title: A computational study of structure-reactivity relationships in Na-adduct oligosaccharides in collision-induced dissociation reactions.
abstract: Elucidating the fragmentation mechanisms in oligosaccharides using theoretical calculations is useful in analyzing the experimentally obtained mass spectra. Semi-empirical and ab initio quantum mechanics calculations were used to study the relationship between the structure and reactivity and the chemical properties of oligosaccharides. In these calculations, sodium-cationized oligosaccharides were investigated to determine Na+ ion affinity at several binding positions; in addition, the dependence of the glycosidic bond cleavage on the Na+ position was examined. The calculated structures reported in this study are directed at interpreting experimentally observed fragment ions, resulting from the cleavage of the glycosidic bonds. The calculated results for oligosaccharides containing between three and five monosaccharide units (27 oligosaccharides) were compared with experimental data generated by matrix-assisted laser-desorption/ionization (MALDI) using a quadrupole ion trap (QIT) with a time-of-flight (TOF) mass spectrometer (MS).
authors.affiliation: Computational Biology Research Center (CBRC), National Institute of Advanced Industrial Science and Technology (AIST), 2-41-6 Aomi, Koutou, Tokyo 135-0064, Japan. k-fukui@aist.go.jp
authors.forename: Kazuhiko
authors.initials: K
authors.lastname: Fukui
authors.forename: Akihiko
authors.initials: A
authors.lastname: Kameyama
authors.forename: Yuri
authors.initials: Y
authors.lastname: Mukai
authors.forename: Katsutoshi
authors.initials: K
authors.lastname: Takahashi
authors.forename: Noriko
authors.initials: N
authors.lastname: Ikeda
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Akiyama
authors.forename: Hisashi
authors.initials: H
authors.lastname: Narimatsu
mesh_terms: D002240:Carbohydrate Sequence; D019295:Computational Biology; D015394:Molecular Structure; D009844:Oligosaccharides / Q000737:chemistry*; D012964:Sodium / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013329:Structure-Activity Relationship
chemical_list: D009844:Oligosaccharides; D012964:Sodium