Electrochemical simulation of biotransformation reactions of citrinin and dihydroergocristine compared to UV irradiation and Fenton-like reaction

Abstract

Mycotoxins occur widely in foodstuffs and cause a variety of mold-related health risks to humans and animals. Elucidation of the metabolic fate of mycotoxins and the growing number of newly discovered mycotoxins have enhanced the demand for fast and reliable simulation methods. The viability of electrochemistry coupled with mass spectrometry (EC/ESI-MS), Fenton-like oxidation, and UV irradiation for the simulation of oxidative phase I metabolism of the mycotoxins citrinin (CIT) and dihydroergocristine (DHEC) was investigated. The specific reaction products are compared with metabolites produced by human and rat liver microsomes in vitro. Depending on the applied potential between 0 and 2000 mV vs. Pd/H by using a flow-through cell, CIT and DHEC are oxidized to various products. Besides dehydrogenation and dealkylation reactions, several hydroxylated DHEC and CIT species are produced by EC and Fenton-like reaction, separated and analyzed by LC-MS/MS and ESI-HRMS. Compared to reaction products from performed microsomal incubations, several mono- and dihydroxylated DHEC species were found to be similar to the reaction products of EC, Fenton-like reaction, and UV-induced oxidation. Consequentially, nonmicrosomal efficient and economic simulation techniques can be useful in early-stage metabolic studies, even if one-to-one simulation is not always feasible.

Analysis of electrochemical and liver microsomal transformation products of lasalocid by LC/HRMS

“…The solvent mixture contained 60% methanol. It is known from the literature that adduct formation with methanol occurs at a double bound or aromatic system within the EC cell 29–31 . The single methanol accumulation was identified nine times.…”

“…Typical EC modification reactions like (de-) hydrogenation (À/+H), oxidation (+O) as hydroxylation (+OH), (de-) hydration (À/+H 2 O), and (de-)methylation (À/+CH 3 ) were identified.The solvent mixture contained 60% methanol. It is known from the literature that adduct formation with methanol occurs at a double bound or aromatic system within the EC cell [29][30][31]. The single methanol accumulation was identified nine times.…”

Prediction of Transformation Products of Monensin by Electrochemistry Compared to Microsomal Assay and Hydrolysis

“…Stereoisomers of TP 2 were not found, but the intensity of TP 2 is much lower than for TP 5/6, which is why only one TP with water addition was identified. The addition of methanol to substances by EC was described previously in studies on mycotoxins [33,34].…”

Root uptake and metabolization of Alternaria toxins by winter wheat plants using a hydroponic system

“…In our study, the cultivation conditions (light, oxygen, metals in nutrient solution, etc.) may accelerate the degradation of ATs (Bazin et al 2013 ; Keller et al 2017 ; Kotthoff et al 2019 ). However, these factors were not systematically investigated in our study.…”