title: Chemical Synthesis of Deoxynivalenol-3-β-d-[(13)C₆]-glucoside and Application in Stable Isotope Dilution Assays.
abstract: Modified mycotoxins have been gaining importance in recent years and present a certain challenge in LC-MS/MS analysis. Due to the previous lack of a labeled isotopologue of the modified mycotoxin deoxynivalenol-3-glucoside, in our study we synthesized the first (13)C-labeled internal standard. Therefore, we used the Königs-Knorr method to synthesize deoxynivalenol-3-β-d-[(13)C₆]-glucoside originated from unlabeled deoxynivalenol and [(13)C₆]-labeled glucose. Using the synthesized isotopically-labeled standard deoxynivalenol-3-β-d-[(13)C₆]-glucoside and the purchased labeled standard [(13)C15]-deoxynivalenol, a stable isotope dilution LC-MS/MS method was firstly developed for deoxynivalenol-3-glucoside and deoxynivalenol in beer. The preparation and purification of beer samples was based on a solid phase extraction. The validation data of the newly developed method gave satisfying results. Intra- and interday precision studies revealed relative standard deviations below 0.5% and 7%, respectively. The recoveries ranged for both analytes between 97% and 112%. The stable isotope dilution assay was applied to various beer samples from four different countries. In summary, deoxynivalenol-3-glucoside and deoxynivalenol mostly appeared together in varying molar ratios but were quantified in rather low contents in the investigated beers.
authors.affiliation: Analytical Food Chemistry, Technische Universit&#228;t M&#252;nchen, Alte Akademie 10, D-85354 Freising, Germany. katharina.habler@tum.de.
authors.forename: Katharina
authors.initials: K
authors.lastname: Habler
authors.affiliation: Food Chemistry and Molecular Sensory Science, Technische Universit&#228;t M&#252;nchen, Lise-Meitner-Straße 34, D-85354 Freising, Germany. oliver.frank@tum.de.
authors.forename: Oliver
authors.initials: O
authors.lastname: Frank
authors.affiliation: Analytical Food Chemistry, Technische Universit&#228;t M&#252;nchen, Alte Akademie 10, D-85354 Freising, Germany. michael.rychlik@tum.de.
authors.forename: Michael
authors.initials: M
authors.lastname: Rychlik
mesh_terms: D002247:Carbon Isotopes / Q000737:chemistry*; D002853:Chromatography, Liquid; D005960:Glucosides / Q000138:chemical synthesis* / Q000737:chemistry; D007554:Isotopes / Q000737:chemistry*; D015394:Molecular Structure; D011865:Radioisotope Dilution Technique; D053719:Tandem Mass Spectrometry; D014255:Trichothecenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D002247:Carbon Isotopes; D005960:Glucosides; D007554:Isotopes; D014255:Trichothecenes; C542050:deoxynivalenol-3-glucoside
keywords: LC-MS/MS; beer; deoxynivalenol-3-glucoside; labeled standard; modified mycotoxin; stable isotope dilution assay; synthesis