TY - JOUR A1 - Herter, Sven-Oliver A1 - Koch, Matthias A1 - Haase, Hajo T1 - First Synthesis of Ergotamine-13CD3 and Ergotaminine-13CD3 from Unlabeled Ergotamine N2 - Ergot alkaloids (EAs) formed by Claviceps fungi are one of the most common food contaminants worldwide, affecting cereals such as rye, wheat, and barley. To accurately determine the level of contamination and to monitor EAs maximum levels set by the European Union, the six most common EAs (so-called priority EAs) and their corresponding epimers are quantified using high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The quantification of EAs in complex food matrices without appropriate internal tandards is challenging but currently carried out in the standard method EN 7425:2021 due to their commercial unavailability. To address the need for isotopically labeled EAs, we focus on two semi-synthetic approaches for the synthesis of these reference standards. Therefore, we investigate the feasibility of the N6-demethylation of native ergotamine to yield norergotamine, which can subsequently be remethylated with an isotopically labeled methylating reagent, such as iodomethane (13CD3-I), to yield isotopically labeled ergotamine and its C8-epimer ergotaminine. Testing the isotopically labeled ergotamine/-inine against native ergotamine/-inine with HPLC coupled to high-resolution HR-MS/MS proved the structure of ergotamine-13CD3 and ergotaminine-13CD3. Thus, for the first time, we can describe their synthesis from unlabeled, native ergotamine. Furthermore, this approach is promising as a universal way to synthesize other isotopically labeled EAs. KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Standards KW - Organic Synthesis KW - Isotope PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600167 DO - https://doi.org/10.3390/toxins16040199 VL - 16 IS - 4 SP - 1 EP - 12 PB - MDPI AN - OPUS4-60016 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Epping, Ruben A1 - Lisec, Jan A1 - Koch, Matthias T1 - Changes in Black Truffle (Tuber melanosporum) Aroma during Storage under Different Conditions N2 - The enticing aroma of truffles is a key factor for their culinary value. Although all truffle species tend to be pricy, the most intensely aromatic species are the most sought after. Research into the aroma of truffles encompasses various disciplines including chemistry, biology, and sensory science. This study focusses on the chemical composition of the aroma of black truffles (Tuber melanosporum) and the changes occurring under different storage conditions. For this, truffle samples were stored under different treatments, at different temperatures, and measured over a total storage time of 12 days. Measurements of the truffle aroma profiles were taken with SPME/GC–MS at regular intervals. To handle the ample data collected, a systematic approach utilizing multivariate data analysis techniques was taken. This approach led to a vast amount of data which we made publicly available for future exploration. Results reveal the complexity of aroma changes, with 695 compounds identified, highlighting the need for a comprehensive understanding. Principal component analyses offer initial insights into truffle composition, while individual compounds may serve as markers for age (formic acid, 1-methylpropyl ester), freshness (2-Methyl-1-propanal; 1-(methylthio)-propane), freezing (tetrahydrofuran), salt treatment (1-chloropentane), or heat exposure (4-hydroxy-3-methyl-2-butanone). This research suggests that heat treatment or salt contact significantly affects truffle aroma, while freezing and cutting have less pronounced effects in comparison. The enrichment of compounds showing significant changes during storage was investigated with a metabolomic pathway analysis. The involvement of some of the enriched compounds on the pyruvate/glycolysis and sulfur pathways was shown. KW - Mass Spectrometry KW - Metabolomics KW - Tuber melanosporum KW - Truffle Aroma PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601731 DO - https://doi.org/10.3390/jof10050354 VL - 10 IS - 5 SP - 1 EP - 22 PB - MDPI AN - OPUS4-60173 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Koch, Matthias T1 - PFAS-Analytik – Ein Überblick N2 - Die Gruppe der PFAS (Per- und polyfluorierte Alkylsubstanzen) mit mehr als 10.000 Substanzen stellt ein zunehmendes Problem bei der Bewertung und Entsorgung belasteter Abfälle dar. Die zuverlässige PFAS-Analytik stellt hier aufgrund der Vielzahl an Einzelparametern mit zum Teil sehr großen Konzentrationsunterschieden eine komplexe Herausforderung dar. Der Vortrag gibt zunächst einen Überblick über grundlegende Anforderungen an die LC-MS/MS Analytik von PFAS-Targetsubstanzen. Am Beispiel eines von BAM und SenMVKU organisierten Ringversuches 2024 zur Bestimmung von PFAS in Bodenproben (Feststoffe und Eluate) wird auf spezifische Fragestellungen zur PFAS-Analytik eingegangen. Zur Verbesserung von Richtigkeit und Vergleichbarkeit ist die Einhaltung von Normvorgaben und die Anwendung von Qualitätssicherungsmaßnahmen unerlässlich. Hierzu gehören u.a. die Verwendung zuverlässiger Kalibrierstandards, die Kalibrierung mit definierten n-Isomeren, die Quantifizierung der Summe aus n-/br-Isomeren, der Einsatz isotopenmarkierter interner Standards für die LC-MS/MS Analyse, die Verwendung von Matrix-Referenzmaterialien sowie die Teilnahme an Ringversuchen. T2 - Schaffung von Laborkapazitäten zur Untersuchung PFAS-belasteter Abfälle CY - Potsdam, Germany DA - 11.09.2024 KW - PFAS KW - Ringversuch KW - Qualitätssicherung KW - Referenzmaterial PY - 2024 AN - OPUS4-61014 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Temgoua Tonleu, Ranil C. A1 - Koch, Matthias T1 - Simulation of the Environmental Degradation of TBBPA by EC-LC-MS N2 - Oxidative degradation processes of tetrabromobisphenol A (TBBPA), a brominated flame retardant (BFR) in wood, plastics and electronics, were investigated by electrochemistry (EC) coupled online to electrospray ionization mass spectrometry (ESI/MS). Oxidative phase I and II metabolites production was achieved using an electrochemical flow-through cell equipped with a boron doped diamond electrode. Structural elucidation and prediction of oxidative metabolism pathways of TBBPA according to type II ipso-substitution were based on retention time, m/z ratio in negative mode and fragmentation pattern. Using the data obtained through high resolution MS analysis and the identification of single electron transfer (SET) as the initial step of a two-electron oxidation provided the necessary information to propose a mechanism for the electrochemical oxidation of TBBPA. Oxidation reactions involving aromatic hydroxylation and β-scission were the main degradation observed when studying the electrochemical behavior of TBBPA. Computational chemistry experiments using density functional theory (DFT) allowed to identify mono-hydroxylated reaction intermediate and dismissed the mechanism involving two concurrent hydroxylation. TBBPA oxidation products were compared to known metabolites of its biological and environmental degradation confirming the ability of electrochemistry to simulate β-scission reactions. T2 - Mass Spectrometry Forum 2024 CY - Vienna, Austria DA - 21.02.2024 KW - Emerging pollutants KW - Chemical characterization KW - Electrochemistry KW - Chemical and material safety KW - Mass spectrometry KW - Environment-material interactions PY - 2024 AN - OPUS4-59571 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholl, Juliane A1 - Lisec, Jan A1 - Haase, Hajo A1 - Koch, Matthias T1 - Identification of transformation products from fluorinated lithium-ion battery additives TPFPB and TPFPP: forever chemicals of tomorrow? N2 - AbstractFluorinated organic compounds (FOCs) represent a class of synthetic chemicals distinguished by their resilient carbon–fluorine bonds, which demonstrate an ability to withstand environmental degradation over an extended period. The integration of FOCs into cutting-edge applications, including lithium-ion batteries (LiBs), presents considerable potential for environmental harm that has not yet been sufficiently addressed. This study focuses on the environmental fate of two fluorinated aromatics, tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), given their important role in improving the performance of LiBs. To achieve this, laboratory simulation methods including total oxidizable precursor assay, electrochemistry (EC), Fenton reaction, UV-C irradiation, and hydrolysis were employed. Liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry were used for identification of transformation products (TPs) and prediction of their molecular formulae. Despite the structural similarity between TPFPB and TPFPP, distinct differences in electrochemical behavior and degradation pathways were observed. TPFPB readily underwent hydroxylation and hydrolysis, resulting in a wide range of 49 TPs. A total of 28 TPs were newly identified, including oligomers and highly toxic dioxins. In contrast, TPFPP degraded exclusively under harsh conditions, requiring the development of innovative conditioning protocols for EC. In total, the simulation experiments yielded nine structurally different compounds, including seven previously undescribed, partially defluorinated TPs. This study highlights the potential risks associated with the use of FOCs in LiBs and provides insight into the complex environmental behavior of FOCs. KW - Mass Spectrometry KW - LiBs KW - POPs KW - Transformation products KW - Electrochemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611339 DO - https://doi.org/10.1007/s00216-024-05526-z SP - 1 EP - 15 PB - Springer Science and Business Media LLC AN - OPUS4-61133 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Junge, Florian A1 - Wittwer, Philipp A1 - Sommerfeld, Thomas A1 - Gehrenkemper, Lennart A1 - Zoister, Christian A1 - Nickl, Philip A1 - Koch, Matthias A1 - Meermann, Björn A1 - Haag, Rainer T1 - Adsorber Charge Dominates over Hydrophobic or Fluorophilic Functionalization in Influencing Adsorption of PFCA onto Polystyrene Resins N2 - A systematic series of industrial-relevant polystyrene-based anion exchange resins that are functionalized with hydro- or fluorocarbon chains are compared regarding their adsorption behavior toward perfluorocarboxylic acids (PFCA) in respect to their charge, chain length, and type of chain. The results clearly show the dominance of electrostatic interactions in the adsorption process as uncharged adsorber materials showed no adsorption at all. In contrast, the charged adsorber materials showed in general a PFCA removal of 80% to 30% over the experiment depending on effluent fraction. Unexpectedly, for perfluorobutanoic acid (PFBA) the highest removal rate is found with consistently >90%. Despite observing significant benefits in the adsorption of PFCA for fluoroalkylated adsorbers in comparison to their non-fluorinated counterparts, this effect of fluoroalkylation is comparatively small and can not be clearly attributed to fluorophilic interactions between the fluoroalkyl chains. These findings help clarifying that the introduction of fluorocarbon moieties in adsorber materials is not necessary in order to remove fluorocarbon molecules from the environment. KW - PFAS KW - Remediation KW - Adsorption KW - Fluorophilic interactions PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601883 DO - https://doi.org/10.1002/admi.202400199 SN - 2196-7350 SP - 1 EP - 10 PB - John Wiley & Sons CY - Hoboken, New Jersey, USA AN - OPUS4-60188 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -