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Compared with those of berries, the stems and leaves of the genus Vaccinium are important and underestimated sources of polyphenols with high antioxidant activity. In the course of this work, aqueous methanol extracts of the aerial parts of common bilberry (Vaccinium myrtillus L.) and bog bilberry (Vaccinium uliginosum L.) were studied to analyze the component compositions of their biologically active polyphenolic compounds. The aqueous methanol fractions of the stems and leaves of the studied samples contained 8.7 and 4.6% extractives, respectively, and were comparable in total polyphenol content, but presented significant differences in antioxidant activity. The identification of polyphenolic compounds was carried out via the following two-stage analytical procedure: (1) non-targeted screening of dominant structures via the 2D NMR method and (2) analysis of HPLC-HRMS data via the scanning of precursor ions for a specific ion. A total of 56 phenolic compounds were identified, including the glycosides quercetin, proanthocyanidins, and catechins, as well as various conjugates of caffeic and p-coumaric acids, including iridoids. Some of the latter, such as caffeoyl and p-coumaroyl hydroxydihydromonotropein, as well as a number of lignan glycosides, were described for the first time in V. uliginósum and V. myrtillus. [ABSTRACT FROM AUTHOR]

Among N‐((2‐substituted)benzyl)phenylethanamines, N‐(2‐hydroxybenzyl)phenylethanamines are a special type of compounds which are thermolabile and degrade in the course of analysis by means of gas chromatography–mass spectrometry (GC–MS). This can lead to substantial errors, in the identification of legally controlled compounds of this series containing methoxy groups at positions 2 and 5 of the benzene ring of the phenylethyl fragment by GC–MS, which is commonly used in forensic and toxicological laboratories. Exemplified by the five isomeric 2‐(dimethoxyphenyl)‐N‐(2‐hydroxybenzyl)ethanamines, it was shown that their derivatization with trifluoroacetic anhydride (same as in the case of the N‐(2‐methoxybenzyl)‐, N‐(2‐fluorobenzyl)‐, N‐(2‐chlorobenzyl)‐, and N‐(2‐bromobenzyl)substitutes phenylethanamines [NBOMe, NBF, NBCl, and NBBr, respectively] series described earlier) results in only one product, N‐monosubstituted derivative, for each positional isomer within a series, which makes it possible to reliably identify each compound by the GC–MS method. In addition, chromatographic conditions for sufficient separation of trifluoroacetyl derivatives of these positional isomers of the NBOH series in 25 min are proposed, which is an important aspect for analysis in forensic laboratories engaged in the determination of narcotic drugs and new psychoactive substances. As an alternative approach, a method for identifying positional isomers of the NBOH series by the high‐performance liquid chromatography–high‐resolution mass spectrometry (HPLC‐HRMS) method without derivatization is proposed. [ABSTRACT FROM AUTHOR]

The objective of this study was to analyze the chemical profile of extracts from different fruit parts of the perennial arborescent cactus Opuntia leucotricha by applying ultra-high-performance liquid chromatography–high-resolution mass spectrometry (UHPLC-HRMS) and to evaluate their biological properties (antioxidant and enzyme inhibitory capacities). Extracts were obtained from the fruit pulp (without or with seeds), seeds, and peel by ultrasound-assisted extraction (UAE) using the conventional solvent methanol 50% and two Natural Deep Eutectic Solvents (NADESs) (glycerol:urea, 1:1 and citric acid:sorbitol, 1:2). A total of 33 compounds were identified, including phenolics, fatty acids, and others. Phenolic acids were the most abundant class of phenolics identified in all fruit parts, with the highest concentration observed in the methanol extracts from peel (593.02 µg/gDW), followed by seed-containing pulp (69.03 µg/gDW), pulp (57.83 µg/gDW), and seeds (39.97 µg/gDW). The second most effective extractant was NADES 1 (glycerol:urea, 1:1), which was also successful in extracting compounds with antioxidant capacity. Overall, the extracts demonstrated considerable enzyme inhibitory activities, with the greatest effects observed against α-amylase and α-glucosidase. The results indicate that O. leucotricha fruits could be a promising source of bioactive compounds, and NADES a viable alternative to organic solvents for their industrial exploitation. [ABSTRACT FROM AUTHOR]

The World Health Organization (WHO) promotes research aimed at developing new drugs from natural compounds. Fungi are important producers of bioactive molecules, and they are often effective against other fungi and/or bacteria and are thus a potential source of new antibiotics. Basidiomycota crude extracts, which have previously been proven to be active against Pseudomonas aeruginosa ATCC27853, were subjected to liquid chromatographic separation by RP-18, leading to six macro-fractions for each fungal extract. The various fractions were tested for their bioactivities against P. aeruginosa ATCC27853, and ten of them were characterized by HPLC-HRMS and NMR. Further chromatographic separations were performed for a few selected macro-fractions, yielding seven pure compounds. Bioactivity was mainly found in the lipophilic fractions containing fatty acids and their derivatives, such as hydroxy or keto C-18 unsaturated acids, and in various complex lipids, such as glycolipids and related compounds. More hydrophilic molecules, such as GABA, phenethylamine, two chromogenic anthraquinoids and pistillarin, were also isolated, and their antibacterial activities were recorded. The novelties of this research are as follows: (i) the genera Cortinarius and Mycena have never been investigated before for the synthesis of antibiotic compounds; (ii) the molecules produced by these genera are known, but their production has never been reported in the investigated fungi; (iii) the determination of bacterial siderophore synthesis inhibition by certain compounds from Cortinarius and Mycena. [ABSTRACT FROM AUTHOR]

Compared with those of berries, the stems and leaves of the genus Vaccinium are important and underestimated sources of polyphenols with high antioxidant activity. In the course of this work, aqueous methanol extracts of the aerial parts of common bilberry (Vaccinium myrtillus L.) and bog bilberry (Vaccinium uliginosum L.) were studied to analyze the component compositions of their biologically active polyphenolic compounds. The aqueous methanol fractions of the stems and leaves of the studied samples contained 8.7 and 4.6% extractives, respectively, and were comparable in total polyphenol content, but presented significant differences in antioxidant activity. The identification of polyphenolic compounds was carried out via the following two-stage analytical procedure: (1) non-targeted screening of dominant structures via the 2D NMR method and (2) analysis of HPLC-HRMS data via the scanning of precursor ions for a specific ion. A total of 56 phenolic compounds were identified, including the glycosides quercetin, proanthocyanidins, and catechins, as well as various conjugates of caffeic and p-coumaric acids, including iridoids. Some of the latter, such as caffeoyl and p-coumaroyl hydroxydihydromonotropein, as well as a number of lignan glycosides, were described for the first time in V. uliginósum and V. myrtillus.

• A data processing platform, HDPairFinder, was developed to automatically recognize H/D isotope labeled chemicals in HPLC-HRMS data. • Cross-correlation was proposed to address the RT shift caused by the deuterium isotopic effect. • A suite of bioinformatic algorithms was incorporated to effectively remove false positive features. • AMINES, a library of over 38000 amino-containing chemicals, was constructed to facilitate compound annotation. • Over 1000 highly confident H/D-labeled amino-containing compounds can be identified from the data of environmental water samples. The combination of hydrogen/deuterium (H/D) formaldehyde-based isotopic methyl labeling with solid-phase extraction and high-performance liquid chromatography–high resolution mass spectrometry (HPLC-HRMS) is a powerful analytical solution for nontargeted analysis of trace-level amino-containing chemicals in water samples. Given the huge amount of chemical information generated in HPLC-HRMS analysis, identifying all possible H/D-labeled amino chemicals presents a significant challenge in data processing. To address this, we designed a streamlined data processing pipeline that can automatically extract H/D-labeled amino chemicals from the raw HPLC-HRMS data with high accuracy and efficiency. First, we developed a cross-correlation algorithm to correct the retention time shift resulting from deuterium isotopic effects, which enables reliable pairing of H- and D-labeled peaks. Second, we implemented several bioinformatic solutions to remove false chemical features generated by in-source fragmentation, salt adduction, and natural 13C isotopes. Third, we used a data mining strategy to construct the AMINES library that consists of over 38,000 structure-disjointed primary and secondary amines to facilitate putative compound annotation. Finally, we integrated these modules into a freely available R program, HDPairFinder.R. The rationale of each module was justified and its performance tested using experimental H/D-labeled chemical standards and authentic water samples. We further demonstrated the application of HDPairFinder to effectively extract N-containing contaminants, thus enabling the monitoring of changes of primary and secondary N-compounds in authentic water samples. HDPairFinder is a reliable bioinformatic tool for rapid processing of H/D isotopic methyl labeling-based nontargeted analysis of water samples, and will facilitate a better understanding of N-containing chemical compounds in water. [Display omitted] [ABSTRACT FROM AUTHOR]

Alismatis Rhizoma (AR) is a crucial substance for discovering new triterpenoids to address hyperlipidemia and obesity. Currently, approximately 120 triterpenoids have been identified in AR, making the discovery of new triterpenoids increasingly challenging. Thus, based on the advantages of HPLC-HRMS, it was utilized to identify both reported and new triterpenoids, and then in-silico analysis was employed to predict the functions of these new triterpenoids. Twenty reported triterpenoids and four new triterpenoids (25-methoxy-16-oxo-11-anhydroalisol A, 25-methoxy-16-oxo-alisol A, 25-methoxy-16-oxo-alisol A 23-acetate, and 25-methoxy-16-oxo-alisol A 24-acetate) from AR were identified using HPLC-HRMS, and then KEGG analysis suggested four new triterpenoids might be activated the PPAR signaling pathway to relieve hyperlipemia. The results of PPI and molecular docking indicated PPARA might be the key targets for anti-hyperlipidemia of four new triterpenoids, of which 25-methoxy-16-oxo-11-anhydroalisol A has better binding activity with PPARA. Additionally, 25-methoxy-16-oxo-11-anhydroalisol A has more potential as a candidate drug because of its better absorption, distribution, metabolism, excretion, and lower toxicity. Hence, our findings proved there are new triterpenoids with anti-hyperlipidemia medicinal potential in AR, thereby guiding the direction of future works and reducing the consumption of time and financial resources.

The objective of this study was to analyze the chemical profile of extracts from different fruit parts of the perennial arborescent cactus Opuntia leucotricha by applying ultra-high-performance liquid chromatography–high-resolution mass spectrometry (UHPLC-HRMS) and to evaluate their biological properties (antioxidant and enzyme inhibitory capacities). Extracts were obtained from the fruit pulp (without or with seeds), seeds, and peel by ultrasound-assisted extraction (UAE) using the conventional solvent methanol 50% and two Natural Deep Eutectic Solvents (NADESs) (glycerol:urea, 1:1 and citric acid:sorbitol, 1:2). A total of 33 compounds were identified, including phenolics, fatty acids, and others. Phenolic acids were the most abundant class of phenolics identified in all fruit parts, with the highest concentration observed in the methanol extracts from peel (593.02 µg/gDW), followed by seed-containing pulp (69.03 µg/gDW), pulp (57.83 µg/gDW), and seeds (39.97 µg/gDW). The second most effective extractant was NADES 1 (glycerol:urea, 1:1), which was also successful in extracting compounds with antioxidant capacity. Overall, the extracts demonstrated considerable enzyme inhibitory activities, with the greatest effects observed against α-amylase and α-glucosidase. The results indicate that O. leucotricha fruits could be a promising source of bioactive compounds, and NADES a viable alternative to organic solvents for their industrial exploitation.

Eggs play an important role in a balanced diet; however, the European Food Safety Authority (EFSA) recognizes eggs as a major source of poly and per-fluoroalkyl substances (PFASs). In this study, the presence of PFASs was analysed in eggs produced by hens from Northern Italian regions, a PFASs-contaminated area. Sixty-five samples were analysed by high-performance liquid chromatography coupled with high-resolution mass spectrometry. The greatest presence of PFASs was found in eggs from Veneto and Emilia Romagna, and the most detected PFASs were perfluorobutanoic acid (PFBA) and perfluorooctanesulfonic acid (PFOS) (mean concentrations 0.30 ± 0.15 and 0.05 ± 0.00 ng g−1). Considering the most recent updates for the sum of the main four PFASs, the highest concentration found in the analysed samples was 0.05 ng g−1, well below the maximum limit set by the European Union. The PFAS intake evaluation confirmed that egg consumption does not represent a risk for Italian consumers. [ABSTRACT FROM AUTHOR]

The World Health Organization (WHO) promotes research aimed at developing new drugs from natural compounds. Fungi are important producers of bioactive molecules, and they are often effective against other fungi and/or bacteria and are thus a potential source of new antibiotics. Basidiomycota crude extracts, which have previously been proven to be active against Pseudomonas aeruginosa ATCC27853, were subjected to liquid chromatographic separation by RP-18, leading to six macro-fractions for each fungal extract. The various fractions were tested for their bioactivities against P. aeruginosa ATCC27853, and ten of them were characterized by HPLC-HRMS and NMR. Further chromatographic separations were performed for a few selected macro-fractions, yielding seven pure compounds. Bioactivity was mainly found in the lipophilic fractions containing fatty acids and their derivatives, such as hydroxy or keto C-18 unsaturated acids, and in various complex lipids, such as glycolipids and related compounds. More hydrophilic molecules, such as GABA, phenethylamine, two chromogenic anthraquinoids and pistillarin, were also isolated, and their antibacterial activities were recorded. The novelties of this research are as follows: (i) the genera Cortinarius and Mycena have never been investigated before for the synthesis of antibiotic compounds; (ii) the molecules produced by these genera are known, but their production has never been reported in the investigated fungi; (iii) the determination of bacterial siderophore synthesis inhibition by certain compounds from Cortinarius and Mycena.

The Covid-19 pandemic has affected the global population since 2019. The rapid development and approval of vaccines has brought relief. Yet, effective cures are still being researched. Even if the pandemic situation may end, SARS-CoV-2 will remain and, thus, continued application of the drugs will lead to emissions of the active ingredients into the aquatic environment, as with other anthropogenic micropollutants. However, a general method for trace analysis of antiviral drugs is still missing. To this purpose, favipiravir, remdesivir, its active metabolite GS-441524, molnupiravir and its active metabolite EIDD-1931 were selected as representative analytes. A method was developed based on solid phase extraction and high-performance liquid chromatography combined with electrospray ionization quadrupole time-of-flight high-resolution mass spectrometry. Optimization comprised the choice of chromatographic columns, elution gradient, mass spectrometry and tandem mass spectrometry parameters. Solid phase extraction proved suitable for increase in limits of detection and quantitation. amelioration of the limits of detection and quantitation. Matrix effects were investigated applying the optimized method to a wastewater sample with added virustatics. All five compounds could be separated with reversed phase chromatography, whereas EIDD-1931 profited from hydrophilic interaction liquid chromatography. The optimized method yielded limits of detection and quantification of 2.1·10-1, 6.9·10-1 µg·L-1 for favipiravir, 1.8·10-3, 5.5·10-3 µg·L-1 for remdesivir, 1.9·10-3, 7.6·10-3 µg·L-1 for GS-441524, 2.9·10-3, 8.7·10-3 µg·L-1 for molnupiravir, and 1.3·10-1, 3.8·10-1 µg·L-1 for EIDD 1931. The method was first applied to compound stability testing at pH 2.8 and 9.7. At pH 2.8, remdesivir, GS-441524 and molnupiravir proved stable, whereas about 14% of EIDD-1931 and favipiravir were degraded. All five antiviral compounds were almost completely decomposed at pH 9.7. The application of the method was further demonstrated for potential transformation product detection on favipiravir ozonation monitoring. [ABSTRACT FROM AUTHOR]

An approach to the highly sensitive and selective determination of the bromine-containing antiviral drug umifenovir (Arbidol) and its metabolites in natural and waste water, activated sludge, and bottom sediments by chromatography-mass spectrometry based on a combination of two techniques– inductively coupled plasma mass spectrometry (ICP MS) and electrospray ionization high-resolution mass spectrometry (ESI HRMS) is developed. Reversed-phase chromatographic separation and detection based on ESI HRMS provide the reliable detection and identification of analytes in complex matrices, while the use of ICP-MS with 79Br signal detection makes it possible to exclude matrix effects and use a single analytical standard for quantitative analysis. The use of solid-phase extraction and pressurized liquid extraction as sample preparation methods made it possible to achieve limits of detection at a level of 0.2 ng/L and 2 µg/kg for liquid and solid samples, respectively. The developed approach was successfully tested in the analysis of real samples. It is shown that the concentrations of analytes in urban wastewaters are in the range 4.4–260 ng/L. The highest concentration (up to 3.7 mg/kg) is characteristic of activated sludge, which acts as an effective sorbent for umifenovir and its transformation products. [ABSTRACT FROM AUTHOR]

Tetracycline antibiotics found in waters worldwide pose a tremendous ecological and human health hazard due to bacterial resistances. Various processes are currently investigated to eliminate such anthropogenic micropollutants, among them advanced oxidation processes, where hydroxyl radicals cause disintegration of many organic substances. For mechanistic understanding and optimization for potential in-field use, kinetic descriptions and chemical reaction knowledge are important. Structural identification, quantitation and kinetic description of the substances are investigated via a univariate method, i.e. high-performance liquid-chromatography coupled with mass spectrometry and curve-fitting, and a multivariate method, i.e. absorption spectroscopy and curve resolution-alternating least squares fitting. The latter represented a fast, non-laborious analytical method. The univariate approach revealed four known and two new transformation products. First-order kinetics with follow-up reactions were observed. The univariate method yielded rate constants of about 0.33 min−1 for the degradation of both tetracyclines and distinct rate constants for transformation products, while rate constants of about 0.22 and 0.27 min−1 and an overall rate constant for non-identified transformation products were obtained from multivariate analysis due to the insufficient discriminatory power. Structural characterization, fast and easy kinetic parameter determination of photoinduced degradation may contribute to optimize advanced oxidation processes for the removal of antibiotics from waste water. [ABSTRACT FROM AUTHOR]

The banana is a tropical fruit characterized by its composition of healthy and nutritional compounds. This fruit is part of traditional Ecuadorian gastronomy, being consumed in a wide variety of ways. In this context, unripe Red Dacca banana samples and those submitted to different traditional Ecuadorian heating treatments (boiling, roasting, and baking) were evaluated to profile their phenolic content by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) and the antioxidant activity by ORAC, ABTS, and DPPH assays. A total of sixty-eight phenolic compounds were identified or tentatively identified in raw banana and treated samples, highlighting the content in flavonoids (flavan-3-ols with 88.33% and flavonols with 3.24%) followed by the hydroxybenzoic acid family (5.44%) in raw banana samples. The total phenolic compound content significantly decreased for all the elaborations evaluated, specifically from 442.12 mg/100 g DW in fresh bananas to 338.60 mg/100 g DW in boiled (23.41%), 243.63 mg/100 g DW in roasted (44.90%), and 109.85 mg/100 g DW in baked samples (75.15%). Flavan-3-ols and flavonols were the phenolic groups most affected by the heating treatments, while flavanones and hydroxybenzoic acids showed higher stability against the heating treatments, especially the boiled and roasted samples. In general, the decrease in phenolic compounds corresponded with a decline in antioxidant activity, evaluated by different methods, especially in baked samples. The results obtained from PCA studies confirmed that the impact of heating on the composition of some phenolic compounds was different depending on the technique used. In general, the heating processes applied to the banana samples induced phytochemical modifications. Even so, they remain an important source of bioactive compounds for consumers. [ABSTRACT FROM AUTHOR]

The introduction of synthetic dyes completely changed the industrial production and use of colorants for art materials. From the synthesis of the first synthetic dye, mauveine, in 1856 until today, artists have enjoyed a wider range of colors and selection of chemical properties than was ever available before. However, the introduction of synthetic dyes introduced a wider variety and increased the complexity of the chemical structures of marketed dyes. This work looks towards the analysis of synthetically dyed objects in heritage collections, applying an extraction protocol based on the use of ammonia, which is considered favorable for natural anthraquinone dyes but has never before been applied to acid synthetic dyes. This work also presents an innovative cleanup step based on the use of an ion pair dispersive liquid–liquid microextraction for the purification and preconcentration of historical synthetic dyes before analysis. This approach was adapted from food science analysis and is applied to synthetic dyes in heritage science for the first time in this paper. The results showed adequate recovery of analytes and allowed for the ammonia-based extraction method to be applied successfully to 15 samples of suspected azo dyes from the Azienda Coloranti Nazionali e Affini (ACNA) synthetic dye collection, identified through untargeted HPLC-HRMS analyses. [ABSTRACT FROM AUTHOR]

This study describes a multistage methodology to detect minute amounts of tetrodotoxin in fishes, a plan that may be broadened to include other marine organisms. This methodology was applied to porcupinefish (Diodon hystrix) collected in Punta Chiquirín, El Salvador. A three-stage approach along with post-acquisition processing was employed, to wit: (a) Sample screening by selected reaction monitoring (HPLC-MS/MS-SRM) analyses to quickly identify possible toxin presence via a LC/MS/MS API 3200 system with a triple quadrupole; (b) HPLC-HRFTMS-full scan analyses using an ion trap-Orbitrap spectrometer combined with an MZmine 2-enhanced dereplication-like workflow to collect high-resolution mass spectra; and (c) HPLC-HRMS2 analyses. This is the first time tetrodotoxin has been reported in D. hystrix specimens collected in El Salvador. [ABSTRACT FROM AUTHOR]

Introduction: Viticis Fructus is the dried ripe fruit of Vitex trifolia L. (VTF) or V. trifolia subsp. litoralis Steenis (VTLF). Different botanical sources of the same herbal medicines may have different clinical efficacies, but few studies have reported the comparative identification of VTF and VTLF. Objectives: To establish a high‐performance liquid chromatography (HPLC) method for the simultaneous assay of 11 constituents in Viticis Fructus, to compare the chemical compositions of VTF and VTLF, and to identify chemical markers for the discrimination and quality evaluation of the two botanical origins of Viticis Fructus. Methodology: An HPLC‐diode array detection (DAD)‐high‐resolution mass spectrometry (HRMS) method was developed for the simultaneous separation and quantification of 11 constituents in 21 batches of Viticis Fructus samples from different sources in China. Moreover, chemometrics were performed to compare and discriminate VTF and VTLF samples. Results: The results from 11 batches of VTF and 10 batches of VTLF were compared for 11 components, of which 3,4‐dicaffeoylquinic acid and 3,5‐dicaffeoylquinic acid were identified and quantified in Viticis Fructus for the first time. The quantitative analysis showed significantly higher chlorogenic acid and casticin contents in VTLF than in VTF, and the chemometric analysis indicated that chlorogenic acid and casticin were responsible for the significant differences between VTF and VTLF; these two compounds might be used as chemical markers to distinguish the two original plant sources of Viticis Fructus. Conclusions: The present work provides useful information for understanding the chemical differences between VTF and VTLF. This work also provides feasible methods for the quality evaluation and discrimination of herbal medicines originating from multiple botanical sources. The present study provides useful information for understanding the chemical differences between two botanical origins of Viticis Fructus. The content of 11 components of Viticis Fructus was determined, of which 3,4‐dicaffeoylquinic acid and 3,5‐dicaffeoylquinic acid were identified and quantified in Viticis Fructus for the first time. The chemometric analysis indicated that chlorogenic acid and casticin were responsible for the significant differences between two botanical origins of Viticis Fructus. [ABSTRACT FROM AUTHOR]

The fluoroquinolone ciprofloxacin occurs worldwide in the aquatic environment and has therefore been listed on the 3rd European union watchlist for monitoring. To eliminate sewage and wastewater treatment plants as entry pathways, advanced oxidation processes have been intensely researched. Hence, photolysis at different pH ranges was studied for its capacity to eradicate ciprofloxacin. High-performance liquid chromatography coupled to high-resolution mass spectrometry was used to identify the degradation products and to monitor all compounds. Ecotoxicity was assessed using quantitative structure-activity relationship analysis comprising the Ecological Structure Activity Relationships tool. Two degradation mechanisms were found active: the direct mechanism, i.e. degradation through ultraviolet absorption by the substance, and the indirect mechanism caused by hydroxyl radicals from water photolysis. The radical scavenger tert-butanol and pH variations revealed that the indirect mechanism predominated in general. The direct photo-induced degradation proceeded about 10 times slower. Products could be attributed to the mechanisms. Based on their chemical structures, all identified products were predicted less toxic by quantitative structure-activity relationship than ciprofloxacin. Mechanistic insight suggested that photo-induced advanced oxidation processes proved efficient for ciprofloxacin elimination when generating hydroxyl radicals. Compounds and pH range hampering their occurrence diminish the efficacy of elimination. [ABSTRACT FROM AUTHOR]

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Eggs play an important role in a balanced diet; however, the European Food Safety Authority (EFSA) recognizes eggs as a major source of poly and per-fluoroalkyl substances (PFASs). In this study, the presence of PFASs was analysed in eggs produced by hens from Northern Italian regions, a PFASs-contaminated area. Sixty-five samples were analysed by high-performance liquid chromatography coupled with high-resolution mass spectrometry. The greatest presence of PFASs was found in eggs from Veneto and Emilia Romagna, and the most detected PFASs were perfluorobutanoic acid (PFBA) and perfluorooctanesulfonic acid (PFOS) (mean concentrations 0.30 ± 0.15 and 0.05 ± 0.00 ng g−1). Considering the most recent updates for the sum of the main four PFASs, the highest concentration found in the analysed samples was 0.05 ng g−1, well below the maximum limit set by the European Union. The PFAS intake evaluation confirmed that egg consumption does not represent a risk for Italian consumers.

The introduction of synthetic dyes completely changed the industrial production and use of colorants for art materials. From the synthesis of the first synthetic dye, mauveine, in 1856 until today, artists have enjoyed a wider range of colors and selection of chemical properties than was ever available before. However, the introduction of synthetic dyes introduced a wider variety and increased the complexity of the chemical structures of marketed dyes. This work looks towards the analysis of synthetically dyed objects in heritage collections, applying an extraction protocol based on the use of ammonia, which is considered favorable for natural anthraquinone dyes but has never before been applied to acid synthetic dyes. This work also presents an innovative cleanup step based on the use of an ion pair dispersive liquid–liquid microextraction for the purification and preconcentration of historical synthetic dyes before analysis. This approach was adapted from food science analysis and is applied to synthetic dyes in heritage science for the first time in this paper. The results showed adequate recovery of analytes and allowed for the ammonia-based extraction method to be applied successfully to 15 samples of suspected azo dyes from the Azienda Coloranti Nazionali e Affini (ACNA) synthetic dye collection, identified through untargeted HPLC-HRMS analyses.

Environmental impact of toxic and corrosive synthesis waste generated by the clandestine production of amphetamine-type stimulants (ATS) is a known problem, which can even result in malfunction of wastewater treatment plants (WWTPs), e. g. in case of illegal discharge of large amounts of highly acidic chemical waste into the sewage system, which is generated in clandestine labs converting pre-precursors to the most prevalent ATS precursor benzyl methyl ketone (BMK). ATS synthesis-specific substances, precursor chemicals, intermediates and route-specific by-products may also support wastewater-based epidemiology (WBE) studies to explain abnormally high loads of drugs in wastewater by distinguishing whether these high loads were caused by consumption or disposal of synthesis waste into the sewage system. Although some of these synthesis-specific substances can be detected in traces in the final form of consumption of the product, these substances are removed from the drug product to a large extent during cleaning steps, e.g. the frequently applied steam distillation step to purify the amphetamine raw base after clandestine Leuckart synthesis. In contrast, these synthesis-specific by-products are very prominent in chemical synthesis wastes, whereby their detection in wastewater would prove a disposal of synthesis wastes instead of excretion after drug product consumption. As a prerequisite, such substances need to exhibit a certain chemical and biological stability in wastewater and, therefore, lab-scale experiments were performed in a mixture of WWTP effluent and activated sludge. Fourteen selected synthesis-specific substances, all related to the production of ATS, comprised pre-precursors (e.g. α-phenylacetoacetonitrile (APAAN) or α-phenylacetoacetamide (APAA)), precursors (e.g. BMK), intermediates (e.g. N-formylamphetamine (NFA)), synthesis by-products (e.g. N,N-di-(β-phenylisopropyl)amine (DPIA)) and final products (e.g. amphetamine (AMPH)). Stability of test substances was evaluated by targeted HPLC-MS/MS analysis, while HPLC-HRMS techniques were used for the identification of transformation products (TPs) of substances that have undergone primary degradation. All substances were detectable for five days minimum and seven out of 14 substances underwent at least primary degradation. A total of three TPs were identified: TP164 was formed by oxidation of ephedrine (EPHE) and was further transformed after maximum formation, while TP180-1 and TP180-2 were formed by reduction of APAA and both remained stable. This is the first study investigating the stability of ATS synthesis-specific substances in wastewater demonstrating sufficient stability for wastewater monitoring studies.

The dinoflagellate genus Prorocentrum includes several harmful toxigenic species, predominantly benthic ones. In the past, fast-acting toxicity in mice has been observed in extracts of the epibenthic species P. borbonicum, with the finding of two compounds termed as borbotoxins-A and -B. The presence of palytoxin-like compounds was also suggested from electrophysiological experiments. In the present study, a strain of P. borbonicum was isolated in the continental coast of Colombian Caribbean, in seagrass beds of Thalassia testudinum in Bonito Gordo, Tayrona National Natural Park (PNNT). The morphological and molecular characteristics were consistent with the original and former descriptions for this species. Typical haemolytic activity due to palytoxin was confirmed in P. borbonicum extracts in presence of ouabain, the toxin contents being estimated as 1.9 pg palytoxin equivalents cell-1. HPLC-HRMS analyses of these extracts unambiguously identified the presence of borbotoxins and 42-hidroxy-palytoxin (42-OH-PLTX). This is the first report of palytoxin-like compounds in another dinoflagellate genus than Ostreopsis and the first record of P. borbonicum in Colombia and the Caribbean region.

This study describes a multistage methodology to detect minute amounts of tetrodotoxin in fishes, a plan that may be broadened to include other marine organisms. This methodology was applied to porcupinefish (Diodon hystrix) collected in Punta Chiquirín, El Salvador. A three-stage approach along with post-acquisition processing was employed, to wit: (a) Sample screening by selected reaction monitoring (HPLC-MS/MS-SRM) analyses to quickly identify possible toxin presence via a LC/MS/MS API 3200 system with a triple quadrupole; (b) HPLC-HRFTMS-full scan analyses using an ion trap-Orbitrap spectrometer combined with an MZmine 2-enhanced dereplication-like workflow to collect high-resolution mass spectra; and (c) HPLC-HRMS2 analyses. This is the first time tetrodotoxin has been reported in D. hystrix specimens collected in El Salvador.

The winemaking process generates a large amount of waste which can be profitably converted into a resource. In this work, extracts from stalks, lees, and pomace of Magliocco canino cv (Vitis Vinifera L.) were obtained using ultrasounds. A comprehensive metabolomics profile was carried out by high-resolving power mass spectrometry hyphenated with liquid chromatography. Fifty-nine compounds were annotated and successively verified, bearing different chemical classes. Free amino acids were quantified in the different extracts. Distinction of glycosylated polyphenols vs their aglycones was accomplished by targeted and semi-targeted LC-MS methods; then selected polyphenolic biomarkers were quantified in the studied extracts. The antioxidant activity was evaluated in vitro in a human dermal fibroblasts assay, and the best antioxidant extract was used for the synthesis of an antioxidant DX conjugate by a grafting reaction, to obtain an innovative food ingredient endowed with improved antioxidant activity. The in - vitro endothelium-dependent vasorelaxation, recorded for both stalk and lees extracts could be exploited for the development of new antihypertensive nutraceuticals. [Display omitted] • Targeted and semi-targeted HRMS discriminate glycosylated polyphenols vs free ones. • Stalks and Lees ethanolic extracts exert valuable vasorelaxant activity. • Stalk extract showed remarkable antioxidant power in human dermal fibroblasts assay. • A biopolymer Dextran-based/stalk extract is a novel antioxidant food ingredient. [ABSTRACT FROM AUTHOR]

Hemp-sprouts are emerging as a new class of attractive functional food due to their numerous health benefits when compared to other sprout species. Indeed, the high content of beneficial components including polyphenols and flavonoids makes this type of food a promising and successful market. However, the available literature on this topic is limited and often conflicting as regards to the content of phytocannabinoids. High-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS) was applied in an untargeted metabolomics fashion to extracts of hemp seeds, sprouts and microgreens of nine different genotypes. Both unsupervised and supervised multivariate statistical analysis was performed to reveal variety-specific profiles of phytocannabinoids with surprisingly remarkable levels of phytocannabinoids even in chemotype V samples. Furthermore, a targeted HPLC-HRMS analysis was carried out for the quantitative determination of the major phytocannabinoids including CBDA, CBD, CBGA, CBG, CBCA, CBC, THCA, and trans -Δ9-THC. The last part of the study was focused on the evaluation of the enantiomeric composition of CBCA in hemp seeds, sprouts and microgreens in the different varieties by HPLC-CD (HPLC with online circular dichroism). Chiral analysis of CBCA showed a wide variability of its enantiomeric composition in the different varieties, thus contributing to the understanding of the intriguing stereochemical behavior of this compound in an early growth stage. However, further investigation is needed to determine the genetic factors responsible for the low enantiopurity of this compound. • Comprehensive phytocannabinoid profile was defined in hemp seeds, sprouts and microgreens. • Eight varieties and one accession of hemp from different chemotypes were analyzed. • The main carboxylated and decarboxylated phytocannabinoids were quantified by HPLC-HRMS. • Enantiomeric composition of CBDA, THCA and CBCA in hemp microgreens was investigated. [ABSTRACT FROM AUTHOR]

We report the isolation and characterization of a methylene bridged "dimer" of the opioid antagonist Naloxone, previously detected in experimental Buprenorphine-Naloxone oral films. This compound was found to form via an aldol addition followed by a condensation reaction under acidic conditions between two units of Naloxone and one unit of formaldehyde. HPLC-UV-HRMS analysis revealed the formation of three individual stereoisomers during this reaction, which were separately isolated using solid-phase extraction. These isomers were shown to freely react into one another in solvent, forming an equilibrium. The structure of the unknown compound was determined via HRMS spectrometry and 1D and 2D NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Background: Imidacloprid is among the most widely used insecticides and today is found in surface and ground water worldwide. It has been registered in the EU watchlist for monitoring. To prevent imidacloprid from entering water bodies, advanced oxidation processes (AOP) have been intensely researched. Photo-irradiation proved one of the most efficient methods to degrade and eliminate anthropogenic micropollutants from waters. The ecotoxicity assessment of photoinduced degradation and transformation products especially in the absence of reference standards is still heavily explored. Results: In this study, UVA and UVC irradiation in combination with titanium dioxide P25 as photocatalyst were investigated for their degrading and eliminating effects and effectiveness on imidacloprid. Humic acid was used as natural organic matter additive. High-performance liquid chromatography coupled with high-resolution mass spectrometry allowed to identify and monitor imidacloprid and its degradation intermediates yielding seven new structures and concentration–time (c–t) profiles. The correlation of structures and the application of radical scavengers and photocatalyst helped distinguish between direct photoinduced and indirect hydroxyl radical-induced degradation mechanisms. The identification of hydroxylated products and intermediates indicated the indirect degradation pathway, which could be suppressed by addition of a radical scavenger. The absence of hydroxylated intermediates and fragments pointed towards the direct absorption-induced degradation. Two degradations products were traced back to the direct mechanism, whereas all other products followed the indirect mechanism. The ecotoxicity of the identified compounds was assessed by quantitative structure–activity relationship (QSAR) analysis. Most products were predicted as less ecotoxic. Ecotoxicity equivalents (ETEs) were introduced allowing a classified ranking of the products and an assessment of the overall hazardous potential of the irradiated solution at a given moment. Generally, the number of hydroxyl substituents was inversely correlated to ecotoxicity. From the c-t curves, time-dependent ETE profiles were established. Conclusions: Structure elucidation and c-t profiles from liquid chromatography–high-resolution mass spectrometry allowed to distinguish between direct and indirect degradation mechanisms. Structure specific ecotoxicity assessment could be achieved through QSAR analysis. Ecotoxicity hazard was ranked based on ETEs. The time-dependent ETE profile proved suitable to reflect the effect of irradiation duration and allow to estimate the irradiation time required to eliminate ecotoxicity, which may be relevant for potential applications in wastewater treatment plants. [ABSTRACT FROM AUTHOR]

Summary: The primary source of perfluoroalkyl substances (PFASs) exposure is the diet, mainly fish. Seabass (Dicentrarchus labrax) and seabream (Sparus aurata) are among the most consumed sea fish in Italy. Fish from Northern Italy lakes like perch (Perca fluviatilis) is of particular importance in terms of consumption volume, while Mediterranean shad (Alosa agone) and European whitefish (Coregonus lavaretus) represent niche consumption. These species too could be a cause of consumer exposure to PFAS. The study investigated the presence of PFASs in the above‐mentioned fish species through LC‐HRMS analysis. Only PFBA and PFOS were found both in lake and sea fish while PFBS was found only in lake fish. The found concentrations were used to estimate intake of PFOS, the only detected molecule of the four discussed in the last EFSA report. The Tolerable Weekly Intake of 4.4 ng kg−1 b.w. per week was never exceeded also for the 99th percentile consumers. [ABSTRACT FROM AUTHOR]

HRMS analysis of a set of phosphine-boranes using RP-HPLC-HRMS has been performed using an acetonitrile/water mixture. The data show that all compounds undergo ionization under the measurement conditions to afford cations of [M-H]+, [2M-H]+, [2M-3H]+, [2M-5H]+ or [2M 6H]2+ type. A detailed analysis of their structures led to the conclusion that these species might act as carbonyl-group activators. [ABSTRACT FROM AUTHOR]

Introduction: The mulberry tree (Morus alba L.) is a prolific source of biologically active compounds. There is considerable growing interest in probing M. alba twigs as a source of disruptive antioxidant lead candidates for cosmetic skin care product development. Objective: An integrated approach using high‐performance liquid chromatography (HPLC) coupled with either chemical detection (CD) or high‐resolution mass spectrometry (HRMS) was applied to the hydroalcoholic extract of M. alba to detect and identify lead antioxidant compounds, respectively. Material and methods: The twigs were weighed, powdered and homogenized using a mill and the extract was prepared using 70% aqueous ethanol. The antioxidant metabolites were detected with HPLC coupled with CD (based on the ORAC assay) and their structural identification was carried out using a Q‐Exactive Orbitrap MS instrument. Results: Using this approach, 13 peaks were detected as overall contributors to the antioxidant activity of M. alba, i.e. mulberrosides (A & E), oxyresveratrol & its derivatives, moracin & its derivatives and a dihydroxy‐octadecadienoic acid, which together accounted for >90% of the antioxidant activity, highlighting the effectiveness of the integrated approach based on HPLC‐CD and HPLC‐HRMS. Additionally, a (3,4‐dimethoxyphenyl‐1‐O‐β‐D‐apiofuranosyl‐(1″ → 6′)‐O‐β‐D‐glucopyranoside was also discovered for the first time from the twig extract and is presented here. Conclusion: To our knowledge, this is the first report from M. alba twigs using HPLC‐CD and HPLC‐HRMS that identifies key compounds responsible for the antioxidant property of this native Chinese medicinal plant. The genus Morus consists of over 150 species belonging to the Moraceae family and among them, the Mulberry tree (e.g. Morus alba L.) continues to be a prolific source of biologically active compounds. The hydroalcoholic extract of the twigs was investigated with the aim to identify potential new antioxidant compounds which could be promising candidates for the development of cosmetic skin care product. An integrated approach using HPLC coupled with chemical detection (CD) and high resolution mass spectrometry (HRMS) was applied to detect and identify the antioxidant metabolites, respectively. Using this approach, 13 peaks were detected as contributors of the antioxidant activity. Eleven peaks were assigned to the known metabolites, namely, the Mulberosides (A and E), Oxyresveratrol derivatives, Moracin and its derivatives and a dihydroxy‐octadecadienoic acid derivative. These peaks contributed for41%, 9%, 17% and 20% of the antioxidant activity of the twig extract, respectively. Also, a new compound namely, 3,4‐dimethoxyphenyl‐1‐O‐β‐D‐apiofuranosyl‐(1"→6')‐O‐β‐D‐glucopyranoside was proposed and found to be responsible for 2% of the antioxidant activity. To our knowledge, this is the first report from Morus Alba twigs using HPLC‐CD and HPLC‐HRMS methodology that identifies key compounds responsible to the antioxidant property of this native Chinese medicinal plant. [ABSTRACT FROM AUTHOR]

The aim was to determine the absence of gluten in pet food samples marked as ‘grain-free’ and ‘gluten-free’ diets, to assess the reliability of manufacturer labelling of such products. A total of 15 diets labelled as grain- or gluten-free and 2 commercial diets containing wheat were sampled. An analytical procedure using high-pressure liquid chromatography coupled with mass spectrometry with high power of resolution was developed and applied to determine specific markers of wheat gluten. The results are expressed as mg of wheat flour type ‘00’ present in 1 g of feed. The quantification limit (LOQ) obtained in the flour for ion m/z 894.5043, z = 2, is 4 mg of flour per gram. In 14 out of the 15 samples from a grain- or gluten-free diet the quantifier ion signal was

Abstract The object of this study is a wide selection of dyed cotton and camelid samples from an important collection of 2000-year-old Paracas textiles, now at the Museo Nacional de Arqueología, Antropología e Historia del Perú (MNAAHP; Lima; Peru) and at the National Museum of World Culture (NMWC; Gothenburg; Sweden). The threads, chosen as representative of the whole palette, were selected from eighteen different textiles. A combined spectroscopic and spectrometric analytical approach was selected to characterize the organic and inorganic composition of this wide set of samples. In particular, technical photography was used to gain a general overview of the samples, X-ray fluorescence (XRF) was employed for identifying the mordants and mapping the elemental distribution in the threads, while liquid chromatography coupled with diode array detector and with high-resolution mass spectrometry (HPLC–DAD, HPLC–HRMS) were used for characterizing organic dye composition. This study provides fundamental information on the mordants or other inorganic auxiliaries used in the dyeing processes, rarely investigated up to now, and to the varieties of vegetal sources employed in Paracas textiles. The widening of the Andean dyestuff database is highly important not only to acquire knowledge on Paracas culture, but also to ease the dye characterization of archaeological textiles from the Peruvian region and South American area in general.

Introduction: European aspen (Populus tremula L.) knotwood contains large amounts of polyphenolic metabolites, mainly flavonoids, and can be considered as a promising industrial-scale source of valuable bioactive compounds. Valorization of knotwood extractives requires detailed information on their chemical composition and a relevant analytical methodology., Objective: This study proposes combined analytical strategy for non-targeted screening and identification of polyphenolic plant metabolites and is aimed at comprehensive characterization of knotwood extractives., Materials and Methods: Aspen knotwood acetone extract with determined antioxidant activity was an object of the study. Two-dimensional NMR spectroscopy with Structure Elucidator expert system was used for preliminary search of major components and specific structures. Liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS) with data-dependent MS/MS spectra acquisition was used as a complementary technique providing molecular-level characterization and identification of the detected metabolites., Results: Twenty-eight phenolic metabolites were found and identified. Among them, flavonoids, aromadendrin and naringenin, as well as their glycosylated derivatives (mainly O-glucosides) and methyl ethers, dominated. Taxifolin and its 7-O-glucoside were detected as minor components. Other detected compounds are represented by p-coumaric acid and its rutinoside and small amounts of glycosylated ferulic acid. Nineteen of the detected compounds were discovered in aspen knotwood for the first time. The results were confirmed by preparative isolation of individual compounds and NMR studies., Conclusion: The proposed analytical strategy based on 2D NMR and HPLC-HRMS can be considered a powerful tool in the analysis of plant extractives and allowed for the identification and semi-quantification of a large number of polyphenols in aspen knotwood., (© 2024 John Wiley & Sons Ltd.)

Polycyclic aromatic hydrocarbon (PAH) derivatives are mutagenic, carcinogenic, teratogenic and bioaccumulative pollutants. Investigations on hydroxylated PAHs (OH–PAHs) and Nitrated PAHs (NPAHs) in surface water are not enough. In this study, optimization and validation of an analytical method targeting nine kinds of OH–PAHs and one kind of nitrated PAH in environmental water samples are presented. The method was validated for linearity, limits of detection and quantification and recovery using spiked matrix. The linear range of most target compounds was 0.1–200 ng·mL−1 . However, the linear range of 1–hydroxy pyrene and 3–hydroxy benzo[a]pyrene started at 1 ng·mL−1 and the linear range of 1–hydroxy phenanthrene and 9–hydroxy benzo[a]pyrene could not reach 200 ng·mL−1 . All the correlation coefficients (r2 ) were over 0.997. The instrumental limits of detection (LOD) and method detection limits (MDL) ranged from 0.01 to 0.67 ng·mL−1 and 1.11 to 2.26 ng·L −1, respectively. With this method, a lake in Hebei province, China, were screened. Three kinds of target compounds were detected. The average concentration was around 2.5 ng·L −1, while the highest concentration reached 286.54 ng·L −1 . [ABSTRACT FROM AUTHOR]

Alismatis Rhizoma (AR) is a crucial substance for discovering new triterpenoids to address hyperlipidemia and obesity. Currently, approximately 120 triterpenoids have been identified in AR, making the discovery of new triterpenoids increasingly challenging. Thus, based on the advantages of HPLC-HRMS, it was utilized to identify both reported and new triterpenoids, and then in-silico analysis was employed to predict the functions of these new triterpenoids. Twenty reported triterpenoids and four new triterpenoids (25-methoxy-16-oxo-11-anhydroalisol A, 25-methoxy-16-oxo-alisol A, 25-methoxy-16-oxo-alisol A 23-acetate, and 25-methoxy-16-oxo-alisol A 24-acetate) from AR were identified using HPLC-HRMS, and then KEGG analysis suggested four new triterpenoids might be activated the PPAR signaling pathway to relieve hyperlipemia. The results of PPI and molecular docking indicated PPARA might be the key targets for anti-hyperlipidemia of four new triterpenoids, of which 25-methoxy-16-oxo-11-anhydroalisol A has better binding activity with PPARA. Additionally, 25-methoxy-16-oxo-11-anhydroalisol A has more potential as a candidate drug because of its better absorption, distribution, metabolism, excretion, and lower toxicity. Hence, our findings proved there are new triterpenoids with anti-hyperlipidemia medicinal potential in AR, thereby guiding the direction of future works and reducing the consumption of time and financial resources. [ABSTRACT FROM AUTHOR]

The fluoroquinolones ciprofloxacin, danofloxacin, enoxacin, levofloxacin and lomefloxacin, occur in water bodies worldwide and therefore pose a threat to the aquatic environment. Advanced purification procedures, such as electrochemical oxidation, may act as a remedy since they contribute to eliminating contaminants and prevent micropollutants from entering open water bodies. By electrochemical treatment in a micro-flow reactor equipped with a boron-doped diamond (BDD) electrode, the fluoroquinolones were efficiently degraded. A total of 15 new products were identified using high-performance high-resolution chromatography coupled with high-resolution multifragmentation mass spectrometry. The ecotoxicity of the emerging transformation products was estimated through in silico quantitative structure activity relationship analysis. Almost all transformation products were predicted less ecotoxic than the initial compounds. The fluoroquinolone degradation followed three major mechanisms depending on the voltage during the electrochemical oxidation. At approximately 1 V, the reactions started with the elimination of molecular hydrogen from the piperazine moiety. At approx. 1.25 V, methyl and methylene groups were eliminated. At 1.5 V, hydroxyl radicals, generated at the BDD electrode, led to substitution at the piperazine ring. This novel finding of the three reactions depending on voltage contributes to the mechanistic understanding of electrochemical oxidation as potential remedy against fluoroquinolones in the aquatic environment. [Display omitted] • BDD electrode-induced oxidation mechanisms were analyzed. • 15 new electrochemical oxidation products of fluoroquinolones were identified. • Hydrogen elimination, demethylation and hydroxyl substitution depended on voltage. • Ecotoxicity and pharmacological structure-activity map were correlated. • Electrochemical oxidation reduced the ecotoxicity of fluoroquinolones significantly. [ABSTRACT FROM AUTHOR]

The One Strain Many Compounds approach (OSMAC) is a powerful and comprehensive method that enables the chemo-diversity evaluation of microorganisms. This is achieved by variations of physicochemical cultivation parameters and by providing biotic and abiotic triggers to mimic microorganisms' natural environment in the lab. This approach can reactivate the silent biosynthetic routes of specific metabolites typically not biosynthesized under standard laboratory conditions. In the present study, we combined the OSMAC approach with static headspace solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS), high-performance liquid chromatography-high-resolution tandem mass spectrometry (HPLC-HRMSn), and matrix-assisted laser desorption/ionization high-resolution mass spectrometry imaging (MALDI-HRMSI) to evaluate the chemoecological significance of an apple root-associated endophytic Streptomyces pulveraceus strain ES16. We employed the OSMAC approach by cultivating the endophyte in six different media conditions and performed temporal studies over 14 days. Analysis of the volatilome revealed that only under stressful conditions associated with sporulation, endophytic S. pulveraceus ES16 produces geosmin, a volatile semiochemical known to attract the soil arthropods Collembola (springtails) specifically. Subsequently, targeted metabolic profiling revealed polycyclic tetramate macrolactams (PTMs) production by the endophyte under stress, which are bioactive against various pathogens. Additionally, the endophyte produced the iron-chelating siderophore, mirubactin, under the same conditions. The structures of the compounds were evaluated using HRMSn and by comparison with literature data. Finally, MALDI-HRMSI revealed the produced compounds' spatial-temporal distribution over 14 days. The compounds were profusely secreted into the medium after production. Our results indicate that endophytic S. pulveraceus ES16 can release the signal molecule geosmin, chemical defense compounds such as the PTMs, as well as the siderophore mirubactin into the host plant apoplast or the soil for ecologically meaningful purposes, which are discussed.

ABSTRACT: The presence of pharmaceutically active compounds (PhACs) in aquatic biota has been received much less attention than their presence in surface or waste water, and it was not until the mid-2000s, this gap started to be addressed. Here, we present SQUEEZe (Solid-liQuid Ultrasound Extraction with QuE Z-Sep/C18 as dispersive clean-up): a fast method for analysis of the trace 47 PhACs in fish muscle. Compared to our previously reported method [1], it offers alternatives with improvements in recoveries, number of analytes, sample volume and solvent used.The key aspects of this method are: • The ultrasound extraction was performed with acetonitrile/isopropanol 0.1% V/V formic acid. A clean-up step using QuE Z-Sep/C18 sorbents was employed to reduce lipid content of the extracts and further matrix effects in the detection of the analytes. • A HPLC separation with a Kinetex EVO C18 packed column in 11 min was optimized. MS and MS/MS data were collected using SWATH acquisition on the SCIEX X500R QTOF in (+)-ESI mode. • The method validated at 3 different concentrations levels: 5, 25 and 50 ng/g fish. It presented good intraday/interday reproducibility and absolute recoveries ≥ 60% for majority of analytes in composite homogenate muscle matrix of Squalius cephalus. • 10 out 47 compounds were detected in fish samples.

The aim was to determine the absence of gluten in pet food samples marked as 'grain-free' and 'gluten-free' diets, to assess the reliability of manufacturer labelling of such products. A total of 15 diets labelled as grain- or gluten-free and 2 commercial diets containing wheat were sampled. An analytical procedure using high-pressure liquid chromatography coupled with mass spectrometry with high power of resolution was developed and applied to determine specific markers of wheat gluten. The results are expressed as mg of wheat flour type '00' present in 1 g of feed. The quantification limit (LOQ) obtained in the flour for ion m/z 894.5043, z = 2, is 4 mg of flour per gram. In 14 out of the 15 samples from a grain- or gluten-free diet the quantifier ion signal was < LOQ, while in 1 out of the 15 samples 10 mg of flour/g feed were measured. Adverse reaction to gluten in dogs have been documented in certain breeds Gluten is tricky to detect and measure in pet food Contamination of gluten in pet food samples marked as 'grain-free' and 'gluten-free' diets An analytical procedure was developed using HPLC coupled with HRMS [ABSTRACT FROM AUTHOR]

A sensitive, selective, and quantitative method incorporating high-resolution mass spectrometry was developed for the determination of blood urea nitrogen (BUN) in bronchoalveolar lavage fluid. The method requires no sample cleanup or derivatization prior to analysis. High-performance liquid chromatography (HPLC) on a Hypersil Gold PFP column (100 × 3 mm, 3 μm particle size) connected to a C18 guard column was employed for a 10 min chromatographic separation. The detection of urea was achieved using a Thermo Scientific Q-Exactive Plus instrument incorporating selected ion monitoring (SIM) modes for the protonated adduct of urea. The urea analytical measuring range for the method is 0.047–17.134 mg/dL, resulting in a BUN analytical measurement range of 0.022–8.007 mg/dL, which allows for quantitation over 3 orders of magnitude (R2 = 0.999). In addition, the method is suitable for small sample volumes (15 μL) with a high level of accuracy, precision, and specificity. [ABSTRACT FROM AUTHOR]

The popularity of edible wild fruits has increased in industrialized countries due to their composition and positive effects. The aim of this study has been to characterize the polyphenolics and anthocyanins of black mulberry (Morus nigra L.), cornelian cherry (Cornus mas L.), elderberry (Sambucus nigra L.), hawthorn (Crataegus monogyna L.), lingonberry (Vaccinium vitis-idaea L.) and rose hip (Rosa canina L.) harvested in the north-west of Italy by means of HPLC-DAD-ESI HRMS in positive ion mode. Although there is an abundant amount of literature related to the polyphenolics of cultivated fruit, a new type of comparison has here been conducted between wild and cultivated fruits on their polyphenolic content. The HPLC-DAD-ESI HRMS method has detected 64 different polyphenolic molecules and it can be used to perform qualitative and quantitative analyses. Furthermore, the cornelian cherry and elderberry samples showed the highest polyphenolic compound levels. The quercetin glycosylated compounds showed the highest percentage of flavonols in most of the analyzed wild fruits. [ABSTRACT FROM AUTHOR]

Apple Replant Disease (ARD) is a significant problem in apple orchards that causes root tissue damage, stunted plant growth, and decline in fruit quality, size, and overall yield. Dysbiosis of apple root-associated microbiome and selective richness of Streptomyces species in the rhizosphere typically concurs root impairment associated with ARD. However, possible roles of Streptomyces secondary metabolites within these observations remain unstudied. Therefore, we employed the One Strain Many Compounds (OSMAC) approach coupled to high-performance liquid chromatography-high-resolution tandem mass spectrometry (HPLC-HRMSn) to evaluate the chemical ecology of an apple root-associated Streptomycesciscaucasicus strain GS2, temporally over 14 days. The chemical OSMAC approach comprised cultivation media alterations using six different media compositions, which led to the biosynthesis of the iron-chelated siderophores, ferrioxamines. The biological OSMAC approach was concomitantly applied by dual-culture cultivation for microorganismal interactions with an endophytic Streptomyces pulveraceus strain ES16 and the pathogen Cylindrocarpon olidum. This led to the modulation of ferrioxamines produced and further triggered biosynthesis of the unchelated siderophores, desferrioxamines. The structures of the compounds were elucidated using HRMSn and by comparison with the literature. We evaluated the dynamics of siderophore production under the combined influence of chemical and biological OSMAC triggers, temporally over 3, 7, and 14 days, to discern the strain’s siderophore-mediated chemical ecology. We discuss our results based on the plausible chemical implications of S. ciscaucasicus strain GS2 in the rhizosphere.

Pharmaceuticals are found in waterbodies worldwide. Conventional sewage treatment plants are often not able to eliminate these micropollutants. Hence, Advanced Oxidation Processes (AOPs) have been heavily investigated. Here, metoprolol is exposed to UV irradiation, hydrogen peroxide, and ozonation. Degradation was analyzed using chemical kinetics both for initial and secondary products. Photo-induced irradiation enhanced by hydrogen peroxide addition accelerated degradation more than ozonation, leading to complete elimination. Degradation and transformation products were identified by high-performance liquid-chromatography coupled to high-resolution higher-order mass spectrometry. The proposed structures allowed to apply Quantitative Structure-Activity Relationship (QSAR) analysis to predict ecotoxicity. Degradation products were generally associated with a lower ecotoxicological hazard to the aquatic environment according to OECD QSAR toolbox and VEGA. Comparison of potential structural isomers suggested forecasts may become more reliable with larger databases in the future.

• HPLC-HRMS conditions were selected for detection of MPA and AMPs in plant extracts. • The analytes' concentration in leaves didn't change for five weeks of plant growth. • Analytical characteristics were evaluated for determination of nerve agent markers. In this research an accumulation of nerve agent markers in garden cress (Lepidium sativum) as a model plant object was studied using LC-QTOF hybrid system. For the determination of methylphosphonic acid and alkyl methylphosphonates, which are specific markers of sarin, soman, VR and VX, simple and sensitive approach was developed. Direct analysis of aqueous extracts on the reversed phase column with polar endcapping allowed to achieve satisfactory retention factor for methylphosphonic acid, which has high polarity and is usually very weakly retained on the ordinary reversed phase columns. Application of the QTOF mass spectrometer with high mass resolution led to the increase in the accuracy of the conducted measurements. The HPLC-HRMS technique developed exclusively for this study has been validated for linearity, limit of detection, limit of quantification, precision, accuracy and matrix effect prior to the analysis of plant extract samples. Hydroponic growth model was employed to examine accumulation of nerve agent markers in garden cress. It was found that after elimination of nerve agent markers from the plant growth medium, garden cress was able to store these substances for at least 5 weeks providing high retrospectivity of the analysis. Moreover, during the cress growth, no metabolization of alkyl methylphosphonates was observed. This allows not only to reveal the fact of nerve agents release into environment, but also to define its type after a long period of time. [ABSTRACT FROM AUTHOR]

Abstract Quantification of a large number of compounds in the absence of authentic standards is always a challenge. More than 600 pyrrolizidine alkaloids (PAs) have been found in plants however only limited number of PAs standards are commercially available. As PAs are the most widely distributed natural plant toxins with threat to human health, risk assessment calls for quantitative analytical methods with a wide scope including PAs without available standards. In this study, a method was developed that allows simultaneous quantification of 12 PAs in the honey samples by using HPLC-HRMS with authentic standards. This method was further extended to screen for other potential PAs in the honey using multi-target screening combined with a quantitative prediction model in the cases that authentic PAs were not available. The prediction model was subsequently validated by cross-validation and additional PAs standards which were not included in the model. The maximum concentration prediction error was 50.8%. Graphical abstract Image 1 Highlights • Semi-quantification of other PAs by quantitative prediction model without standards. • Method validation for the analysis 12 PAs in honey. • Multi-target screening of potential PAs in honey samples. [ABSTRACT FROM AUTHOR]

Abstract Knowledge about translocation of plant protection products (PPP's) in plants is important to understand the uptake via the root system. Here we report the combination of analysis of tissue extracts by LC-HRMSn, autoradiography of 14C-labeled compounds and MALDI-MSI, which combine qualitative and quantitative information of chemical composition and the spatial distribution of PPP's and their metabolites in situ. Therefore, the uptake of the phenylamide fungicide metalaxyl was studied in tomato plants (Solanum lycopersicum) using a hydroponic system. The plants have been cultivated in perlite until the two-leaf stage and were transferred into the hydroponic test system afterwards. The radioactive labeled fungicide was readily taken up by the roots during the normal water consumption and radioactivity was translocated uniformly to the aboveground part of the tomato plants, while only small proportion of the applied radioactivity were observed in the roots. The distribution of metalaxyl after the plant uptake experiment in the primary roots where analyzed by a transversal tissue section in the zone of maturation. Metalaxyl is mainly localized in root xylem and in cortex located at the epidermis. With LC-HRMSn and radiochemical analyses of stem and leaf, no parent compound was detectable. Four polar metabolites were the main identified components of the residue and could be visualized by MALDI-imaging mass spectrometry. With these results we could show, that the fungicide metalaxyl is taken up by the plant via the roots during the regular water consumption and transported to xylem. Graphical abstract Image Highlights • Combination of LC-HRMSn, autoradiography of 14C-labeled compounds and MALDI-MSI. • Spatial distribution of Metalaxyl and its metabolites in situ. • Four metabolites were identified and could be visualized by MALDI-MSI. [ABSTRACT FROM AUTHOR]