Glutathione-Conjugates of Deoxynivalenol in Naturally Contaminated Grain Are Primarily Linked via the Epoxide Group
Abstract
:1. Introduction
2. Results and Discussion
2.1. DON–GSH and Related Adducts in DON–Treated Wheat and Naturally Contaminated Grain
2.2. Mercapturates of DON
2.3. Separation of DON–Thiol Adducts
2.4. DON–Acetates
3. Conclusions
4. Materials and Methods
4.1. Chemicals and Reagents
4.2. Preparation of Reference Standard Mixtures
4.3. Samples and Extraction
4.4. LC-HRMS(/MS) Analyses
4.5. Oxidation of DON–GSH to DON–GS(O)H with Hydrogen Peroxide
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
Abbreviations
Cys | l-cysteine |
DON | 4-deoxynivalenol |
γ-GluCys | γ-l-glutamyl-l-cysteine |
CysGly | l-cysteinyl-l-glycine |
GSH | l-glutathione |
HRMS | high-resolution mass spectrometry |
LC | liquid chromatography |
MS/MS | tandem mass spectrometry |
NAC | N-acetylcysteine |
PFPP | pentafluorophenylpropyl |
tR | retention time |
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Compound | Ion Species ESI+ | Calculated Mass (m/z) | Ion Species ESI− | Calculated Mass (m/z) |
---|---|---|---|---|
Deoxynivalenol (DON) | - | - | [M + formate]− | 341.1242 |
3/15-O-acetyl-DON | [M + H]+ | 339.1438 | - | - |
[M + NH4]+ | 356.1704 | |||
[M + Na]+ | 361.1258 | |||
DON–GSH | [M + H]+ | 604.2171 | [M − H]− | 602.2025 |
DON–GS(O)H | [M + H]+ | 620.2120 | [M − H]− | 618.1974 |
DON–CysGly | [M + H]+ | 475.1745 | [M − H]− | 473.1599 |
DON–γ-GluCys | [M + H]+ | 547.1956 | [M − H]− | 545.1811 |
DON–Cys | [M + H]+ | 418.1530 | [M − H]− | 416.1385 |
DON–NAC | [M + H]+ | 460.1636 | [M − H]− | 458.1490 |
DON-3-β-d-glucoside | [M + NH4]+ | 476.2126 | [M + formate]− | 503.1770 |
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Uhlig, S.; Stanic, A.; Hofgaard, I.S.; Kluger, B.; Schuhmacher, R.; Miles, C.O. Glutathione-Conjugates of Deoxynivalenol in Naturally Contaminated Grain Are Primarily Linked via the Epoxide Group. Toxins 2016, 8, 329. https://doi.org/10.3390/toxins8110329
Uhlig S, Stanic A, Hofgaard IS, Kluger B, Schuhmacher R, Miles CO. Glutathione-Conjugates of Deoxynivalenol in Naturally Contaminated Grain Are Primarily Linked via the Epoxide Group. Toxins. 2016; 8(11):329. https://doi.org/10.3390/toxins8110329
Chicago/Turabian StyleUhlig, Silvio, Ana Stanic, Ingerd S. Hofgaard, Bernhard Kluger, Rainer Schuhmacher, and Christopher O. Miles. 2016. "Glutathione-Conjugates of Deoxynivalenol in Naturally Contaminated Grain Are Primarily Linked via the Epoxide Group" Toxins 8, no. 11: 329. https://doi.org/10.3390/toxins8110329