JMSSJ On-line, Vol. 50 (2002) No. 4, pp. 204-207
Negative-Mode Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry of Maltoheptaose and Cyclomaltooligosaccharides
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    Tohru YAMAGAKI*a) and Hiroshi NAKANISHIb)

    *a) Department of Chemistry, School of Science, The University of Tokyo (7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan) b) National Institute of Advanced Industrial Science and Tech-nology ( 1-1 Higashi, Tsukuba, Ibaraki 305-8566, Japan)

  We used norharmane (9H-pyrido[3,4-b]indole) as a matrix for negative-mode ionization of neutral oligosaccharides in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). In-source decay (ISD) fragmentation occurred, producing fragment ions [(M-C4H8O4)-H]- in negative-mode linear MALDI-MS. The ISD product ion [(M-C4H8O4)-H]- of maltoheptaose was predominantly observed but deprotonated molecule was not. In the MALDI mass spectrum of cellohexaose, the ISD product ion [(M-C4H8O4)-H]- was observed, as was deprotonated molecule [M-H]-. In positive-mode MALDI-MS spectra of oligosaccharides, these ISD product ions were not observed. In cyclomaltooligosaccharides of cyclodextrins (CD), only deprotonated molecules [M-H]- were observed clearly and ISD product ions were not seen in negative-mode MALDI-MS. The result of sugar branched cyclodextrin of glucosyl-βCD was the same. The ISD product ion [(M-C4H8O4)-H]- of maltoheptaose would thus occur at the reducing end and corresponded to 2, 4A fragmentation. In the post-source decay (PSD) fragment spectra of cyclodextrins, PSD product ions [(M-C4H8O4)-H]- produced by 2, 4A and Z cleavage were observed. The formation of PSD product ions [(M-C4H8O4)-H]- of cyclodextrins would thus relate to that of ISD product ions of linear oligosaccharides in negative-mode MALDI-MS.

Key words:   Oligosaccharide,MALDI-MS,Negative-mode,In- source decay (ISD),Post-source decay (PSD)fragmentation

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