TY - JOUR A1 - Koch, Matthias A1 - Mauch, Tatjana A1 - Riedel, Juliane T1 - Development of a Hydrazine-Based Solid-Phase Extraction and Clean-Up Method for Highly Selective Quantification of Zearalenone in Edible Vegetable Oils by HPLC-FLD N2 - Rapid, cost-efficient, and eco-friendly methods are desired today for routine analysis of the Fusarium mycotoxin zearalenone (ZEN) in edible vegetable oils. Liquid chromatography with fluorescence detection (HPLC-FLD) is commonly used to reliably control the specified ZEN maximum levels, which requires efficient sample clean-up to avoid matrix interferences. Therefore, a highly selective extraction and clean-up method based on reversible covalent hydrazine chemistry (RCHC) using hydrazine-functionalized silica was developed. This efficient solid-phase extraction (SPE) involves reversible hydrazone formation of ZEN with the hydrazine moiety covalently bound to a solid phase. Optimal conditions were achieved with 1 mL SPE cartridges filled with 400 mg of hydrazine-functionalized silica. The developed RCHC-SPE method was validated in an interlaboratory comparison study (ILC) with twelve participants analyzing six edible vegetable oils with a focus on maize oils. The derived method parameters (ZEN recovery 83%, repeatability 7.0%, and reproducibility 18%) meet the performance criteria of Commission Regulation (EC) No 401/2006. The developed RCHC-SPE-based HPLC-FLD method allows the reliable quantification of ZEN in the range of 47–494 μg/kg for different types of edible vegetable oils, also for matrix-reach native oils. Due to the high efficiency, the significantly reduced matrix load helps to extend the lifetime of analytical equipment. Furthermore, the re-useability of the RCHC-SPE cartridges contributes to an eco-friendly approach and reduced analysis costs. To our knowledge, this is the first report on ZEN quantification in edible vegetable oils based on manual RCHC-SPE cartridges. Due to its high performance, the developed RCHC-SPE method is a promising alternative to the current European standard method EN 16924:2017 (HPLC-FLD part). KW - Mycotoxin KW - Food KW - Reversible covalent hydrazine chemistry (RCHC) KW - Quantitative determination PY - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-554812 VL - 14 IS - 8 PB - MDPI CY - Basel AN - OPUS4-55481 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Siegel, David A1 - Merkel, Stefan A1 - Koch, Matthias A1 - Nehls, Irene T1 - Quantification of the Alternaria mycotoxin tenuazonic acid in beer N2 - Tenuazonic acid (TA) is a major water soluble Alternaria mycotoxin. In the present work, a method for the quantification of TA in beer by liquid chromatography-ion-trap multistage mass spectrometry after derivatization with 2,4-dinitrophenylhydrazine is described. The method is based on a rapid workup procedure and features a LOD of 2 µg/kg without preconcentration using 400 mg of sample. Validation was performed for a working range of 8-500 µg/kg. A total of 43 beers of different brewing styles (pilsener, wheat beer, bock beer, dark beer and alcohol free beer) was analysed. TA was detected in 37 samples, 16 samples were above the LOQ. An average content of 11 µg/kg was found, the highest incidence being 175 ± 13 µg/kg. To our knowledge, this is the first report on the occurrence of TA in beer and beverages in general. KW - Tenuazonic acid KW - Mycotoxin KW - Beer KW - 2,4-Dinitrophenylhydrazine KW - Derivatization KW - Liquid chromatography/electrospray ionisation ion-trap multistage mass Spectrome PY - 2010 U6 - https://doi.org/10.1016/j.foodchem.2009.10.070 SN - 0308-8146 VL - 120 IS - 3 SP - 902 EP - 906 PB - Elsevier CY - Amsterdam [u.a.] ; Jena AN - OPUS4-21372 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Drzymala, Sarah A1 - Weiz, S. A1 - Heinze, J. A1 - Marten, S. A1 - Prinz, Carsten A1 - Zimathies, Annett A1 - Garbe, L.-A. A1 - Koch, Matthias T1 - Automated solid-phase extraction coupled online with HPLC-FLD for the quantification of zearalenone in edible oil N2 - Established maximum levels for the mycotoxin zearalenone (ZEN) in edible oil require monitoring by reliable analytical methods. Therefore, an automated SPE-HPLC online system based on dynamic covalent hydrazine chemistry has been developed. The SPE step comprises a reversible hydrazone formation by ZEN and a hydrazine moiety covalently attached to a solid phase. Seven hydrazine materials with different properties regarding the resin backbone, pore size, particle size, specific surface area, and loading have been evaluated. As a result, a hydrazine-functionalized silica gel was chosen. The final automated online method was validated and applied to the analysis of three maize germ oil samples including a provisionally certified reference material. Important performance criteria for the recovery (70–120 %) and precision (RSDr <25 %) as set by the Commission Regulation EC 401/2006 were fulfilled: The mean recovery was 78 % and RSDr did not exceed 8 %. The results of the SPE-HPLC online method were further compared to results obtained by liquid&–liquid extraction with stable isotope dilution analysis LC-MS/MS and found to be in good agreement. The developed SPE-HPLC online system with fluorescence detection allows a reliable, accurate, and sensitive quantification (limit of quantification, 30 µg/kg) of ZEN in edible oils while significantly reducing the workload. To our knowledge, this is the first report on an automated SPE-HPLC method based on a covalent SPE approach. KW - Dynamic covalent hydrazine chemistry (DCHC) KW - Maize germ oil KW - Food KW - Mycotoxin KW - ZEA KW - Isomerisation KW - Occurrence KW - Edible oil KW - SIDA KW - LC-MS/MS KW - Quantification PY - 2015 U6 - https://doi.org/10.1007/s00216-015-8541-5 SN - 1618-2642 SN - 1618-2650 VL - 407 IS - 12 SP - 3489 EP - 3497 PB - Springer CY - Berlin AN - OPUS4-33067 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Drzymala, Sarah A1 - Binder, J. A1 - Brodehl, Antje A1 - Penkert, M. A1 - Rosowski, M. A1 - Garbe, L.-A. A1 - Koch, Matthias T1 - Estrogenicity of novel phase I and phase II metabolites of zearalenone and cis-zearalenone N2 - Zearalenone and its cis-isomer, cis-zearalenone, are nonsteroidal mycotoxins that elicit an estrogenic response upon binding to the estrogen receptor. This study compares the estrogenicity of eleven congeners including novel metabolites as 15-OH-zearalenone, zearalenone-14-sulfate, α-cis-zearalenol and β-cis-zearalenol using the E-Screen assay. Overall, a change in the configuration from trans to cis retains significant estrogenic activity. In contrast, alterations of the aromatic moiety including hydroxylation and sulfation showed a markedly decreased estrogenicity when compared to zearalenone. KW - Zearalenone KW - Mycotoxin KW - MCF-7 KW - E-screen assay KW - Estrogenicity KW - Isomerization PY - 2015 U6 - https://doi.org/10.1016/j.toxicon.2015.08.027 SN - 0041-0101 SN - 1879-3150 VL - 105 SP - 10 EP - 12 PB - Elsevier CY - Oxford [u.a.] AN - OPUS4-34167 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Borzekowski, Antje A1 - Drewitz, T. A1 - Keller, Julia A1 - Pfeifer, Dietmar A1 - Kunte, Hans-Jörg A1 - Koch, Matthias A1 - Rohn, S. A1 - Maul, R. T1 - Biosynthesis and characterization of zearalenone-14-sulfate, zearalenone-14-glucoside and zearalenone-16-glucoside using common fungal strains N2 - Zearalenone (ZEN) and its phase II sulfate and glucoside metabolites have been detected in food and feed commodities. After consumption, the conjugates can be hydrolyzed by the human intestinal microbiota leading to liberation of ZEN that implies an underestimation of the true ZEN exposure. To include ZEN conjugates in routine analysis, reliable standards are needed, which are currently not available. Thus, the aim of the present study was to develop a facilitated biosynthesis of ZEN-14-sulfate, ZEN-14-glucoside and ZEN-16-glucoside. A metabolite screening was conducted by adding ZEN to liquid fungi cultures of known ZEN conjugating Aspergillus and Rhizopus strains. Cultivation conditions and ZEN incubation time were varied. All media samples were analyzed for metabolite formation by HPLC-MS/MS. In addition, a consecutive biosynthesis was developed by using Fusarium graminearum for ZEN biosynthesis with subsequent conjugation of the toxin by utilizing Aspergillus and Rhizopus species. ZEN-14-sulfate (yield: 49%) is exclusively formed by Aspergillus oryzae. ZEN-14-glucoside (yield: 67%) and ZEN-16-glucoside (yield: 39%) are formed by Rhizopus oryzae and Rhizopus oligosporus, respectively. Purities of ≥73% ZEN-14-sulfate, ≥82% ZEN-14-glucoside and ≥50% ZEN-16-glucoside were obtained by 1H-NMR. In total, under optimized cultivation conditions, fungi can be easily utilized for a targeted and regioselective synthesis of ZEN conjugates. KW - Mycotoxin KW - Zearalenone KW - Conjugate KW - Biosynthesis KW - Fusarium KW - Aspergillus KW - Rhizopus PY - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-444246 SN - 2072-6651 VL - 10 IS - 3 SP - Article 104, 1 EP - 15 PB - MDPI CY - Basel AN - OPUS4-44424 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Keller, Julia A1 - Hantschke, Luisa A1 - Haase, H. A1 - Koch, Matthias T1 - Synthesis and Structural Identification of a Biaryl Ether-Linked Zearalenone Dimer N2 - A new dimer of the food-relevant mycotoxin zearalenone was isolated after electrochemical and chemical oxidation. The structure was determined as a 16-O-15'-biaryl ether-linked dimer based on spectroscopic analyses (1H- and 13C-NMR, COSY, HMBC, and HSQCAD) and high-Resolution mass spectrometry analysis (Q-TOF). KW - Mycotoxin KW - Dimerization KW - HRMS KW - NMR PY - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-464940 SN - 1420-3049 VL - 23 IS - 10 SP - 2624 EP - 2628 PB - MDPI CY - Basel AN - OPUS4-46494 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Koch, Matthias A1 - Riedel, Juliane A1 - Rasenko, Tatjana A1 - Bremser, Wolfram T1 - Development of certified reference material and analytical method for zearalenone in edible oil N2 - Quality and safety of food products require their reliable analysis. Contaminants, in particular mycotoxins, are key-components for food safety. About 25 % of the world's food crops are contaminated with mycotoxins posing a severe health risk to humans. In order to strengthen food safety and consumer protection the European Commission (EC) set maximum levels for priority mycotoxins in certain foods for human consumption. In 2013, the EC and CEN (European Committee for Standardization) started an initiative to standardize analytical methods for mycotoxins in food which gained increasing relevance, e.g. zearalenone (ZEN). ZEN, an estrogenic mycotoxin produced by several Fusarium species, contaminates cereal crops worldwide. Due to its lipophilic nature ZEN is often found in edible oils (particularly in maize germ oils) derived from contaminated plants. Therefore, an European maximum level of 400 µg/kg is currently in force. To perform reliable food analysis a sustainable metrological infrastructure is of major importance enabling the quantification of priority mycotoxins (here: ZEN). To achieve this goal, an integrated approach is needed targeted at the development of validated analytical methods and certified reference materials (CRM). A highly selective method for ZEN in edible oils will be presented, based on solid phase extraction (SPE) using hydrazine-functionalized particles. This method was developed for manual application using commercial SPE cartridges as well as for automated SPE-HPLC online coupling. While ZEN is covalently coupled to the solid phase by means of a hydrazone bond, undesired matrix components can be removed very efficiently. Finally, ZEN is decoupled from the solid phase, leading to highly purified extracts which are measured by HPLC-FLD. The development of the first European Reference Material (ERM®) for ZEN in maize germ oil (ERM®-BC715) will be presented and discussed. This ERM®-project underpins the urgent need for mycotoxin-CRMs to support food safety and public health. T2 - 40. Generalversammlung ISO/REMCO CY - Berlin, Germany DA - 27.06.2017 KW - Certified reference materials KW - Mycotoxin KW - Food PY - 2017 AN - OPUS4-40902 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -