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Dynamic covalent hydrazine chemistry as a selective extraction and cleanup technique for the quantification of the Fusarium mycotoxin zearalenone in edible oils
Authors:David Siegel  Karsten Andrae  Matthias Proske  Cindy Kochan  Matthias Koch  Marcus Weber  Irene Nehls
Affiliation:1. BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Str. 11, 12489 Berlin, Germany;2. Konrad-Zuse-Zentrum für Informationstechnik Berlin, Takustr. 7, 14195 Berlin, Germany
Abstract:A novel, cost-efficient method for the analytical extraction of the Fusarium mycotoxin zearalenone (ZON) from edible oils by dynamic covalent hydrazine chemistry (DCHC) was developed and validated for its application with high performance liquid chromatography-fluorescence detection (HPLC-FLD). ZON is extracted from the edible oil by hydrazone formation on a polymer resin functionalised with hydrazine groups and subsequently released by hydrolysis. Specifity and precision of this approach are superior to liquid partitioning or gel permeation chromatography (GPC). DCHC also extracts zearalanone (ZAN) but not α-/β-zearalenol or -zearalanol. The hydrodynamic properties of ZON, which were estimated using molecular simulation data, indicate that the compound is unaffected by nanofiltration through the resin pores and thus selectively extracted. The method's levels of detection and quantification are 10 and 30 μg/kg, using 0.2 g of sample. Linearity is given in the range of 10–20,000 μg/kg, the average recovery being 89%. Bias and relative standard deviations do not exceed 7%. In a sample survey of 44 commercial edible oils based on various agricultural commodities (maize, olives, nuts, seeds, etc.) ZON was detected in four maize oil samples, the average content in the positive samples being 99 μg/kg. The HPLC-FLD results were confirmed by HPLC–tandem mass spectrometry and compared to those obtained by a liquid partitioning based sample preparation procedure.
Keywords:Zearalenone   Extraction   Edible oil   Maize   Dynamic covalent hydrazine chemistry   Hydrazone   SPE   Hydrodynamic radius   HPLC-FLD
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