Glucosylation and Glutathione Conjugation of Chlorpyrifos and Fluopyram Metabolites Using Electrochemistry/Mass Spectrometry
Abstract
:1. Introduction
2. Results and Discussion
2.1. Glutathione Conjugation of CPF TPs: Online EC/MS vs. Liver Microsomes
2.2. Glucosylation of CPF TPs in Online EC/MS
2.3. Glutathione Conjugation and Glucosylation of FLP TPs
3. Experimental
3.1. Chemicals and Reagents
3.2. Electrochemical Oxidation and Analysis of TPs
3.3. Adduct Formation with Biomolecules
3.4. Offline LC-MS/MS Analysis of Bioconjugates
3.5. Confirmation by HRMS
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Not available. |
Abbreviation/Symbol | tR (min) | Calculated [M + H]+ | Product Ions by QTRAP-MS/MS | Measured [M + H]+ | δm/m (ppm) | Type of Conjugate |
---|---|---|---|---|---|---|
C1 | 19.5 | 487.0007 | 308, 291, 180, 179, 205, 233 | 487.0030 | 4.7 | TCP + GSH – H2O |
C2 | 20.2 | 469.0346 | 469, 451/453, 433, 437, 405 | 469.0312 | 1.3 | TCP + GSH – HCl |
C3C5 | 21.530.4 | 621.0407 | 621, 603/605, 564, 593, 541, 469, 314, 288, 171, 154 | 621.0534 | 4.8 | CPF + GSH – HCl |
C4 | 23.3 | 605.0635 | 605, 564, 587, 573, 569, 555, 540, 339, 327, 298, 251, 154 | 605.0520 | 2.2 | Oxon +GSH – HCl |
C6 | 29.6 | 626.9704 | 609, 538, 369, 322, 308, 231 | 627.0068 | −7.2 | U |
C7 | 15.6 | 359.9803 | 360, 362, 364, 324, 198, 180 | 359.9891 | −5.2 | TCP + Glc – H2O |
C8 | 18.4 | 478.0431 | 316, 163, 153, 137, 162 | 478.0410 | 6.5 | Oxon + Glc – HCl |
C9 | 20.5 | 494.0203 | 515, 314, 171, 163 | 494.0299 | −3.2 | CPF + Glc – HCl |
C10 * | 23.84 | 702.1280 | 705, 513, 429, 395, 308, 173, 145, 129, 291, 179, 162 | 702.1832 | −5.1 | Hydroxyl FLP + GSH – H2O |
C11 * | 28.9 | 701.2423 | 703, 413, 395, 307, 289, 573, 173, 145, 129 | 701.2093 | −4.3 | Hydroxyl FLP + n-Glc – H2O |
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Mekonnen, T.F.; Panne, U.; Koch, M. Glucosylation and Glutathione Conjugation of Chlorpyrifos and Fluopyram Metabolites Using Electrochemistry/Mass Spectrometry. Molecules 2019, 24, 898. https://doi.org/10.3390/molecules24050898
Mekonnen TF, Panne U, Koch M. Glucosylation and Glutathione Conjugation of Chlorpyrifos and Fluopyram Metabolites Using Electrochemistry/Mass Spectrometry. Molecules. 2019; 24(5):898. https://doi.org/10.3390/molecules24050898
Chicago/Turabian StyleMekonnen, Tessema Fenta, Ulrich Panne, and Matthias Koch. 2019. "Glucosylation and Glutathione Conjugation of Chlorpyrifos and Fluopyram Metabolites Using Electrochemistry/Mass Spectrometry" Molecules 24, no. 5: 898. https://doi.org/10.3390/molecules24050898