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The native oligosaccharides of lacto-N-neotetraose (Gal beta1-4GlcNAc beta1-3Gal beta1-4Glc; LNnT) and lacto-N-tetraose (Gal beta1-3GlcNAc beta1-3Gal beta1-4Glc; LNT) were analyzed by using curved-field reflectron matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Since a curved-field reflectron TOFMS enables a simultaneous focusing of a wide mass range of metastable fragment ions, the relative ion intensities in the post-source decay (PSD) mass spectra can be discussed. The PSD mass spectra of LNnT and LNT were distinguishable in their relative ion intensities. In the case of LNT, beta-elimination could occur in the N-acetyl glucosamine (GlcNAc) at the C-3 position, which was bonded by galactose (Gal); however, it did not occur in LNnT. The 3-O elimination caused a difference in the relative ion intensities in the PSD mass spectra of LNnT and LNT. The beta1-3 glycosyl linkage cleaved more easily than the beta1-4 glycosyl linkage in the MALDI-PSD fragmentation. An analysis of the relative ion intensities in the MALDI-PSD mass spectra of oligosaccharides was very useful for distinguishing the linkage isomers and for characterizing the types of glycosyl linkages.

analytical sciences

Distinguishing of Linkage Isomers of Lactotetra Oligosaccharides by Using the Relative Ion Intensity Analysis of Post-source Decay Fragment Ions in Curved-field Reflectron Matrix-assisted Laser Desorption/ionization Time-of-flight Mass Spectrometry