylsilyl-oxime derivatives of plant disaccharides as obtained by gas chromatography coupled to ion-trap mass spectrometry

Abstract

The characteristic fragmentation pattern of six reducing and two non reducing type disaccharides-(neohesperidose, acuminose, sambubiose, rutinose, vicianose, primverose, and two arabinosyl-inositols) has been described. These saccharides have not been previously identified by on-line chromatographic techniques. Unambiguous specific characteristics of the TMS (oxime)s such as mass distribution, syn/anti oximes ratios and elution order proved to be associated with their reducing or non reducing character, with their aldosyl property and with the position of their O-glycosidic linkages. The practical utility of the mass fragmentation study of these rare disaccharides was demonstrated, at the first time, by the simultaneous, on-line identification and quantification of the acuminose, vicianose, primverose and arabinosyl-inositol contents of tea leaves, from green and black tea blends of Indian and Chinese origin.

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

“…Other papers on carbohydrates of interest include those on the trisaccharide antibiotic kanamycin A (DeJongh et al, 1973), aminocyclitol antibiotics (DeJongh et al, 1967), ascorbic acid (Vecchi & Kaiser, 1967), sialic (neuraminic) acids (Kamerling et al, 1974;Reuter & Schauer, 1986), muramic acid (Bal et al, 2002), plant disaccharides (Boldizsár et al, 2011) and iminosugars (Rodríguez-Sánchez et al, 2014).…”

Mass spectral fragmentation of trimethylsilylated small molecules

“…Another function of sugar MO‐TMS derivatives is the specificity of their syn / anti isomer ratios. For ketoses, the syn / anti ratio values are typically smaller than 1, while for reducing disaccharides, those values are varying from 2 to 4 (Boldizsár, Füzfai, & Molnár‐Perl, ).…”

“…Sugars are also frequently found as disaccharides and oligosaccharides, with various published fragmentation patterns for the TMS and MO‐TMS derivatives. Disaccharides have been reported to show significant ion pair ratios of the cyclic monosaccharide units at m/z 259.119/349.169 and m/z 361.169/451.219, with one TMSOH neutral loss differentiation for each pair (Szafranek, Wisniewski, & Vouros, ; Füzfai, Boldizsár, & Molnar‐Perl, ; Boldizsár, Füzfai, & Molnár‐Perl, ). Reducing sugars (such as maltose) have one monosaccharide with an open aldehyde group which can be distinguished from non‐reducing sugars (such as sucrose) by forming methoxyamine syn ‐ and anti ‐isomeric derivatives (Fiehn, ).…”