•Deethylene-ENR was screened and detected in real fish samples for the first time.•A new method for residue analysis of ENR and its metabolites in fish was developed.•The detection rate of ENR ...metabolites in the analyzed crucian carp samples was high.•Deethylene-ENR may be of concern as a possible risk candidate in aquatic products.
The abuse of enrofloxacin (ENR) in aquaculture and the lack of monitoring of other metabolites except ciprofloxacin (CIP) may lead to unknown harmful effects on human health. In this study, ENR metabolites were screened in real fish samples based on ultrahigh-performance liquid chromatography coupled with Q-Orbitrap mass spectrometry combined with Compound Discoverer software, and another metabolite deethylene-ENR besides CIP was detected and identified for the first time. Correspondingly, a method for the determination of ENR and CIP and the semi-quantitative analysis of deethylene-ENR in aquatic products was established. Method validation illustrated that excellent linearity and satisfactory recoveries of analytes were obtained. Limits of detection of ENR and CIP were both 0.1 μg kg−1, and their limits of quantification both 1 μg kg−1. CIP and deethylene-ENR were detected in 12 of 14 ENR-positive fish samples, so deethylene-ENR should be of concern as a possible risk candidate in aquatic products.
A single workflow based on three approaches (target, suspected and non-target screening) using liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS) in data ...independent acquisition mode (DIA) was developed to assess the presence of emerging pollutants (EPs) in water and sediments from a Mediterranean River Basin. Identification of potential contaminants was based on mass accuracy, isotopic ratio pattern, theoretical fragmentation, and retention time using Waters UNIFI software. In the suspect screening against a library containing 2200 components, 68 contaminants were tentatively identified, 6 of which were confirmed and quantified with analytical standards. Non-target screening (NTS) required additional manual processing and the aid of an on-line database (ChemSpider) to tentatively identify compounds. Eprosartan, an antihypertensive drug not included in the library used for suspected screening, was confirmed and semi-quantified. The identification of Eprosartan proved the workflow to be functional for NTS. Target screening of 171 pesticides and 33 pharmaceuticals and personal care products (PPCPs) including the compounds confirmed using suspect (6) and non target (1) screening achieved monitoring of the most abundant contaminants from the head to the mouth of the Turia basin to establish their spatial distribution. QTOF-MS screening versatility with its high-resolution capability allows for a comprehensive assessment of EPs in the aquatic environment.
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•Suspected, non-target and target screening to establish River contamination profile•Identification 68 contaminants against a database of 2000 compounds•Non-target screening identifies additional compounds as Eprosartan•New findings enrich target screening up to 171 pesticides and 33 pharmaceuticals
•488 sphingolipid, glycerophospholipids, and glycolipids species were quantified.•TG was the highest levels in both standard and magnetic fermented goat milk.•Standard fermentation promoted the ...degradation of SM and SPH to Cer and HexCer.•Magnetic fermentation improved the TG, DG and HexCer and reduced Cer yield.•Magnetic stimulation may be a promising method for goat milk fermentation.
Standard fermentation (SF) mainly affected the metabolism of glycerophospholipid and sphingolipid, and increased the total lipid content of goat milk. Content of total lipid was decreased by magnetic fermentation compared with SF, mainly due to triacylglycerol and diacylglycerol. Comprehensive characteristic of lipids dynamic changes during standard and magnetic fermentation was performed using high-throughput quantitative lipidomics. Totally, 488 lipid molecular species covering 12 subclasses were detected, and triacylglycerol was the highest levels, followed by diacylglycerol and phosphoethanolamine in the whole fermentation stage. Specifically, except for ceramide and simple Glc series, the content of all polar lipids in SF was dropped and neutral lipids subjoined. Compared with SF, the decrease of triacylglycerol (1752.47 to 784.78 μg/mL), diacylglycerol (60.36 to 24.89 μg/mL) and simple Glc series (4.36 to 2.40 μg/mL) were observed, while ceramide (6.54 to 25.87 μg/mL) increased, suggesting magnetic fermentation as effective approach to potentially improve the nutritional of goat milk.
Peatlands are among the largest natural sources of atmospheric methane (CH4) worldwide. Microbial processes play a key role in regulating CH4 emissions from peatland ecosystems, yet the complex ...interplay between soil substrates and microbial communities in controlling CH4 emissions as a function of global change remains unclear. Herein, we performed an integrated analysis of multi‐omics data sets to provide a comprehensive understanding of the molecular processes driving changes in greenhouse gas (GHG) emissions in peatland ecosystems with increasing temperature and sulfate deposition in a laboratory incubation study. We sought to first investigate how increasing temperatures (4, 21, and 35°C) impact soil microbiome–metabolome interactions; then explore the competition between methanogens and sulfate‐reducing bacteria (SRBs) with increasing sulfate concentrations at the optimum temperature for methanogenesis. Our results revealed that peat soil organic matter degradation, mediated by biotic and potentially abiotic processes, is the main driver of the increase in CO2 production with temperature. In contrast, the decrease in CH4 production at 35°C was linked to the absence of syntrophic communities and the potential inhibitory effect of phenols on methanogens. Elevated temperatures further induced the microbial communities to develop high growth yield and stress tolerator trait‐based strategies leading to a shift in their composition and function. On the other hand, SRBs were able to outcompete methanogens in the presence of non‐limiting sulfate concentrations at 21°C, thereby reducing CH4 emissions. At higher sulfate concentrations, however, the prevalence of communities capable of producing sufficient low‐molecular‐weight carbon substrates for the coexistence of SRBs and methanogens was translated into elevated CH4 emissions. The use of omics in this study enhanced our understanding of the structure and interactions among microbes with the abiotic components of the system that can be useful for mitigating GHG emissions from peatland ecosystems in the face of global change.
Changing environmental conditions could change microbial activity leading to changes in greenhouse gas emissions. For example, elevated temperatures in peatland ecosystems can induce the microbial communities to develop high growth yield and stress tolerator trait‐based strategies leading to a shift in their composition and function.
Lignin is a promising renewable source of valuable organic compounds and environmentally benign materials. However, its involvement in economic circulation and the creation of new biorefining ...technologies require an understanding of its chemical composition and structure. This problem can be overcome by applying mass spectrometry analytical techniques in combination with advanced chemometric methods for mass spectra processing. The present study is aimed at the development of mass defect filtering to characterize the chemical composition of lignin at the molecular level. This study introduces a novel approach involving resolution-enhanced Kendrick mass defect (REKMD) analysis for the processing of atmospheric pressure photoionization Orbitrap mass spectra of lignin. The set of priority Kendrick fractional base units was predefined in model experiments and provided a substantially expanding available mass defect range for the informative visualization of lignin mass spectra. The developed REKMD analysis strategy allowed to obtain the most complete data on all the homologous series typical of lignin and thus facilitated the interpretation and assignment of elemental compositions and structural formulas to oligomers detected in extremely complex mass spectra, including tandem ones. For the first time, the minor modifications (sulfation) of lignin obtained in ionic liquid-based biorefining processes were revealed.
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•The REKMD is a novel approach to the analysis Orbitrap mass spectra of lignin.•The set of fractional base units was defined for visualization of mass spectra.•The REKMD analysis strategy was developed for the analysis of tandem mass spectra.•The minor modifications (sulfation) of ionic liquid lignin were revealed.
The comprehensive and efficient characterization of components in traditional Chinese medicine is crucial for elucidating its active constituents and uncovering its mechanism. Identifying the ...compounds of the Bushen Huoxue Prescription (BHP) is difficult because of its complex composition and the large difference in concentration among its compounds. In this study, a hydrophilic interaction liquid chromatography coupled with reversed‐phase LC (HILIC × RPLC) offline 2D‐LC tandem high‐resolution mass spectrometry method was established to analyze the total compounds of the BHP. Database screening and molecular networking were performed to identify the compounds. In contrast to conventional 1D chromatography, 2D chromatography increased peak capacity, enriched trace ingredients, and prevented the masking of high‐abundance compounds. A total of 165 compounds were identified, and 14 potential compounds needed to be further identified. This study provided an effective method for comprehensively analyzing the complex system of traditional Chinese medicine compounds.
Comprehensive ingredient research is of great significance for understanding the effective material basis of herbal medicines, but due to the diversity and complexity of their phytochemicals, such ...research is challenging. Here, a multifaceted strategy was proposed to analyze and identify the composition of HuangLian JieDu Decoction based on offline two‐dimensional liquid chromatography combined with ultraviolet detection and high‐resolution mass spectrometry. Multiple components were separated by two‐dimensional liquid chromatography, which consisted of hydrophilic interaction chromatography and reversed‐phase liquid chromatography, and then further characterized by high‐resolution mass spectrometry with a full mass spectrometry/precursor ion list/data‐dependent secondary scan data acquisition method. For data processing, database screening and molecular networking were used to identify the components in HuangLian JieDu Decoction. The offline two‐dimensional liquid chromatography combined with ultraviolet detection and a high‐resolution mass spectrometry system showed good orthogonality of 76.35% and a high peak capacity of 5175, effectively separating multiple components. Finally, 527 compounds, including 164 alkaloids, 133 terpenoids, 88 flavonoids, 60 phenylpropanoids, 38 organic acids, and 44 other compounds, were characterized. This integrated approach is suitable for the comprehensive characterization of herbal medicines and other complex chemical systems.
The current research explains the stress degradation behavior of Apixaban, which is an anticoagulant or blood thinner. The degradation was conducted using hydrolytic, oxidative, thermal, and ...photolytic conditions. Apixaban is relatively stable in oxidative, thermal, and photolytic conditions; however, considerable degradation was observed in acid and base hydrolysis. Degradation products were identified using ultra‐high performance liquid chromatography‐mass spectrometry, isolated using semi‐preparative high‐performance liquid chromatography, and structural characterization by high‐resolution mass spectrometry and nuclear magnetic resonance spectroscopy. A total of five degradation products were identified and isolated in acid and base degradation. Degradation products 1, 2, and 3 were observed in acid conditions, whereas in base conditions, along with those three, two more degradation products 4 and 5 were identified. The representative thing was that among the five degradation products, two sets of positional isomers 1, 4, and 2, 5 were observed; out of which 2 and 5 are novel. The remaining degradation products 1, 3, and 4 are already reported tentatively using a single analytical technique of mass analysis without any evidence from nuclear magnetic resonance spectroscopy. Hence, the present study focused on using high‐resolution mass, and nuclear magnetic resonance spectroscopy data for concrete confirmation of structures for degradation products.
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•Pros and cons of zebrafish larvae as metabolism tool for urine screenings.•Findings in larvae compared to human, human in vitro liver tools, and cell lines.•Studies allow scientist ...to use larvae model for setting up mass spectral methods.
New psychoactive substances (NPS) are an emerging topic amongst abused compounds. New varieties appear constantly on the market, without any knowledge about their toxicodynamic and/or -kinetic properties and knowledge of their metabolism is crucial for the development of analytical methods employed for their detection. Controlled human studies would of course be best suited but due to ethical reasons and lack of preclinical safety data, they are usually not available. Often, in vitro models are used to evaluate similarities to human in vivo hepatic phase I and II metabolism and systems explored include primary human hepatocytes, pooled human S9 fraction, and HepaRG, a human hepatic cell line. All these in vitro models have considerable limitations and drug distribution, reabsorption, enterohepatic circulation, and renal elimination cannot be studied. In the recent years, zebrafish (Danio rerio) larvae (embryos) were discussed as a potential in vivo model to overcome these limitations. To date, no studies demonstrating its suitability for studying NPS metabolism in the context of analytical toxicology are available. The aim of this study was to elucidate whether zebrafish larvae can serve as a surrogate for human hepatic metabolism of NPS to develop toxicological screening procedures. Here, we used methyl 2‐(1‐(5‐fluoropentyl)‐1H‐pyrrolo2,3‐bpyridine‐3‐carboxamido)‐3,3‐dimethylbutanoate (7′N‐5F‐ADB), a new synthetic cannabinoid, whose human metabolism was recently described in the literature, as a model compound to evaluate zebrafish larvae as a new tool for metabolism studies. Different conditions for zebrafish larvae and HepaRG protocols were tested. As zebrafish larvae and HepaRG cell incubations provided the highest number of metabolites and the most authentic spectrum of human metabolites. The most suitable larvae protocol was the incubation via medium and the analysis of the extracted zebrafish larvae. The zebrafish larvae model might be a promising preclinical surrogate for human hepatic metabolism of NPS.
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