Journal of the Mass Spectrometry Society of Japan
Online ISSN : 1880-4225
Print ISSN : 1340-8097
ISSN-L : 1340-8097
52 巻, 2 号
選択された号の論文の4件中1~4を表示しています
一般論文
  • —Dissociation of Ionized Maleamide and Fumaramide—
    Susumu TAJIMA, Masaaki UBUKATA, Masao FUJISHIGE
    2004 年 52 巻 2 号 p. 57-62
    発行日: 2004年
    公開日: 2005/10/28
    ジャーナル フリー
    The unimolecular decompositions of the geometrical isomers maleamide (cis-NH2COCH=CHCONH2; 1, MW: 114) and fumaramide (trans-NH2COCH=CHCONH2; 2, MW: 114) have been investigated by use of collision-induced dissociation (CID) spectra versus collision energy. These ions, 1 and 2, show as primary fragmentation channels the losses of NH2 and CONH to give the ions m/z 98 and 71, respectively, but the relative abundance of these ions is different with each other. This will be attributable to amide-amide interaction in cis-isomer. The fragment ions m/z 71 correspond to the molecular ion of acrylamide, CH2=CHCONH2, which is formed by hydrogen atom migration from NH2 to ethylenic carbon in the molecular ions 1 and 2, followed by CONH loss. The additional dissociation channels are observed for 2, the losses CO and CONH2 to give the ions at m/z 86 and 70, respectively. These two reactions were weak for 1. These ions, except for m/z 71 ion, retain the structure difference between the geometrical isomers. The [M-NH2]+ ions decompose further by the losses of H2O and CO to generate the ions at m/z 80 and 70, respectively. The former reaction for 1 is different from that for 2. This reaction accompanies with double hydrogen atom transfers, and was not described in previous report.
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速報
  • Atsushi TAKAMIZAWA, Susumu FUJIMAKI, Shigemitsu OKAZAKI, Kenzo HIRAOKA
    2004 年 52 巻 2 号 p. 68-71
    発行日: 2004年
    公開日: 2005/10/28
    ジャーナル フリー
    A preliminary study on the laser spray and electrospray was made using an orthogonal time-of-flight mass spectrometer. Explosive vaporization and mist formation occurred when an aqueous solution effusing out from the tip of the stainless steel capillary was irradiated from the opposite side of the capillary by a 10.6 μm infrared laser. Little ion signals could be detected when the plume was sampled through the ion sampling orifice. When a high voltage (∼3 kV) was applied to the stainless steel capillary, strong ion signals appeared. The ion intensities were found to be more than one order of magnitude stronger than those obtained by the conventional electrospray for aqueous solutions of arginine and lysozyme. The present method is regarded as the electric-field assisted MALDI in which the LC solvents (water etc.) act as liquid matrices. The laser spray will be a versatile method for the biological mass spectrometry because this method is compatible with the natural solvent, water.
総合論文
  • 山垣 亮
    2004 年 52 巻 2 号 p. 72-83
    発行日: 2004年
    公開日: 2005/10/28
    ジャーナル フリー
    When we analyze oligosaccharides by mass spectrometry, the fragment ions at glycosyl linkages show their sequences. However, it is difficult to distinguish between the linkage isomers or to analyze the types of glycosyl linkages. We have studied the post-source decay (PSD) of oligosaccharides in MALDI-MS, and we focused our attention on the abundance of the PSD ions to distinguish the linkage isomers. For example, the PSD ions produced by the cleavage of the α1→4 glycosyl linkage had higher abundance than those of α1→6 glycosyl linkage. The PSD ions produced by the cleavage of sialyl 2→3 linkages showed higher abundance than those of sialyl 2→6 linkages, and so on. These analyses of the linkage isomers of oligosaccharides have been performed systematically by MALDI-TOF mass spectrometry equipped with curved-field reflectron.
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