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Diagnostic MS/MS fragmentation patterns for the discrimination between Schiff bases and their Amadori or Heyns rearrangement products.
Carbohydr Res. 2020 May; 491:107985.CR

Abstract

Schiff bases, the Amadori and Heyns rearrangement products are the most important isomeric intermediates involved in the early Maillard reaction; distinguishing between them by analytical mass spectroscopic techniques remains a challenge. Here we demonstrate that MS/MS fragmentation patterns can be used for the discrimination between glucose derived Schiff bases, Amadori, and Heyns compounds with glycine. An ESI-qTOF-MS system operated in the positive mode under both acidic and neutral conditions was employed to generate unique MS/MS fragmentation patterns of the molecules. Analysis of the MS data has indicated that acidic medium is suitable for generating characteristic and diagnostic ions. At high collision energy (20 eV), the spectrum of Schiff base was largely uninformative, whereas both Amadori and Heyns compounds undergo characteristic fragmentations with high diagnostic value. At low collision energy values (10eV), we observed formation of prominent diagnostic ions from the Schiff base precursor, as well as extensive dehydration reactions of all three molecules. Under acidic conditions, the diagnostic fragmentation pattern of the Amadori compound featured consecutive dehydration reactions. At higher values (20 eV) it underwent the α-fission at the carbonyl group and produced a prominent diagnostic ion [AA + H + CH2]+ at m/z 88. The Schiff base was found to preferentially undergo the retro-aldol degradation and produce diagnostic ions at m/z 118 [AA + H + diose]+ and m/z 140 [AA + Na + diose]+, together with their sugar complements at m/z 85 [tetrose + H-2H2O]+ and m/z 143 [tetrose + Na]+. In the case of Heyns compound, several diagnostic ions were also detected, including the ions at m/z 154 [M + H-2H2O-C2H4O2]+, m/z 170 [AA + Na + triose]+ and m/z 142 [AA + H + Furan]+.

Authors+Show Affiliations

Department of Food Science & Agricultural Chemistry, McGill University, 21111 Lakeshore, Ste Anne de Bellevue, Quebec, Canada, H9X 3V9. Electronic address: varoujan.yaylayan@mcgill.ca.Department of Biochemistry, University of Missouri, Columbia, MO, 65211, USA.Department of Food Science & Agricultural Chemistry, McGill University, 21111 Lakeshore, Ste Anne de Bellevue, Quebec, Canada, H9X 3V9. Electronic address: varoujan.yaylayan@mcgill.ca.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32213351

Citation

Xing, Haoran, et al. "Diagnostic MS/MS Fragmentation Patterns for the Discrimination Between Schiff Bases and Their Amadori or Heyns Rearrangement Products." Carbohydrate Research, vol. 491, 2020, p. 107985.
Xing H, Mossine VV, Yaylayan V. Diagnostic MS/MS fragmentation patterns for the discrimination between Schiff bases and their Amadori or Heyns rearrangement products. Carbohydr Res. 2020;491:107985.
Xing, H., Mossine, V. V., & Yaylayan, V. (2020). Diagnostic MS/MS fragmentation patterns for the discrimination between Schiff bases and their Amadori or Heyns rearrangement products. Carbohydrate Research, 491, 107985. https://doi.org/10.1016/j.carres.2020.107985
Xing H, Mossine VV, Yaylayan V. Diagnostic MS/MS Fragmentation Patterns for the Discrimination Between Schiff Bases and Their Amadori or Heyns Rearrangement Products. Carbohydr Res. 2020;491:107985. PubMed PMID: 32213351.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Diagnostic MS/MS fragmentation patterns for the discrimination between Schiff bases and their Amadori or Heyns rearrangement products. AU - Xing,Haoran, AU - Mossine,Valeri V, AU - Yaylayan,Varoujan, Y1 - 2020/03/14/ PY - 2019/10/02/received PY - 2020/03/02/revised PY - 2020/03/12/accepted PY - 2020/3/28/pubmed PY - 2021/1/5/medline PY - 2020/3/28/entrez KW - Amadori compound KW - Collision induced fragmentations KW - Diagnostic ions KW - Heyns compound KW - Maillard reaction KW - Schiff base KW - Tandem mass spectrometry (MS/MS) SP - 107985 EP - 107985 JF - Carbohydrate research JO - Carbohydr Res VL - 491 N2 - Schiff bases, the Amadori and Heyns rearrangement products are the most important isomeric intermediates involved in the early Maillard reaction; distinguishing between them by analytical mass spectroscopic techniques remains a challenge. Here we demonstrate that MS/MS fragmentation patterns can be used for the discrimination between glucose derived Schiff bases, Amadori, and Heyns compounds with glycine. An ESI-qTOF-MS system operated in the positive mode under both acidic and neutral conditions was employed to generate unique MS/MS fragmentation patterns of the molecules. Analysis of the MS data has indicated that acidic medium is suitable for generating characteristic and diagnostic ions. At high collision energy (20 eV), the spectrum of Schiff base was largely uninformative, whereas both Amadori and Heyns compounds undergo characteristic fragmentations with high diagnostic value. At low collision energy values (10eV), we observed formation of prominent diagnostic ions from the Schiff base precursor, as well as extensive dehydration reactions of all three molecules. Under acidic conditions, the diagnostic fragmentation pattern of the Amadori compound featured consecutive dehydration reactions. At higher values (20 eV) it underwent the α-fission at the carbonyl group and produced a prominent diagnostic ion [AA + H + CH2]+ at m/z 88. The Schiff base was found to preferentially undergo the retro-aldol degradation and produce diagnostic ions at m/z 118 [AA + H + diose]+ and m/z 140 [AA + Na + diose]+, together with their sugar complements at m/z 85 [tetrose + H-2H2O]+ and m/z 143 [tetrose + Na]+. In the case of Heyns compound, several diagnostic ions were also detected, including the ions at m/z 154 [M + H-2H2O-C2H4O2]+, m/z 170 [AA + Na + triose]+ and m/z 142 [AA + H + Furan]+. SN - 1873-426X UR - https://www.unboundmedicine.com/medline/citation/32213351/Diagnostic_MS/MS_fragmentation_patterns_for_the_discrimination_between_Schiff_bases_and_their_Amadori_or_Heyns_rearrangement_products_ L2 - https://linkinghub.elsevier.com/retrieve/pii/S0008-6215(19)30580-4 DB - PRIME DP - Unbound Medicine ER -