Since 2006, the responsible regulatory bodies have proposed five health-based guidance values (HBGV) for bisphenol A (BPA) that differ by a factor of 250,000. This range of HBGVs covers a considerable part of the range from highly toxic to relatively non-toxic substances. As such heterogeneity of regulatory opinions is a challenge not only for scientific risk assessment but also for all stakeholders, the Senate Commission on Food Safety (SKLM) of the German Research Foundation (DFG) analyzed the reasons for the current discrepancy and used this example to suggest improvements for the process of HBGV recommendations. A key aspect for deriving a HBGV is the selection of appropriate studies that allow the identification of a point of departure (PoD) for risk assessment. In the case of BPA, the HBGV derived in the 2023 EFSA assessment was based on a study that reported an increase of Th17 cells in mice with a benchmark dose lower bound (BMDL40) of 0.53 µg/kg bw/day. However, this study does not comply with several criteria that are important for scientific risk assessment: (1) the selected end-point, Th17 cell frequency in the spleen of mice, is insufficiently understood with respect to health outcomes. (2) It is unclear, by which mechanism BPA may cause an increase in Th17 cell frequency. (3) It is unknown, if an increase of Th17 cell frequency in rodents is comparably observed in humans. (4) Toxicokinetics were not addressed. (5) Neither the raw data nor the experimental protocols are available. A further particularly important criterion (6) is independent data confirmation which is not available in the present case. Previous studies using other readouts did not observe immune-related adverse effects such as inflammation, even at doses orders of magnitude higher than in the Th17 cell-based study. The SKLM not only provides here key criteria for the use of such studies, but also suggests that the use of such a “checklist” requires a careful and comprehensive scientific judgement of each item. It is concluded that the Th17 cell-based study data do not represent an adequate basis for risk assessment of BPA.

BACKGROUND Three different organic sunflower seed cakes, produced from seeds differing in the contents of hulls, were extracted by two different extraction methods, conventional extraction (CE) and ultrasound-assisted extraction (UAE). The total phenolic compounds (TPCs) contents of the extracts were evaluated by the Folin-Ciocalteu reagent (FCR) and high-performance liquid chromatography (HPLC) methods. In addition, antioxidant capacity of extracts was evaluated through the TEAC and DPPH assays. RESULTS Our results showed that both extracts displayed high TPCs and antioxidant capacity. The UAE method showed significantly higher TPCs and antioxidant capacity values compared to CE. Individual phenolic compounds such as chlorogenic acid (CGA) isomers (3-, 4- and 5-O-caffeoylquinic acids), di-CGA isomers, as well as feruloylquinic and coumaroylquinic acids were identified according to their exact masses by HPLC coupled to time-of-flight mass spectrometry. CONCLUSION The present results reveal that the UAE method could be effectively used to facilitate the extraction of phenolic compound from sunflower seed cake. This article is protected by copyright. All rights reserved.

Sucralose is an artificial sweetener whose stability during the thermal treatment of food is controversially discussed. In the present work, sucralose was subjected to different kinds of heat treatment either as such, in the presence of protein, or as an ingredient of food. Compared with sucrose, sucralose showed remarkable instability and discoloration after heating at 85-90 degrees C for 1 h. A chlorinated furan-3-one and different chlorinated dicarbonyl compounds were identified by High-performance liquid chromatography-time-of-flight mass spectrometry (HPLC-TOF-MS) for the first time, indicating that both the 4-chlorogalactosyl residue and the 1,6-dichlorofructosyl residue give rise to novel chlorinated sugar degradation products. When sucralose was heated in the presence of protein, the formation of 3-chlorotyrosine was detected, indicating that sucralose can invoke chlorination of other biomolecules. The influence of the addition of sucralose (0.03-0.1%) to dough on pH value, color development, and HMF formation was tested in baking experiments (muffins, coconut macaroons, cookies). A significantly higher HMF concentration was observed in bakery products, including sucralose, and a chlorinated 1,2-dicarbonyl compound was detected qualitatively in baked cookies. This work shows that sucralose is not stable during baking processes at high temperatures and low moisture contents, thereby confirming recommendations from the German Institute of Risk Assessment not to use sucralose for baking.

In the brewing process, methionine is a decisive amino acid for (off-)flavor formation. A significant part of methionine is oxidized to methionine sulfoxide (MetSO) in malt. We hypothesized that MetSO and MetSO(2) are metabolized to volatile compounds during yeast fermentation and examined whether the yeast Saccharomyces cerevisiae is able to catabolize l-MetSO and l-MetSO(2) in free and dipeptide-bound forms. We also investigated the stability of l-methionine sulfoximine and S-methylmethionine. Cell viability in the presence of the test compounds was at least 90%. Both free and peptide-bound test substances were metabolized by Saccharomyces cerevisiae. l-MetSO was degraded most rapidly as the free amino acid, while l-MetSO(2) was degraded most rapidly bound in dipeptides. We observed a different degradation behavior of the (R) and (S) diastereoisomers for l-MetSO and l-methionine sulfoximine. Furthermore, we detected methionol as the only metabolite of MetSO. Methionol sulfoxide was not formed. MetSO(2) was not converted to methionol or methionol sulfone but to the respective alpha-hydroxy acid. We conclude that the reduction of MetSO to methionine proceeds faster than transamination. The occurrence of MetSO or MetSO(2) in brewing malt will not lead to the formation of hitherto unknown volatile metabolites of the Ehrlich pathway.

The utilization of the glycated amino acids formyline and pyrraline as well as their peptide-bound derivatives by 14 Saccharomyces yeasts, including 6 beer yeasts (bottom and top fermenting), one wine yeast, 6 strains isolated from natural habitats and one laboratory reference yeast strain (wild type) was investigated. All yeasts were able to metabolize glycated amino acids via the Ehrlich pathway to the corresponding Ehrlich metabolites. While formyline and small amounts of pyrraline entered the yeast cells via passive diffusion, the amounts of dipeptide-bound MRPs, especially the dipeptides glycated at the C-terminus, decreased much faster, indicating an uptake into the yeast cells. Furthermore, the glycation-mediated hydrophobization in general leads to an faster degradation rate compared to the native lysine dipeptides. While the utilization of free formyline is yeast-specific, the amounts of (glycated) dipeptides decreased faster in the presence of brewer's yeasts, which also showed a higher formation rate of Ehrlich metabolites compared to naturally isolated strains. Due to rapid uptake of alanyl dipeptides, it can be assumed that the Ehrlich enzyme system of naturally isolated yeasts is overloaded and the intracellularly released MRP is primarily excreted from the cell. This indicates adaptation of technologically used yeasts to (glycated) dipeptides as a nitrogen source.

Current reports increasingly associate dietary "advanced glycation end products" ("AGEs") resulting from the Maillard reaction (glycation) between reducing sugars and amino compounds in foods with pathophysiological consequences, such as chronic inflammation, atherosclerosis, and metabolic syndrome. Heated foods are therefore suggested to pose a potential risk for human health. However, studies in this field are very often based on questionable quantitative data and inadequate structural characterization. To improve the situation, the present perspective suggests quality criteria for future studies and the assessment of the currently available literature.

Food proteins may be modified during processing and storage through reactions with reducing sugars (Maillard reaction, glycation) or by reactive oxygen species (protein oxidation). Little is known about particular reactions at the interface of glycation and oxidation. In the present study, the glycated amino acid pyrraline (6-(2-formyl-5-hydroxymethyl-1-pyrrolyl)-l-norleucine) and the proteinogenic amino acids tyrosine and tryptophan were subjected to different types of oxidation. The stability of the amino acids was assessed by HPLC with UV detection, whereas oxidation products were assigned by HPLC with triple quadrupole or time-of-flight mass spectrometric detection. Conditions that lead to oxidation of aromatic proteinogenic amino acids can also lead to oxidation of pyrraline. Pyrraline was particularly unstable in the presence of permanganate, hypochlorite, and under hydroxyl radical-generating conditions (iron, ethylenediaminetetraacetic acid, ascorbic acid). Evidence obtained by high-resolution mass spectrometry revealed the oxidation of pyrraline to 6-(2,5-diformyl-1-pyrrolyl)-l-norleucine, 6-(2-carboxy-5-hydroxymethyl-1-pyrrolyl)-l-norleucine, 6-(2-formyl-5-carboxy-1-pyrrolyl)-l-norleucine, and 6-(2,5-dicarboxy-1-pyrrolyl)-l-norleucine in the presence of potassium permanganate. The latter product was isolated by semipreparative HPLC and characterized by NMR. Under hydroxyl radical-generating conditions, pyrraline is hydroxylated at the ring under formation of 6-(2-formyl-4-hydroxy-5-hydroxymethyl-1-pyrrolyl)-l-norleucine or 6-(2-formyl-3-hydroxy-5-hydroxymethyl-1-pyrrolyl)-l-norleucine. This study shows that the so-called "advanced glycation end products" are no end products of the Maillard reaction, but may undergo further chemical degradation reactions.

Sunflower oil cake (SFC), a by-product of oil manufacturing, possesses a high protein content but is often disregarded due to its undesirable green color caused by phenolic compounds (PCs) during alkaline extraction. This study aimed at improving the color of extracted sunflower protein concentrate (SPC) without eliminating the PCs by employing two anti-greening additives, ascorbic acid (ASC) and N-acetylcysteine (NAC), at different concentrations (4, 8, and 12 mg/g meal) during extraction. Moreover, the effects of these additives on the chemical, structural, and functional properties of extracted proteins were assessed. The results showed that the SPC extracted without additives (control) and with 4 and 8 mg/g additives exhibited green color, while the most significant greening inhibition was attained with 12 mg/g of either ASC or NAC. All the extraction solutions resulted in SPC with comparable water solubility exceeding 90

LebensmittelchemieVolume 78, Issue S1 p. S1-014-S1-014 Abstract Abbau von N-Carboxymethylcadaverin (CM-CAD) durch Transaminasen in Escherichia coli E. Weidhaas, E. Weidhaas Dresden/DSearch for more papers by this authorP. Vougioukas, P. Vougioukas Dresden/DSearch for more papers by this authorE. F. Aveta, E. F. Aveta München/DSearch for more papers by this authorJ. Lassak, J. Lassak München/DSearch for more papers by this authorM. Hellwig, M. Hellwig Dresden/DSearch for more papers by this author E. Weidhaas, E. Weidhaas Dresden/DSearch for more papers by this authorP. Vougioukas, P. Vougioukas Dresden/DSearch for more papers by this authorE. F. Aveta, E. F. Aveta München/DSearch for more papers by this authorJ. Lassak, J. Lassak München/DSearch for more papers by this authorM. Hellwig, M. Hellwig Dresden/DSearch for more papers by this author First published: 01 March 2024 https://doi.org/10.1002/lemi.202452009AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Literatur 1Hellwig M., et al. J. Agric. Food Chem. 2019 67, 1963-1972. 10.1021/acs.jafc.8b06748 CASPubMedWeb of Science®Google Scholar 2Adamczyk P. A.,Reed J. L., Current Opinion in Systems Biology 2017 6, 80-88 Google Scholar 3Walczak M., et al. Lebensmittelchemie 2022 76, S2-282 Google Scholar 4Bui T.P.N., et al. J. Agric. Food Chem. 2019 67, 6594-6602 10.1021/acs.jafc.9b02208 CASPubMedWeb of Science®Google Scholar Volume78, IssueS1Supplement: Abstracts der Vorträge der Regionalverbände und die der Posterflashtalks der AG JLCMarch/April 2024Pages S1-014-S1-014 ReferencesRelatedInformation

The aromatic amino acids tryptophan, phenylalanine, and tyrosine are targets for oxidation during food processing. We investigated whether S. cerevisiae can use nonproteinogenic aromatic amino acids as substrates for degradation via the Ehrlich pathway. The metabolic fate of seven amino acids (p-, o-, m-tyrosine, 3,4-dihydroxyphenylalanine (DOPA), 3-nitrotyrosine, 3-chlorotyrosine, and dityrosine) in the presence of S. cerevisiae was assessed. All investigated amino acids except dityrosine were metabolized by yeast. The amino acids 3-nitrotyrosine and o-tyrosine were removed from the medium as fast as p-tyrosine, and m-tyrosine, 3-chlorotyrosine, and DOPA more slowly. In summary, 11 metabolites were identified by high-performance liquid chromatography-mass spectrometry (HPLC-MS/MS). DOPA, 3-nitrotyrosine, and p-tyrosine were metabolized predominantly to the Ehrlich alcohols, whereas o-tyrosine and m-tyrosine were metabolized predominantly to alpha-hydroxy acids. Our results indicate that nonproteinogenic aromatic amino acids can be taken up and transaminated by S. cerevisiae quite effectively but that decarboxylation and reduction to Ehrlich alcohols as the final metabolites is hampered by hydroxyl groups in the o- or m-positions of the phenyl ring. The data on amino acid metabolism were substantiated by the analysis of five commercial beer samples, which revealed the presence of hydroxytyrosol (ca. 0.01-0.1 mg/L) in beer for the first time.

Methionine is an essential amino acid for mammals and it is limiting for monogastric animals. It can be oxidized easily by UV light. This could influence the bioaccessibility and bioavailability of methionine. In this work, the photosensitized degradation of peptide-bound methionine in the presence of riboflavin was investigated in a model system. Capillary electrophoresis was employed to analyze the time course of the degradation. The products were identified by liquid chromatography coupled to mass spectrometry (LC–MS/MS). Benzoyl methionine was degraded by 50

Dietary exposure to N-nitrosamines has recently been assessed by the European Food Safety Authority (EFSA) to result in margins of exposure that are conceived to indicate concern with respect to human health risk. However, evidence from more than half a century of international research shows that N-nitroso compounds (NOC) can also be formed endogenously. In this commentary of the Senate Commission on Food Safety (SKLM) of the German Research Foundation (DFG), the complex metabolic and physiological biokinetics network of nitrate, nitrite and reactive nitrogen species is discussed with emphasis on its influence on endogenous NOC formation. Pioneering approaches to monitor endogenous NOC have been based on steady-state levels of N-nitrosodimethylamine (NDMA) in human blood and on DNA adduct levels in blood cells. Further NOC have not been considered yet to a comparable extent, although their generation from endogenous or exogenous precursors is to be expected. The evidence available to date indicates that endogenous NDMA exposure could exceed dietary exposure by about 2–3 orders of magnitude. These findings require consolidation by refined toxicokinetics and DNA adduct monitoring data to achieve a credible and comprehensive human health risk assessment.

LebensmittelchemieVolume 77, Issue S3 p. S3-280-S3-280 Weitere Themen Abbau von Nɛ-Carboxymethyllysm (CML) über die Decarboxylasen SpeC und SpeF in Escherichia coli P. Vougioukas, P. Vougioukas Dresden/D DLC Patroklos Vougioukas, Professur für Spezielle Lebensmittelchemie, TU Dresden, D-01062 DresdenSearch for more papers by this authorM. Walczak, M. Walczak Dresden/DSearch for more papers by this authorE. Aveta, E. Aveta München/DSearch for more papers by this authorJ. Mehler, J. Mehler München/DSearch for more papers by this authorN. Gericke, N. Gericke München/DSearch for more papers by this authorJ. Lassak, J. Lassak München/DSearch for more papers by this authorM. Hellwig, M. Hellwig Dresden/DSearch for more papers by this author P. Vougioukas, P. Vougioukas Dresden/D DLC Patroklos Vougioukas, Professur für Spezielle Lebensmittelchemie, TU Dresden, D-01062 DresdenSearch for more papers by this authorM. Walczak, M. Walczak Dresden/DSearch for more papers by this authorE. Aveta, E. Aveta München/DSearch for more papers by this authorJ. Mehler, J. Mehler München/DSearch for more papers by this authorN. Gericke, N. Gericke München/DSearch for more papers by this authorJ. Lassak, J. Lassak München/DSearch for more papers by this authorM. Hellwig, M. Hellwig Dresden/DSearch for more papers by this author First published: 01 August 2023 https://doi.org/10.1002/lemi.202359248AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Literatur [1]Hellwig, M. et al. J. Agric. Food Chem. 2019, 67, 1963–1972. [2]Hellwig, M. et al J. Agric. Food Chem. 2015, 63, 6723–6730. [3]Bui, T.P.N. et al. J. Agric. Food Chem. 2019, 67, 6594–6602. [4]Walczak M. et al., Lebensmitteichemie 2022, 76, S2–282. Volume77, IssueS3Supplement: Abstracts der Vorträge, Posterflashtalks und Poster von den 51. Deutschen Lebensmittelchemietagen 2023August 2023Pages S3-280-S3-280 ReferencesRelatedInformation

Proteins are an important part of our regular diet. During food processing, their amino acid composition can be chemically altered by the reaction of free amino groups with sugars - a process termed glycation. The resulting Maillard reaction products (MRPs) have low bioavailability and thus predominantly end up in the colon where they encounter our gut microbiota. In the following review, we summarize bacterial strategies to efficiently metabolize these non-canonical amino acids. A particular focus will be on the complex regulatory mechanisms that allow a tightly controlled expression of metabolic genes to successfully occupy the ecological niches that result from the chemical diversity of MRPs.

This opinion of the Senate Commission on Food Safety (SKLM) of the German Research Foundation (Deutsche Forschungsgemeinschaft, DFG) presents arguments for an updated risk assessment of diet-related exposure to acrylamide (AA), based on a critical review of scientific evidence relevant to low dose exposure. The SKLM arrives at the conclusion that as long as an appropriate exposure limit for AA is not exceeded, genotoxic effects resulting in carcinogenicity are unlikely to occur. Based on the totality of the evidence, the SKLM considers it scientifically justified to derive a tolerable daily intake (TDI) as a health-based guidance value.

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC-TOFMS) is one the most powerful analytical platforms for chemical investigations of complex biological samples. It produces large datasets that are rich in information, but highly complex, and its consistency may be affected by random systemic fluctuations and/or changes in the experimental parameters. This study details the optimization of a data processing strategy that compensates for severe 2D pattern misalignments and detector response fluctuations for saliva samples analyzed across 2 years. The strategy was trained on two batches: one with samples from healthy subjects who had undergone dietary intervention with high/low-Maillard reaction products (dataset A), and the second from healthy/unhealthy obese individuals (dataset B). The combined untargeted and targeted pattern recognition algorithm (i.e., UT fingerprinting) was tuned for key process parameters, the signal-to-noise ratio (S/N), and MS spectrum similarity thresholds, and then tested for the best transform function (global or local, affine or low-degree polynomial) for pattern realignment in the temporal domain. Reliable peak detection achieved its best performance, computed as % of false negative/positive matches, with a S/N threshold of 50 and spectral similarity direct match factor (DMF) of 700. Cross-alignment of bi-dimensional (2D) peaks in the temporal domain was fully effective with a supervised operation including multiple centroids (reference peaks) and a match-and-transform strategy using affine functions. Regarding the performance-derived response fluctuations, the most promising strategy for cross-comparative analysis and data fusion included the mass spectral total useful signal (MSTUS) approach followed by Z-score normalization on the resulting matrix.

This review aims to summarize our current knowledge of the impact of advanced glycation products (AGEs) in the diet on the development of allergies. The association between modern dietary patterns that contain high amounts of thermally processed food products, and the development of allergies is of great concern. One group of molecules generated by such dietary patterns is AGEs resulting from the Maillard reaction (MR). Evidence suggests that the MR could influence the allergenicity of food proteins because it alters the structure of proteins by modifying lysine and arginine residues with various types of AGE structures. Several studies, including ours, have indicated that certain AGEs affect innate immune responses via the engagement of AGE-binding receptors. AGEs could also influence the composition of the gut microbiome and its metabolites. Collectively, AGEs may alter the risk of multiple disorders, including allergies, by interacting with innate immunity and changing the gut microbiome.

LebensmittelchemieVolume 77, Issue S3 p. S3-264-S3-264 Weitere Themen Fermentation oxidierter Methionin-Derivate durch Saccharomyces cerevisae K.I. Behringer, K.I. Behringer Braunschweig/D Institut für Lebensmittelchemie, TU Braunschweig, D-38106 BraunschweigSearch for more papers by this authorV. Fritz, V. Fritz Braunschweig/DSearch for more papers by this authorM. Hellwig, M. Hellwig Dresden/DSearch for more papers by this author K.I. Behringer, K.I. Behringer Braunschweig/D Institut für Lebensmittelchemie, TU Braunschweig, D-38106 BraunschweigSearch for more papers by this authorV. Fritz, V. Fritz Braunschweig/DSearch for more papers by this authorM. Hellwig, M. Hellwig Dresden/DSearch for more papers by this author First published: 01 August 2023 https://doi.org/10.1002/lemi.202359232AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Literatur [1]Hellwig, M. Angew. Chem. Int. Ed. Engl. 2019, 58, 16742–16763. [2]Lund, M.N., Heinonen, M., Baron, C.P., Estévez, M. Mol. Nutr. Food Sci. 2011, 55, 83–95. [3]Estévez, M., Luna, C. Food Sci. Nutr. 2017, 57, 3781–3793. [4]Hellwig, M., Löbmann, K., Orywol, T., Voigt, A. J. Agric. Food Chem. 2014, 62, 4425–4433. [5]Tannenbaum, S. R., Barth, H., Le Roux, J.P. J. Agric. Food Chem. 1969, 17, 1353–1354. [6]Meltretter, J., Wüst, J., Pischetsrieder, M. J. Agric. Food Chem. 2014, 62, 10903–10915. [7]Baxter, J.H., Lai, C.-S., Phillips, R. R., Dowlati, L., Chio, J.J., Luebbers, S.T., Dimler, S.R., Johns, P. W. J. Chrom. A 2007, 1157, 10–16. [8]Fleischer K., Hellwig M., Eur. Food Res. Technol. 2023, 249: 199–206. [9]Hellwig M., Börner, M., Beer, F., van Pée, K.H., Henle, T. ChemBioChem 2017, 18, 266–275. Volume77, IssueS3Supplement: Abstracts der Vorträge, Posterflashtalks und Poster von den 51. Deutschen Lebensmittelchemietagen 2023August 2023Pages S3-264-S3-264 ReferencesRelatedInformation

The Senate Commission on Food Safety (SKLM) of the German Research Foundation (DFG) has reviewed the currently available data in order to assess the health risks associated with the use of acetaldehyde as a flavoring substance in foods. Acetaldehyde is genotoxic in vitro. Following oral intake of ethanol or inhalation exposure to acetaldehyde, systemic genotoxic effects of acetaldehyde in vivo cannot be ruled out (induction of DNA adducts and micronuclei). At present, the key question of whether acetaldehyde is genotoxic and mutagenic in vivo after oral exposure cannot be answered conclusively. There is also insufficient data on human exposure. Consequently, it is currently not possible to reliably assess the health risk associated with the use of acetaldehyde as a flavoring substance. However, considering the genotoxic potential of acetaldehyde as well as numerous data gaps that need to be filled to allow a comprehensive risk assessment, the SKLM considers that the use of acetaldehyde as a flavoring may pose a safety concern. For reasons of precautionary consumer protection, the SKLM recommends that the scientific base for approval of the intentional addition of acetaldehyde to foods as a flavoring substance should be reassessed.