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Ionization and collision-induced fragmentation of N-linked and related carbohydrates using divalent cations

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Journal of the American Society for Mass Spectrometry

Abstract

Maltoheptaose and several N-linked glycans were ionized by electrospray as adducts with the divalent cations Mg2+, Ca2+, Mn2+, Co2+ and Cu2+. [M + metal] ions were the major species in all cases with calcium giving the highest sensitivity. In addition, copper gave [M + Cu]+ ions. Other cations gave singly charged ions only by elimination of a protonated monosaccharide. Fragmentation of the [M + metal]2+ ions produced both singly and doubly charged ions with the relative abundance of doubly charged ions decreasing in the order Ca > Mg > Mn > Co > Cu. Singly charged ions were formed by elimination of a protonated monosaccharide residue followed, either by successive monosaccharide residue losses, or by a 2,4A cross-ring cleavage of the reducing-terminal monosaccharide. Formation of doubly charged fragments from [M + metal]2+ ions involved successive monosaccharide-residue losses either with or without O,2A or 2,4A cross-ring cleavages of the reducing-terminal monosaccharide. Abundant diagnostic doubly charged ions formed by loss of the 3-antenna from the O,2A cross-ring product were specific to [M + Ca]2+ ions. Fragmentation of [M + Cu]+ ions was similar to that of the corresponding [M + H]+ ions in that most cross-ring fragments were absent.

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Authors and Affiliations

  1. Department of Biochemistry, Oxford Glycobiology Institute, South Parks Road, OX1 3QU, Oxford, UK

    David J. Harvey

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  1. David J. Harvey
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Correspondence to David J. Harvey.

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This article is submitted to recognize Julie Leary and the 2000 Biemann Medal Award.

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Harvey, D.J. Ionization and collision-induced fragmentation of N-linked and related carbohydrates using divalent cations. J Am Soc Spectrom 12, 926–937 (2001). https://doi.org/10.1016/S1044-0305(01)00268-9

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  • DOI: https://doi.org/10.1016/S1044-0305(01)00268-9

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