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Identification of MS/MS diagnostic ions to distinguish Schiff bases of Nα- or Nε-mono-glycated and Nα,Nε-di-glycated lysines from their Amadori isomers

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Abstract

Lysine is the principal amino acid that participates in the Maillard reaction between polypeptides and reducing sugars in foods and in vivo. For mechanistic studies of the early Maillard reaction, diagnostic MS/MS fragmentations have been recently employed to discriminate between Amadori rearrangement products (ARP) and Schiff bases of glycated aliphatic amino acids. However, the utility of this method to identify ARP and Schiff bases of glycated dibasic amino acids, such as lysine, has not been explored yet. In this study, we report the potential of MS/MS fragmentations in the negative ionization mode to distinguish Schiff bases of Nα,Nε-diglycated lysines from their Amadori isomers, as well as utilization of 15 N-labeled lysines and the MS/MS fragmentations under positive ionization mode to distinguish between the Nα- and Nε-regioisomers of mono-glycated lysine. The applicability of this approach is exemplified in a mass-spectrometric analysis of a solid-state reaction between lysine and glucose in a ball mill. The analysis of the MS/MS fragmentation pattern of the glycated adduct has revealed the simultaneous formation of mono-glycated adducts, mainly Nε-Schiff bases, and di-glycated adducts, predominantly a mixture of Nα,Nε-Schiff–Schiff and Nα,Nε-Schiff–Amadori isomers.

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Acknowledgements

The authors acknowledge funding for this research from the Natural Sciences and Engineering Research Council of Canada (NSERC) and Le Fonds de Recherche du Québec—Nature et Technologie (FRQNT). The authors acknowledge the valuable support from Dr. Alexander Sean Wahba (Department of Chemistry, McGill University) regarding mass spectrometry.

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Authors and Affiliations

  1. Department of Food Science and Agricultural Chemistry, McGill University, 21111 Lakeshore, Ste Anne de Bellevue, QC, H9X 3V9, Canada

    Haoran Xing & Varoujan Yaylayan

  2. Department of Biochemistry, University of Missouri, Columbia, MO, 65211, USA

    Valeri V. Mossine

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  1. Haoran Xing
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  2. Valeri V. Mossine
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  3. Varoujan Yaylayan
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Correspondence to Varoujan Yaylayan.

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Xing, H., Mossine, V.V. & Yaylayan, V. Identification of MS/MS diagnostic ions to distinguish Schiff bases of Nα- or Nε-mono-glycated and Nα,Nε-di-glycated lysines from their Amadori isomers. Eur Food Res Technol 248, 2753–2763 (2022). https://doi.org/10.1007/s00217-022-04083-y

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