Matrix-assisted laser desorption/ionisation mass spectrometry for the direct analysis of enzymatically digestedkappa-iota- and hybridiota/nu-carrageenans

Abstract : Enzymatically digested oligosaccharides of kappa-, iota- and hybrid iota/nu-carrageenans were analysed using matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry in the negative-ion mode. nor-Harmane was used as matrix. Depending on the stock concentration and the laser intensity applied, the oligosaccharides exhibited losses of sulphate units (neutralised by the Na+ ion, and thus non-stable), leaving the primary backbone structure in most cases with only the deprotonated sulphate groups (carrying the negative charge, stable). This meant that kappa- and iota-oligosaccharides could not be easily distinguished from one another since they share the same primary backbone structure. However, for the hybrid iota/nu-oligosaccharides the primary backbone structure could be identified since the nu-carrageenan repeating unit differs from that of the kappa/iota-carrageenan unit. For all types of oligosaccharides, the results indicated cleavage of an anhydrogalactose unit from the non-reducing end. Specifically, for the hybrid oligosaccharides of iota/nu-carrageenans, this type of fragmentation means that the nu-carrageenan unit is not positioned on the non-reducing end of the hybrid oligosaccharides. Dehydration reactions, and exchange reactions of Na+ with K+ and Ca2+, were also observed.
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Aristotelis Antonopoulos, Julie Hardouin, Patrick Favetta, William Helbert, Agnès Delmas, et al.. Matrix-assisted laser desorption/ionisation mass spectrometry for the direct analysis of enzymatically digestedkappa-iota- and hybridiota/nu-carrageenans. Rapid Communications in Mass Spectrometry, Wiley, 2005, 19 (16), pp.2217-2226. ⟨10.1002/rcm.2051⟩. ⟨hal-02146666⟩

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