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. 2017 Nov 30;7:16623. doi: 10.1038/s41598-017-16811-6

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© The Author(s) 2017

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

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Fragmentation spectra. (A) MALDI-TOF/TOF-MS/MS fragmentation spectrum of the N-glycan Hex7HexNAc6Fuc2(α2,6)NeuAc1 with m/z 3005.48 [M + Na]⁺. The fragment ion at m/z 707.2 [M + Na]⁺ is indicative for Hex1HexNAc1(α2,6)NeuAc1. The mass shift of + 28 Da from a non-modified N-acetylneuraminic acid to an ethyl esterified N-acetylneuraminic acid indicates α2,6-linkage. The position of the α2,6NeuAc as well as the antenna fucose cannot be identified. (B) MALDI-TOF/TOF-MS/MS fragmentation spectrum of the N-glycan Hex4HexNAc5Fuc3 with m/z 2142.78 [M + Na]⁺. Fragment ions for antenna-fucosylation (m/z 712.1 [M + Na]⁺, m/z 874.1 [M + Na]⁺) as well as core-fucosylation (m/z 1077.0 [M + Na]⁺) were identified. (C) LC-MS/MS fragmentation spectrum of the N-glycan Hex3 HexNAc6Fuc3 with m/z 1142.05 [M + H]²⁺. Indicative fragment ions at m/z 407 [M + H]⁺ (HexNAc2) and m/z 553 [M + H]⁺ (HexNAc2dHex1) show the presence of LacdiNAc structures. Annotation was performed in GlycoWorkbench 2.1 stable build 146 (http://www.eurocarbdb.org/) using the Glyco-Peakfinder tool (http://www.eurocarbdb.org/ms-tools/). The presence of structural isomers cannot be excluded. Hex = hexose; blue circle = Glc, glucose; yellow circle = Gal, galactose; green circle = Man, mannose; blue square = GlcNAc, N-acetylglucosamine; yellow square = GalNAc, N-acetylgalactosamine; white square = HexNAc, N-acetylhexosamine; red triangle = Fuc, deoxyhexose, fucose; purple diamond = NeuAc, N-acetylneuraminic acid; *reducing end adduct.