Carotenoids consist of a series of conjugated isoprene units that are characteristically highly conjugated through double bonds, leading to the formation of many isomers that are susceptible to ...oxidation and other chemical modifications. Extreme hydrophobicity and high complexity make carotenoids difficult to identify and quantify. We implemented the use of a common Syncronis C18 column with strong eluting solvent, here isopropanol, to successfully separate a mixture of 23 carotenoids standards with different structural properties. In addition, the method differentiated between three groups of isomeric carotenoids (lycopene/δ‐carotene/γ‐carotene/ε‐carotene/α‐carotene/β‐carotene, α‐cryptoxanthin/β‐cryptoxanthin, and zeaxanthin/lutein) by optimizing the gradient profile and using liquid chrmatography–mass spectrometry. The LOD ranged from 0.05 to 5.51 ng/mL, and the recovery of carotenoids in Mytilus coruscus was from 63.54 to 93.25%, with standard deviations <10%. Twenty‐five carotenoids were detected with a total content of 857 ± 55.1 mg/kg, and three isomeric carotenoids were identified: ε‐carotene, α‐carotene, and β‐carotene. Our results show that this methodology is a significant improvement over other alternatives for analyzing carotenoids because of its compatibility with carotenoids of different categories, and most importantly, its ability to resolve isomeric carotenes, which is significant not only for assessing carotenoid species, but also for the tracing of metabolic pathways of carotenoids.
New Psychoactive Substances (NPS) are an ever-changing class of compounds designed to imitate the effects of current recreational drugs. Such a diverse market is difficult to assess by traditional ...means, while collected information can become obsolete before it is available. Wastewater-based epidemiology is one technique which can capture information on where and when NPS appear at the community level. The aim of this study was to identify NPS in wastewater samples using a suspect screening approach. Weekend samples were collected from 50 wastewater treatment plants from Australian capital cities and regional areas across all eight States and Territories and screened against a database containing almost 200 NPS. A total of 22 different NPS were found across all regional and metropolitan wastewater treatment plants. Results showed that the most detected compounds were of the cathinone class, with both Alpha-PVP and methcathinone found in every region. In addition, five different synthetic cannabinoids were detected, at least once in half of the regions analysed. Herein, we report the first comprehensive nationwide analysis of NPS and show the utility of liquid chromatography-high resolution mass spectrometry screening for delivering spatial information of the NPS being consumed in communities.
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•Most comprehensive screening study of new psychoactive substances•50 sites around Australia covering 60% of the population were investigated.•22 New Psychoactive Substances tentatively identified, detected and/or confirmed.•Synthetic cathinones (methacthinone and alpha PVP) most commonly found.
Metabolism studies are one of the important steps in pharmaceutical research. LC-MS combined with metabolomics data-processing approaches have been developed for rapid screening of drug metabolites. ...Mass defect filter (MDF) is one of the LC/MS-based metabolomics data processing approaches and has been applied to screen drug metabolites. Although MDF can remove most interference ions from an incubation sample, the true positive rate of the retaining ions is relatively low (approximately 10%). To improve the efficacy of MDF, we developed a two-stage data-processing approach by combining MDF and stable isotope tracing (SIT) for metabolite identification. Pioglitazone (PIO), which is an antidiabetic drug used to treat type 2 diabetes mellitus, was taken as an example drug. Our results demonstrated that this new approach could substantially increase the validated rate from about 10% to 74%. Most of these validated metabolite signals (13/14) could be verified as PIO structure-related metabolites. In addition, we applied this approach to identify uncommon metabolite signals (a mass change beyond the window of 50 Da around its parent drug, MDF1). SIT could remove most interference ions (approximately 98%) identified by MDF1, and four out of five validated metabolite signals could be verified as PIO structure-related metabolites. Interestingly, a lot of the verified metabolites (10/17) were novel PIO metabolites. Among these novel metabolites, nine were thiazolidinedione ring-opening signals that might be related to the toxicity of PIO. Our developed approach could significantly improve the efficacy in drug metabolite identification compared with that of MDF.
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•A combination of MDF and SIT was developed for drug metabolite identification.•Our developed approach provided a high validation rate (79%) in identified signals.•Seventeen validated signals were verified as PIO structure-related metabolites.•Ten PIO structure-related metabolites were novel PIO metabolite signals.
Hydroxylated polycyclic aromatic hydrocarbons are metabolites of persistent organic pollutants which are formed during the bioactivation process of biological matrices and whose toxicity is being ...studied. The aim of this work was the development of a novel analytical method for the determination of these metabolites in human tissues, known to have bioaccumulated their parent compounds. Samples were treated by salting‐out assisted liquid‐liquid extraction and the extracts were analyzed by ultra‐high performance liquid chromatography coupled to mass spectrometry with a hybrid quadrupole‐time‐of‐flight analyzer. The proposed method achieved limits of detection in the 0.15–9.0 ng/g range for the five target analytes (1‐hydroxynaphthalene, 1‐hydroxypyrene, 2‐hydroxynaphthalene, 7‐hydroxybenzoapyrene, and 9‐hydroxyphenanthrene). The quantification was achieved by matrix‐matched calibration using 2,2´‐biphenol as internal standard. For all compounds, relative standard deviation, calculated for six successive analyses, was below 12.1%, demonstrating good precision for the developed method. None of the target compounds was detected in the 34 studied samples. Moreover, an untargeted approach was applied to study the presence of other metabolites in the samples, as well as their conjugated forms and related compounds. For this objective, a homemade mass spectrometry database covering 81 compounds was created and none of them was detected in the samples.
Hemp seed oil is well known for its nutraceutical, cosmetic and pharmaceutical properties due to a perfectly balanced content of omega 3 and omega 6 polyunsaturated fatty acids. Its importance for ...human health is reflected by the success on the market of organic goods in recent years. However, it is of utmost importance to consider that its healthy properties are strictly related to its chemical composition, which varies depending not only on the manufacturing method, but also on the hemp variety employed. In the present work, we analyzed the chemical profile of ten commercially available organic hemp seed oils. Their cannabinoid profile was evaluated by a liquid chromatography method coupled to high-resolution mass spectrometry. Besides tetrahydrocannabinol and cannabidiol, other 30 cannabinoids were identified for the first time in hemp seed oil. The results obtained were processed according to an untargeted metabolomics approach. The multivariate statistical analysis showed highly significant differences in the chemical composition and, in particular, in the cannabinoid content of the hemp oils under investigation.
Emerging contaminants (ECs) such as pharmaceuticals, personal care products, drugs of abuse and polar pesticides are under particular attention due to their high consumption, frequent detection in ...the environment and reported ecotoxicological risk. This study investigates the occurrence and distribution of multiclass of ECs in surface waters at basin scale of two Atlantic coastal lagoons of Uruguay, South America. For this purpose, a target screening approach covering up to 362 compounds was employed using nanoflow liquid chromatography – high resolution mass spectrometry (nanoLC/HRMS). 56 compounds were identified including five banned pesticides in the European Union: atrazine, carbendazim, chlorpyrifos ethyl, diazinon, and ethion. Pharmaceuticals, hormones and drugs of abuse showed maximum detection frequencies and concentrations downstream cities. The highest occurrence of pesticides was found in lagoons and streams with neighboring agricultural activity. ECs were also found in coastal sea. Environmental risk assessment revealed that the hormones 17α-ethinylestradiol and 17-β-estradiol showed the highest risk to aquatic organisms in these basins. This study represents the first basin- scale monitoring of ECs in superficial waters encompassing streams, lagoons, and coastal seas in Uruguay, South America.
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•362 emerging contaminants monitored from streams to coastal sea•56 different pollutants identified by nanoflow-LC/HRMS•Pharmaceuticals, hormones and drugs of abuse presented maximum concentrations downstream the cities•Higher occurrence of pesticides in agricultural areas•The hormones 17α-ethinylestradiol and 17-β-estradiol showed the highest ecotoxicological risks
Chronic wounds result from the failure of the normal wound healing process. Any delay during the tissue repair process could be defined as chronic wound healing, potentially having a highly ...detrimental impact on human health. To face this problem, in the last years, the use of different technologies alternative to therapeutic agents is gaining more attention. The Helix aspersa snail slime‐based products are increasingly being used for skin injury, thanks to their ability to make tissue repair processes faster. To date, a comprehensive overview of pure snail slime metabolome is not available. Besides, Au nanoparticles (AuNPs) technology is spreading rapidly in the medical environment, and the search for AuNPs “green” synthetic routes that involve natural products as precursor agents is demanded, alongside with a deep comprehension of the kind of species that actively take part in synthesis and product stabilization. The aim of this work is to characterize the metabolic profile of a pure snail slime sample, by an untargeted high‐resolution mass spectrometry‐based analysis. In addition, insights on AuNPs synthesis and stabilization by the main components of pure snail slime used to induce the synthesis were obtained. The untargeted analysis provided a large list of important classes of metabolites, that is, fatty acid derivatives, amino acids and peptides, carbohydrates and polyphenolic compounds that could be appreciated in both samples of slime, with and without AuNPs. Moreover, a direct comparison of the obtained results suggests that mostly nitrogen and sulfur‐bearing metabolites take part in the synthesis and stabilization of AuNPs.
The consumption of food and drugs adulterated with female sex hormones can have an extremely adverse effect on human health. Therefore, developing appropriate monitoring methods for the ...identification of various exogenous female sex hormones is crucial for minimizing and eliminating the related health risks. Herein, 17 female hormones categorized into two groups: estrogen and progestin, were analyzed using reversed‐phase liquid chromatography coupled to Orbitrap or triple quadrupole mass spectrometry. The fragmentation patterns for all compounds were discovered, and fragmented structures were also derived from them through liquid chromatography–high‐resolution mass spectrometry followed by qualitative sample analysis. In addition, a quantitative analysis of 67 samples of illicit drugs and dietary supplements was performed using the validated liquid chromatography‐tandem mass spectrometry method. Female hormone components were detected in two samples of an unauthorized injectable solution and a tablet‐type drug. Medroxyprogesterone was detected in the samples in the range of 96.4–206 ng/g. Notably, eight components similar in structure to steroids were simultaneously detected as male sex hormones by confirming their fragmentation ion patterns using liquid chromatography–high‐resolution mass spectrometry. The developed methods thus offer a dependable and practically applicable approach for the screening and detection of exogenous female sex hormones in real food and drug samples to ensure public health.
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