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Analysis of neutral oligosaccharides for structural characterization by matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry.
J Mass Spectrom. 2005 Mar; 40(3):380-8.JM

Abstract

We have acquired multi-stage mass spectra (MSn) of four branched N-glycans derived from human serum IgG by matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry (MALDI-QIT-TOF-MS) in order to demonstrate high sensitivity structural analysis. [M+H]+ and [M+Na]+ ions were detected in the positive mode. The detection limit of [M+Na]+ in MS/MS and MS3 measurements for structural analysis was found to be 100 fmol, better than that for [M+H]+. The [M+H]+ ions subsequently fragmented to produce predominantly a Y series of fragments, whereas [M+Na]+ ions fragmented to give a complex mixture of B and Y ions together with some cross-ring fragments. Three features of MALDI-QIT-CID fragmentation of [M+Na]+ were cleared by the analysis of MS/MS, MS3 and MS4 spectra: (1) the fragment ions resulting from the breaking of a bond are more easily generated than that from multi-bond dissociation; (2) the trimannosyl-chitobiose core is either hardly dissociated, easily ionized or it is easy to break a bond between N-acetylglucosamine and mannose; (3) the fragmentation by loss of only galactose from the non-reducing terminus is not observed. We could determine the existence ratios of candidates for each fragment ion in the MS/MS spectrum of [M+Na]+ by considering these features. These results indicate that MSn analysis of [M+Na]+ ions is more useful for the analysis of complicated oligosaccharide structures than MS/MS analysis of [M+H]+, owing to the higher sensitivity and enhanced structural information. Furthermore, two kinds of glycans, with differing branch structures, could be distinguished by comparing the relative fragment ion abundances in the MS3 spectrum of [M+Na]+. These analyses demonstrate that the MSn technology incorporated in MALDI-QIT-TOF-MS can facilitate the elucidation of structure of complex branched oligosaccharides.

Authors+Show Affiliations

Life Science Laboratory, Analytical and Measuring Instruments Division, Shimadzu Corporation, 1, Nishinokyo Kuwabaracho, Nakagyo-ku, Kyoto 604-8511, Japan.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15712371

Citation

Ojima, Noriyuki, et al. "Analysis of Neutral Oligosaccharides for Structural Characterization By Matrix-assisted Laser Desorption/ionization Quadrupole Ion Trap Time-of-flight Mass Spectrometry." Journal of Mass Spectrometry : JMS, vol. 40, no. 3, 2005, pp. 380-8.
Ojima N, Masuda K, Tanaka K, et al. Analysis of neutral oligosaccharides for structural characterization by matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry. J Mass Spectrom. 2005;40(3):380-8.
Ojima, N., Masuda, K., Tanaka, K., & Nishimura, O. (2005). Analysis of neutral oligosaccharides for structural characterization by matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry. Journal of Mass Spectrometry : JMS, 40(3), 380-8.
Ojima N, et al. Analysis of Neutral Oligosaccharides for Structural Characterization By Matrix-assisted Laser Desorption/ionization Quadrupole Ion Trap Time-of-flight Mass Spectrometry. J Mass Spectrom. 2005;40(3):380-8. PubMed PMID: 15712371.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Analysis of neutral oligosaccharides for structural characterization by matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry. AU - Ojima,Noriyuki, AU - Masuda,Katsuyoshi, AU - Tanaka,Koichi, AU - Nishimura,Osamu, PY - 2005/2/16/pubmed PY - 2005/5/20/medline PY - 2005/2/16/entrez SP - 380 EP - 8 JF - Journal of mass spectrometry : JMS JO - J Mass Spectrom VL - 40 IS - 3 N2 - We have acquired multi-stage mass spectra (MSn) of four branched N-glycans derived from human serum IgG by matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry (MALDI-QIT-TOF-MS) in order to demonstrate high sensitivity structural analysis. [M+H]+ and [M+Na]+ ions were detected in the positive mode. The detection limit of [M+Na]+ in MS/MS and MS3 measurements for structural analysis was found to be 100 fmol, better than that for [M+H]+. The [M+H]+ ions subsequently fragmented to produce predominantly a Y series of fragments, whereas [M+Na]+ ions fragmented to give a complex mixture of B and Y ions together with some cross-ring fragments. Three features of MALDI-QIT-CID fragmentation of [M+Na]+ were cleared by the analysis of MS/MS, MS3 and MS4 spectra: (1) the fragment ions resulting from the breaking of a bond are more easily generated than that from multi-bond dissociation; (2) the trimannosyl-chitobiose core is either hardly dissociated, easily ionized or it is easy to break a bond between N-acetylglucosamine and mannose; (3) the fragmentation by loss of only galactose from the non-reducing terminus is not observed. We could determine the existence ratios of candidates for each fragment ion in the MS/MS spectrum of [M+Na]+ by considering these features. These results indicate that MSn analysis of [M+Na]+ ions is more useful for the analysis of complicated oligosaccharide structures than MS/MS analysis of [M+H]+, owing to the higher sensitivity and enhanced structural information. Furthermore, two kinds of glycans, with differing branch structures, could be distinguished by comparing the relative fragment ion abundances in the MS3 spectrum of [M+Na]+. These analyses demonstrate that the MSn technology incorporated in MALDI-QIT-TOF-MS can facilitate the elucidation of structure of complex branched oligosaccharides. SN - 1076-5174 UR - https://www.unboundmedicine.com/medline/citation/15712371/Analysis_of_neutral_oligosaccharides_for_structural_characterization_by_matrix_assisted_laser_desorption/ionization_quadrupole_ion_trap_time_of_flight_mass_spectrometry_ L2 - https://doi.org/10.1002/jms.798 DB - PRIME DP - Unbound Medicine ER -