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Dietary biomarkers show great promise for objectively assessing the food intake in humans. In this study, potential urinary biomarkers for red bell pepper intake were identified based on a dietary intervention study and a comprehensive metabolomics approach. Spot urine samples from 14 volunteers were collected in the two phases of the study (control phase: abstaining from any bell pepper/paprika products; case phase: consumption of a defined amount of fresh red bell pepper and abstaining from any further bell pepper/paprika products) and analyzed by high-performance liquid chromatography high-resolution mass spectrometry (HPLC-HRMS). Comparison of the obtained metabolomics data using statistical analysis revealed that the respective urine metabolomes differ significantly, which was attributable to the bell pepper intake. Some of the most discriminating metabolites were selected and isolated from human urine for unequivocal structure elucidation by nuclear magnetic resonance (NMR) spectroscopy. Herein, seven novel glucuronidated metabolites most likely derived from capsanthin and capsianosides were identified, implying their potential application as dietary biomarkers for the entire Capsicum genus.

Aronia melanocarpa (MICHX.) ELLIOTT, which belongs to the Rosaceae family, has increasingly come into focus of research due to the high content of polyphenols. In addition to antioxidative properties, further health-promoting effects of these polyphenols are still of interest. Especially, the proanthocyanidins offer thereby huge opportunities due to their high structural heterogeneity. Therefore, the present study focuses on the topoisomerase inhibiting effects of oligomeric proanthocyanidins (PACs), which are potentially depended on their degree of polymerization. The investigated PACs isolated from Aronia berries were characterized by chromatographic techniques and liquid chromatography-high-resolution mass spectrometry. Four PAC enriched fractions were obtained from Aronia pomace containing 47 PACs with a degree of polymerization from three to six. Due to the low yield of hexamers, the potential inhibiting effects against human topoisomerase were investigated for the trimer to pentamer fractions. The relaxation and decatenation assays were performed to examine the inhibiting effect on topoisomerases under cell-free conditions. Moreover, rapid isolation of topoisomerase cleavage complexes in human colon carcinoma HT29 cells was performed to evaluate the effect on topoisomerases in a cell-based system. The fractions demonstrated inhibitory potential on topoisomerases I and II. In sum, an increasing effect strength depending on the degree of polymerization was shown.

Fungi belonging to the genus Stachybotrys are frequently detected in water-damaged indoor environments, and a potential correlation between emerging health problems of inhabitants of affected housing and the fungi is controversially discussed. Secondary metabolites (i.e., mycotoxins) produced by Stachybotrys, such as the highly toxic macrocyclic trichothecenes (MCTs), are of potential concern to human health. The present study, however, focused on the potential effects of the more broadly and abundantly formed group of phenylspirodrimanes (PSDs). The phase I and II metabolism of four structurally different PSDs were investigated in vitro using hepatic models in combination with high-performance liquid chromatography high-resolution mass spectrometry (HPLC-HRMS) analysis. In addition to metabolite detection by HRMS, isolation and structure elucidation by nuclear magnetic resonance spectroscopy (NMR) was part of the conducted study as well.

Plants from the Solanaceae family are known to be sources of several nutritionally relevant steroidal glycoalkaloids (SGAs). With the aim of quantitatively investigating the occurrence of the main SGA from tomatoes, eggplants, and potatoes in various food samples and evaluating their relevance in the human diet, a rapid single-step extraction liquid chromatography-tandem mass spectrometry method was developed. Over the course of isolating several commercially unavailable SGAs from tomato products to use them as reference standards, a previously unknown derivative was detected, structurally characterized, and identified as a novel isomer of esculeoside B-1 and B-2. After validation of the method, 36 food items exclusively derived from Solanaceae plants were analyzed for their SGA contents and a specific occurrence of each alkaloid in tomato, eggplant, or potato products was revealed. This is the first study reporting quantitative data on the occurrence of esculeoside A, B-1, B-2, and iso-esculeoside B in tomato products obtained by using appropriate reference compounds rather than applying a semi-quantitative approach based on α-tomatine as a reference. Some of the analyzed tomato products contained the esculeosides in concentrations of >500 mg/kg, clearly indicating their relevance in the human diet and the need of investigating their potential bioactivities in the future.

The occurrence of glucose-derived β-carboline alkaloids tangutorid E (Tan E) and tangutorid F (Tan F) as well as their dehydroxy-derivatives (DH-Tan E/F) was investigated in a broad variety of foodstuffs by LC-MS/MS-based stable isotope dilution analysis (SIDA). For that purpose, the target compounds and their 13C6-stable isotope-labeled analogues were synthesized from l-tryptophan and (13C6-)d-glucose and used to develop a rapid LC-MS/MS-SIDA method. After validation for several food matrices, the method was applied to the analysis of these β-carbolines in 80 food items. Quantitative amounts were detected in 46.3, 50.0, and 42.5% of the samples regarding Tan E, Tan F, and DH-Tan E/F, respectively, with corresponding ranges of 0.01-6.75, 0.01-5.07, and 0.01-0.75 mg/kg; the highest amounts were found in processed tomato products. A combination of the obtained occurrence data in foods with average food consumption data led to the calculation of rough estimates for the chronic daily intake of those alkaloids, yielding values of 0.44, 0.36, and 0.13 μg/kg body weight/day for Tan E, Tan F, and DH-Tan E/F, respectively. Evidently, the consumption of processed tomato-based products accounts for the majority of the total daily intake of the investigated β-carbolines; the potential bioactivities of Tan E, Tan F, and DH-Tan E/F have yet to be investigated.

Citrinin (CIT) is a nephrotoxic mycotoxin produced by Penicillium, Monascus, and Aspergillus species. CIT appears as a contaminant in cereals, cereal-based products, fruits, nuts, and spices. During the biotransformation of CIT, its major urinary metabolite dihydrocitrinone (DHC) is formed. Albumin interacts with several compounds (including mycotoxins) affecting their tissue distribution and elimination. CIT-albumin interaction is known; however, the complex formation of DHC with albumin has not been reported previously. In this study, we aimed to investigate the interaction of DHC with albumin, employing fluorescence spectroscopy, circular dichroism, and molecular modeling studies. Furthermore, species differences and thermodynamics of the interaction as well as the effects of albumin on the acute in vitro toxicity of DHC and CIT were also tested. Our main observations/conclusions are as follows: (1) Fluorescence signal of DHC is strongly enhanced by albumin. (2) Formation of DHC-albumin complexes is supported by both fluorescence spectroscopic and circular dichroism studies. (3) DHC forms similarly stable complexes with human albumin (K~105 L/mol) as CIT. (4) DHC-albumin interaction did not show significant species differences (tested with human, bovine, porcine, and rat albumins). (5) Based on modeling studies and investigations with site markers, DHC occupies the Heme binding site (subdomain IB) on human albumin. (6) The presence of albumin significantly decreased the acute in vitro cytotoxic effects of both DHC and CIT on MDCK cell line.

Plants from the Solanaceae family are known to be sources of several nutritionally relevant steroidal glycoalkaloids (SGAs). With the aim of quantitatively investigating the occurrence of the main SGA from tomatoes, eggplants, and potatoes in various food samples and evaluating their relevance in the human diet, a rapid single-step extraction liquid chromatography-tandem mass spectrometry method was developed. Over the course of isolating several commercially unavailable SGAs from tomato products to use them as reference standards, a previously unknown derivative was detected, structurally characterized, and identified as a novel isomer of esculeoside B-1 and B-2. After validation of the method, 36 food items exclusively derived from Solanaceae plants were analyzed for their SGA contents and a specific occurrence of each alkaloid in tomato, eggplant, or potato products was revealed. This is the first study reporting quantitative data on the occurrence of esculeoside A, B-1, B-2, and

Scope As orange juice belongs to one of the most consumed juices worldwide, a human study is performed to identify urinary biomarkers for the consumption of orange juice in order to differentiate between low, medium, and high intake. Methods and results The 32 study participants abstained from citrus fruits, juices and products thereof, except for one portion of orange juice, for eight days. Throughout the study, spot urine samples are collected and quantitatively analyzed by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) regarding their content of several potential biomarkers for orange juice intake after enzymatic treatment with β-glucuronidase. Proline betaine is determined as a long-term biomarker: based on its urinary excretion, orange juice consumption is traceable for at least 72 h after intake. Naringenin and hesperetin are identified as qualitative short-term biomarkers. Synephrine sulfate also showed a fast increase and decrease in a semi-quantitative approach. In the case of phloretin, no correlation between orange juice consumption and the urinary concentration is observed. Conclusion Proline betaine is the most promising biomarker for orange juice consumption and allows to differentiate between low, medium, and high intake. Hesperetin and naringenin (as well as synephrine) are applicable as supporting biomarkers, whereas phloretin does not represent a reliable biomarker for orange juice consumption.

The Escherichia coli (E. coli) strains Nissle 1917 (EcN), 83972 and CFT073 are closely related but differ in their phenotypes and pathogenicity. The aim of this study was to compare the metabolome of these strains based on metabolomic data analysis of bacterial samples using liquid chromatography-high resolution mass spectrometry (LCHRMS). The strains were cultivated in minimum essential medium at 37 °C for 6 h. The sterilized culture supernatant was analyzed, followed by data processing to create feature lists, and statistical analysis to identify discriminating features in the metabolomes of the three strains. Metabolites were identified using the exact masses, isotope patterns, and fragmentation spectra. The results showed that the metabolome of EcN differs significantly from the metabolomes of E. coli 83972 and CFT073. Based on the analysis, yersiniabactin (Ybt), its metal complexes, and its known structural derivatives escherichelin and ulbactin B were identified as discriminating features; the latter has not been described for E. coli before. Additionally, novel Ytb derivatives were found and tentatively identified by LC-MS/HRMS. All these metabolites were determined in significantly higher levels in the metabolome of EcN compared to E. coli 83972, which may explain a large part of the observed differences of the metabolomes.

Molecular networking connects tandem mass spectra of molecules based on the similarity of their fragmentation patterns. However, during ionization, molecules commonly form multiple ion species with different fragmentation behavior. To connect ion species of the same molecule, we developed Ion Identity Molecular Networking. These new relationships improve network connectivity, are shown to reveal novel ion-ligand complexes, enhance annotation within molecular networks, and facilitate the expansion of spectral libraries. Fil: Schmid, Robin. University Of Munster; Alemania Fil: Petras, Daniel. University Of California At San Diego. Skaggs School Of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center.; Estados Unidos Fil: Nothias, Louis Félix. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Wang, Mingxun. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Aron, Allegra T.. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Jagels, Annika. University of Munster; Alemania Fil: Tsugawa, Hiroshi. RIKEN Center for Sustainable Resource Science; Japón Fil: Rainer, Johannes. University of Lübeck; Italia Fil: Garcia-Aloy, Mar. University of Lübeck; Italia Fil: Dührkop, Kai. Universitat Jena; Alemania Fil: Korf, Ansgar. University of Munster; Alemania Fil: Pluskal, Tomáš. Czech Academy of Sciences; República Checa Fil: Kameník, Zdeněk. Czech Academy of Sciences; República Checa Fil: Jarmusch, Alan K.. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Caraballo Rodríguez, Andrés Mauricio. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Weldon, Kelly. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Nothias Esposito, Melissa. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Aksenov, Alexander A.. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Bauermeister, Anelize. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Albarracín Orio, Andrea Georgina. Universidad Católica de Córdoba. Instituto de Investigaciones en Recursos Naturales y Sustentabilidad José Sanchez Labrador S. J. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Recursos Naturales y Sustentabilidad José Sanchez Labrador S. J.; Argentina Fil: Grundmann, Carlismari O.. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Vargas, Fernando. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Koester, Irina. University of California at San Diego; Estados Unidos Fil: Gauglitz, Julia M.. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Gentry, Emily C.. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Hövelmann, Yannick. University of Munster; Alemania Fil: Kalinina, Svetlana A.. University of Munster; Alemania Fil: Pendergraft, Matthew A.. University of California at San Diego; Estados Unidos Fil: Panitchpakdi, Morgan W.. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Tehan, Richard. Oregon State University; Estados Unidos Fil: Le Gouellec, Audrey. Universite Grenoble Alpes; Francia. Centre National de la Recherche Scientifique; Francia Fil: Aleti, Gajender. University of California at San Diego; Estados Unidos Fil: Mannochio Russo, Helena. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos Fil: Arndt, Birgit. University of Munster; Alemania Fil: Hübner, Florian. University of Munster; Alemania Fil: Hayen, Heiko. University of Munster; Alemania Fil: Zhi, Hui. University of California at San Diego; Estados Unidos Fil: Raffatellu, Manuela. University of California at San Diego; Estados Unidos Fil: Prather, Kimberly A.. University of California at San Diego; Estados Unidos Fil: Aluwihare, Lihini I.. University of California at San Diego; Estados Unidos Fil: Böcker, Sebastian. Friedrich-Schiller-University, Jena; Alemania Fil: McPhail, Kerry L.. State University of Oregon; Estados Unidos Fil: Humpf, Hans-Ulrich. University of Munster; Alemania Fil: Karst, Uwe. University of Munster; Francia Fil: Dorrestein, Pieter. University of California at San Diego. Skaggs School of Pharmacy & Pharmaceutical Sciences. Collaborative Mass Spectrometry Innovation Center; Estados Unidos

In the course of gaining new insights into the secondary metabolite profile of various Stachybotrys strains, in particular concerning triprenyl phenol-like compounds, so far, unknown metabolites with analogous structural features were discovered. Three novel meroterpenoids containing a chromene ring moiety, namely stachybotrychromenes A–C, were isolated from solid culture of the filamentous fungus Stachybotrys chartarum DSMZ 12880 (chemotype S). Their structures were elucidated by means of comprehensive spectroscopic analysis (1D and 2D NMR, ESI-HRMS, and CD) as well as by comparison with spectroscopic data of structural analogues described in literature. Stachybotrychromenes A and B exhibited moderate cytotoxic effects on HepG2 cells after 24 h with corresponding IC50 values of 73.7 and 28.2 μM, respectively. Stachybotrychromene C showed no significant cytotoxic activity up to 100 μM. Moreover, it is noteworthy that stachybotrychromenes A–C are produced not only by S. chartarum chemotype S but also S. chartarum chemotype A and Stachybotrys chlorohalonata. Electronic supplementary material The online version of this article (10.1007/s12550-018-0312-7) contains supplementary material, which is available to authorized users.

The analysis of the nephrotoxic mycotoxin citrinin in food, feed, and physiological samples is still challenging. Nowadays, liquid chromatography coupled with mass spectrometry is the method of choice for achieving low limits of detection. But matrix effects can present impairments for this method. Stable isotope dilution analysis can prevent some of these problems. Therefore, a stable isotopically labeled standard of citrinin for use in stable isotope dilution analysis was synthesized on large scale. The improved diastereoselective total synthetic strategy offered the possibility to introduce three 13C-labels in two steps by ortho-toluate anion chemistry. This led to a mass difference of 3 Da, sufficient for preventing spectral overlap. Additionally, a stable isotopically labeled form of dihydrocitrinone, the main urinary metabolite of citrinin, was synthesized with the same mass difference. This was achieved by a sequence of cyclisation, oxidation, deprotection, and carboxylation reactions starting from a protected intermediate of the labeled citrinin synthesis. Thus, this method also offers a complete way to synthesize dihydrocitrinone from citrinin on large scale.

Determining the cutting forces poses one of the main challenges in generating gear grinding due to their significant influence on the dynamics of the grinding process. Thus, optimizing the cutting forces can lead to an increased quality of ground gears and a minimized wear of the grinding worm. This paper focusses on the analysis of single and multiple abrasive grits during the cutting process. Research focuses are the grinding forces and scratches in the material. With this data, a cutting force model for generating gear grinding can be enhanced ensuring a more precise analysis of the gear grinding process. Beneath the cutting forces, the ground gear topography including surface roughness can be simulated and evaluated according to common standards.

The genus Stachybotrys belongs to filamentous fungi found in indoor environment, mostly on cellulose-rich substrates after water-damage. The major purpose of this study was to investigate the influence of different building materials in case of mold infestation on the mycotoxin production of Stachybotrys species. Fifteen Stachybotrys mycotoxins including satratoxins, phenylspirodrimanes, and recently discovered stachybotrychromenes were in the focus of the investigations. Artificial and natural infestations were compared to determine whether environmental factors, for example, time of growth, temperature, humidity, and material additives have an influence on the observed mycotoxin profiles. It turned out that mycotoxin profiles from Stachybotrys spp. on building materials can be influenced by cellulose, paints, and paste of the materials. The total toxin levels of artificially and naturally contaminated gypsum board samples ranged up to 30 µg/cm2 , whereas wallpaper samples showed total toxin levels in the range of 20-66 µg/cm2 . A naturally infested sample disclosed the conversion of the dialdehyde components to the corresponding lactone isomers under the influence of light.

The present study aimed at the identification of novel imidazole alkaloids derived from histamine or histidinol and generally investigating the occurrence of suchlike alkaloids in a variety of foodstuffs. Herein, N-caprylhistamine was synthesized and the glucosidic derivative N-caprylhistamine-β-glucoside was isolated from ripe tomato fruits and structurally characterized. The obtained reference standards were used for the extension of an established LC-MS/MS-based method for the quantitation of several imidazole alkaloids in tomato products. After validation for the two additional analytes and demonstrating the applicability of the method to nine other food matrices, 104 food items were screened for the occurrence of the described imidazole alkaloids. Remarkably, all of the investigated alkaloids were only quantifiable in tomato-based products and the occurrence of N-caprylhistamine and N-caprylhistamine-β-glucoside was reported for the first time. These imidazole alkaloids could thus be applicable as specific intake biomarkers for tomatoes and their biological activities as well as metabolic fate should be investigated in future research.

Imidazole alkaloids represent a rather small group of alkaloids and are assumed not to be of significance to the human food chain so far. In this study, novel imidazole alkaloids occurring in tomato products were synthesized and structurally characterized by nuclear-magnetic-resonance spectroscopy and high-resolution mass spectrometry. These alkaloids are amides of either histidinol or histamine and short-chain fatty acids and could be quantitated in all of the 28 analyzed tomato products using a newly developed and validated LC-MS/MS-based method. Levels ranged from approximately 5 μg/kg to almost 3 mg/kg in the analyzed tomato products, and N-caprylhistidinol and its putative isomer were shown to occur in the highest amounts. These imidazole alkaloids are thus regularly ingested in considerable amounts as part of the human diet. In the course of evaluating their effects on the viability of HT-29 cells, all compounds were shown to significantly reduce cell viability starting at concentrations of 100 μM.

The genus Stachybotrys produces a broad diversity of secondary metabolites, including macrocyclic trichothecenes, atranones, and phenylspirodrimanes. Although the class of the phenylspirodrimanes is the major one and consists of a multitude of metabolites bearing various structural modifications, few investigations have been carried out. Thus, the presented study deals with the quantitative determination of several secondary metabolites produced by distinct Stachybotrys species for comparison of their metabolite profiles. For that purpose, 15 of the primarily produced secondary metabolites were isolated from fungal cultures and structurally characterized in order to be used as analytical standards for the development of an LC-MS/MS multimethod. The developed method was applied to the analysis of micro-scale extracts from 5 different Stachybotrys strains, which were cultured on different media. In that process, spontaneous dialdehyde/lactone isomerization was observed for some of the isolated secondary metabolites, and novel stachybotrychromenes were quantitatively investigated for the first time. The metabolite profiles of Stachybotrys species are considerably influenced by time of growth and substrate availability, as well as the individual biosynthetic potential of the respective species. Regarding the reported adverse effects associated with Stachybotrys growth in building environments, combinatory effects of the investigated secondary metabolites should be addressed and the role of the phenylspirodrimanes re-evaluated in future research.

Generally, hard finishing is the final step in manufacturing cylindrical gears. The most established processes for hard finishing are continuous generation grinding and discontinuous profile grinding [1]. Despite the wide industrial application of the continuous generation grinding process, only few scientific investigations exist. One possible reason for this are the complex contact conditions between tool and gear flank. Modelling the complex contact conditions between grinding worm and gear to calculate cutting forces, characteristic values as well as micro- and macroscopic gear geometry are the topics of this paper. The approaches are introduced and results for validation are presented and discussed.

Zusammenfassung Nicht erst seit den Anschlagen von Paris am 13. November 2015 stellt die salafistische Bewegung eine Herausforderung fur die innere wie internationale Sicherheit dar. Der vorliegende Beitrag analysiert Radikalisierungsmuster junger Muslime und identifiziert Grunde fur die Anziehungskraft dieser fundamentalistischen Ideologie. Schlagworter: Salafismus – Radikalisierung – Islamismus ----- Bibliographie: Hubner, Florian/Winkelmann, Thorsten: Salafistische Radikalisierung in Deutschland, GWP, 1-2016, S. 11-16. https://doi.org/10.3224/gwp.v65i1.22213

Zusammenfassung Die Auseinandersetzung mit der aktuellen Fluchtlingsbewegung gewinnt an Scharfe. Vor allem nach den Vorfallen in Koln und anderen deutschen Grosstadten wahrend der Silvesternacht werden die Konsequenzen fur die innere Sicherheit thematisiert. Schlagworter: Fluchtlinge, Migration, Asyl, innere Sicherheit, Islamisierung ----- Bibliographie: Winkelmann, Thorsten/Hubner, Florian: Wie umgehen mit der aktuellen Fluchtlingsbewegung?, GWP, 1-2016, S. 101-108. https://doi.org/10.3224/gwp.v65i1.22223

Scope In this study, the applicability of several β-carboline, imidazole, and steroidal alkaloids as biomarkers for tomato juice intake is evaluated. Methods and results Over the course of a 2-week crossover dietary intervention study, 14 volunteers were given low and high doses of tomato juice after 3 days of avoiding tomato-based products. On the day of consumption and the following days, volunteers provided urine samples that were quantitatively analyzed by high-performance liquid chromatography-tandem mass spectrometry. Herein, glucose-derived β-carboline alkaloids are determined as supporting, yet non-specific dietary biomarkers for tomato juice intake. Several imidazole alkaloids represent further biomarkers, which are shown to specifically indicate consumption of tomato juice for 24 h and partly >24 h. Additionally, steroidal alkaloids derived from esculeogenin B are determined to be specific biomarkers for tomato juice detectable for at least 48 h after consumption. The intake of low and high amounts of tomato juice is significantly distinguishable based on the urinary excretion of all determined biomarkers as well. Conclusions The dietary intake of tomato juice is conclusively traceable based on urinary excretion of multiple β-carboline, imidazole, and steroidal alkaloids, and can be determined for up to 48 h after consumption. Furthermore, different intake doses can clearly be distinguished based on their urinary excretion.

Dietary biomarkers allow the accurate and objective determination of the dietary intake of humans and can thus be valuable for investigating the relation between consumption of foods and biochemical as well as physiological responses. The objective of this study was the identification of potential urinary biomarkers for consumption of tomato juice. In the course of a dietary intervention study, the human urine metabolome of a study cohort was compared between a tomato-free diet and after intake of tomato juice by application of an LC-HRMS-based metabolomics approach. The data acquisition was achieved using an orbitrap mass spectrometer, followed by multistage data processing and univariate as well as multivariate statistical analysis to identify discriminating features. Statistical analysis revealed several unique features detectable after tomato juice intake. The most discriminating markers were putatively identified as hydroxylated and sulfonated metabolites of esculeogenin B, aglycone of the steroidal glycoalkaloid esculeoside B recently found in tomato juice. Furthermore, the β-carboline alkaloids tangutorid E and F and glucuronidated derivatives thereof were identified in urine. Steroidal glycoalkaloids in tomato juice are cleaved after ingestion, and hydroxylated and sulfonated metabolites of their aglycones might serve as urinary biomarkers for tomato juice intake. Similarly, β-carboline alkaloids and glucuronidated derivatives were identified as potential urinary biomarkers. Both the aglycones of the steroidal alkaloids and the β-carboline alkaloids might exhibit biological activities worth investigating.

The analysis of the nephrotoxic mycotoxin citrinin in food, feed, and physiological samples is still challenging. Nowadays, liquid chromatography coupled with mass spectrometry is the method of choice for achieving low limits of detection. But matrix effects can present impairments for this method. Stable isotope dilution analysis can prevent some of these problems. Therefore, a stable isotopically labeled standard of citrinin for use in stable isotope dilution analysis was synthesized on large scale. The improved diastereoselective total synthetic strategy offered the possibility to introduce three

Zusammenfassung Die Ausrufung des Kalifats Ende Juni 2014 stellt bis heute den Hohepunkt der territorialen Eroberungen des Islamischen Staates (kurz: IS) wahrend der letzten Jahre dar. Welche politischen, okonomischen und sozialen Konsequenzen sind mit der Kontrolle dieser Gebiete durch den IS verbunden. Schlagworter: Islamischer Staat, Guerilla, Naher Osten, Syrien, Irak ----- Bibliographie: Winkelmann, Thorsten/Hubner, Florian: Die Staatswerdung einer Terrororganisation: Der Islamische Staat, GWP, 2-2015, S. 173-180. https://doi.org/10.3224/gwp.v64i2.19452

Within the past two decades high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS) has turned from a rare curiosity to a routine system found in most analytical laboratories. In this chapter the principles and applications of this technique will be discussed starting with the different ionization interfaces and followed by a detailed look at the mass analyzers used in most systems. Furthermore, the different experiments that can be performed with modern mass spectrometers will be described, typical applications shown, and the difficulties observed when using HPLC-MS for the quantitative approaches discussed. Finally, future perspectives and new developments will be described.

cope : Urinary biomarkers are used to estimate the nutritional intake of humans. The aim of this study was to distinguish between low, medium and high apple consumption by quantifying possible intake biomarkers in urine samples after apple consumption by HPLC-MS/MS. Apples were chosen as they are the most consumed fruits in Germany. Methods and Results : 30 subjects took part in a seven day study. They abstained from apples and apple products except for one weighed apple portion resembling one, two or four apples. Before apple consumption and during the following days spot urine samples were collected. These urine samples were incubated with β-glucuronidase, diluted and directly measured by HPLC-MS/MS. Phloretin, epicatechin, procyanidin B2 and quercetin were detected in urine using Scheduled MRMTM mode. Phloretin was confirmed as a urinary biomarker of apple intake and had the ability to discriminate between low or medium (1 or 2 apples) and high apple consumption (4 apples). The groups also differ in the excretion of epicatechin and procyanidin B2. Conclusion : Apple consumption can be monitored by urinary biomarkers for a period of at least 12h after consumption. Furthermore the amount of apples consumed can be estimated by the concentration of certain biomarkers. This article is protected by copyright. All rights reserved

(18)O labeling is a well-known method for the stable isotope labeling of proteins and peptides. This study describes a modified procedure for using (18)O labeling on small molecules. Fumonisin B1, a worldwide occurring mycotoxin, which is routinely analyzed by HPLC-MS/MS, was chosen as model compound. (18)O labeling was achieved by acid-catalyzed oxygen exchange from H2(18)O. A mixture of different isotopologues was obtained from the exchange, which, however, could be used as an internal standard for HPLC-MS/MS analysis. The identity of the (18)O-labeled fumonisin B1 was confirmed by NMR and HRMS measurements. The applicability as internal standard has been verified by comparison of results obtained from the method described in this paper to results obtained by reference methods. The presented method is of special interest as the (18)O labeling can be generally applied to a large group of small molecules containing carboxylic groups.

Beveloid gears, also known as conical involute gears, gain more and more importance in industrial practice. They are based on cylindrical gears, but have a variable profile shift along their tooth width. For some time, beveloid gears have been applied to marine transmissions (Winkler 2002; Zhu et al. in Chin J Mech Eng 25:328–337, 2012), but in the last years they have been used increasingly in the automotive industry (Borner et al. in Gear Technol 6:28–35, 2005; Alxneit 2010). A crucial step of the manufacturing process is the grinding process that is necessary to achieve high load carrying capacity and low noise vibration harshness (NVH). During the grinding process the micro-geometry of the tooth flanks can be modified in order to increase the gear quality. For the generation grinding process of beveloids, two types of machine kinematics and two tool concepts are known. The different machine kinematics and tool concepts may lead to unintentional changes in micro-geometry of the flanks which has an impact on load carrying capacity and NVH qualities of the gear. Up to now, no research has been made to quantify the influence of the machine kinematics and the tool concept on load carrying capacity and NVH. Therefore, these influences are analyzed in this work by simulating the gear manufacturing with the help of the two known machine kinematics as well as the two known tool concepts and by meshing the simulated gears in an FE-based tooth contact analysis (TCA). The results of the TCA are parameters regarding the running behavior which are analyzed and compared for the four aforementioned manufacturing concepts.

The mycotoxin T-2 toxin, produced by various Fusarium species, is a widespread contaminant of grain and grain products. Knowledge about its toxicity and metabolism in the human body is crucial for any risk assessment as T-2 toxin can be detected in processed and unprocessed food samples. Cell culture studies using cells of human origin represent a potent model system to study the metabolic fate of T-2 toxin as well as the cytotoxicity in vitro. In this study the metabolism of T-2 toxin was analyzed in a cell line derived from human colon carcinoma cells (HT-29) and primary human renal proximal tubule epithelial cells (RPTEC) using high-performance liquid chromatography coupled with Fourier transformation mass spectrometry (HPLC-FTMS). Both cell types metabolized T-2 toxin to a variety of compounds. Furthermore, cell cycle analysis in RPTEC proved the apoptotic effect of T-2 toxin and its metabolites HT-2 toxin and neosolaniol in micromolar concentrations. © 2012 American Chemical Society.

Procyanidins, as important secondary plant metabolites in fruits, berries, and beverages such as cacao and tea, are supposed to have positive health impacts, although their bioavailability is yet not clear. One important aspect for bioavailability is intestinal metabolism. The investigation of the microbial catabolism of A-type procyanidins is of great importance due to their more complex structure in comparison to B-type procyanidins. A-type procyanidins exhibit an additional ether linkage between the flavan-3-ol monomers. In this study two A-type procyanidins, procyanidin A2 and cinnamtannin B1, were incubated in the pig cecum model to mimic the degradation caused by the microbiota. Both A-type procyanidins were degraded by the microbiota. Procyanidin A2 as a dimer was degraded by about 80% and cinnamtannin B1 as a trimer by about 40% within 8 h of incubation. Hydroxylated phenolic compounds were quantified as degradation products. In addition, two yet unknown catabolites were identified, and the structures were elucidated by Fourier transform mass spectrometry.

Mycotoxins are secondary plant metabolites that have been found to cause severe diseases in humans and livestock. Exposure can take place on a daily basis since mycotoxins can be found not only in food, animal food, and dietary supplements but also in materials used in buildings. For this work, the Alternaria toxins alternariol (AOH) and alternariol methyl ether (AME) are chosen as representatives for this relevant compound class and are investigated regarding their oxidative phase I metabolism using a combination of electrochemical (EC) oxidation and high-resolution electrospray ionization mass spectrometry (HR-ESI-MS). This previously established method has been proven to be a valuable tool for the electrochemical simulation of certain phase I metabolic reactions. A comparison of the electrochemically generated products with those formed during microsomal incubation demonstrates the potential of the method for the successful prediction of the main phase I metabolic reactions of mycotoxins. It can thus find use as a supportive method in the elucidation of the metabolic pathways of various mycotoxins.

For toxicological studies of B-type fumonisin in animals, high amounts of pure fumonisins are needed. In the past, several methods for the isolation and purification of fumonisins have been published, stating the problem of high losses of fumonisins during chromatography on solid phases. In this manuscript we describe a new approach based on liquid-liquid partition techniques using centrifugal partition chromatography in combination with ion exchange chromatography for the large-scale isolation of B-type fumonisins with good recovery rates, minimizing losses of fumonisins during the purification. A batch of cultures grown on solid media of 2 kg maize yields approximately 1 g of pure fumonisins with a purity of >98%.