Search Results (133)

This study investigates the metabolic responses of the model diatom Phaeodactylum tricornutum under different growth conditions, comparing benthic (adherent) and planktonic states. Using a multiblock metabolomics approach combining LC-HRMS², NMR, and GC-MS techniques, we compared the metabolome of P. tricornutum cultivated on three laboratory substrates (glass, polystyrene, and polydimethylsiloxane) and under planktonic conditions. Our results revealed metabolic differences between adherent and planktonic cultures, particularly concerning the lipid and carbohydrate contents. Adherent cultures showed a metabolic profile with an increase in betaine lipids (DGTA/S), fatty acids (tetradecanoic and octadecenoic acids), and sugars (myo-inositol and ribose), suggesting modifications in membrane composition and lipid remodeling, which play a potential role in adhesion. In contrast, planktonic cultures displayed a higher content of cellobiose, specialized metabolites such as dihydroactinidiolide, quinic acid, catechol, and terpenes like phytol, confirming different membrane composition, energy storage capacity, osmoregulation, and stress adaptation. The adaptative strategies do not only concern adherent and planktonic states, but also different adherent culture conditions, with variations in lipid, amino acid, terpene, and carbohydrate contents depending on the physical properties of the support. Our results highlight the importance of metabolic adaptation in adhesion, which could explain the fouling process. Full article

Essential oils are complex mixtures of apolar components, mainly phenylpropanoids, monoterpenes, and sesquiterpenes. Vetiver (Vetiveria zizanioides (L.) Nash) is a non-endemic grass in several tropical regions, widely used for slope stabilization and erosion control because of its long and deep roots that help to bind the soil together, preventing landslides and soil loss. From these roots, vetiver essential oil is obtained, which is extracted and produced worldwide and highly valued for its diverse range of bioactive substances used by the cosmetics and perfume industries. These substances, present in a very complex mixture, are difficult to isolate. Zizanoic acid is a very rare substance in nature and also very interesting because of the biological properties already described. In the present study, zizanoic acid was selectively isolated with 84–87% purity from vetiver commercial essential oils, in which it was present at less than 10%, using KOH-impregnated silica gel column chromatography alone. The experiments were monitored using GC-MS and UHPLC-HRMS, and the isolated substances (zizanoic and valerenic acids) were further determined by NMR experiments. The whole methodology and analytical approach proved to be very efficient for natural product complex mixture analysis and also very selective, allowing for a distinct capacity to recover carboxylic acids from complex biological samples. Full article

In this study, weekly grab samples extracted by solid-phase extraction (SPE) and stir bar sorptive extraction (SBSE) were compared for the analysis of 230 pesticides in surface waters. Samples were collected from three different locations around Melbourne, Australia. Analysis was performed using Gas Chromatography Quadrupole Time of Flight High Resolution Mass Spectrometry (GC-QToF-HRMS). The two extraction techniques were compared, among others, for their limits of detection, recovery, extraction, and quantification efficiency of pesticides, as well as spatial and temporal differences in detected compounds. The target compounds screened were pesticides belonging mainly to the categories of fungicides, insecticides, and herbicides. Although SBSE extracted more pesticides at two out of three sites, SPE extracted total concentrations up to four times higher than SBSE over all sampling sites. The log K_OW of detected pesticides only partially explained the differences in detection, with SBSE performing better in the absorption of hydrophobic compounds. In addition, matrix effects, in particular turbidity, appeared to hinder extraction of contaminants, especially for SBSE. Spatially, SBSE detected 10 pesticides more than SPE at two locations, while the opposite was true at the third location, where turbidity was higher. The types of pesticides detected varied slightly between techniques and locations. The study highlights the complementarity of SBSE and SPE for monitoring pesticides in natural environments. SBSE is an easy-to-use technique and allows for extraction of a higher number of pesticides at trace level, but it might not be the preferred option for highly turbid waters. SPE requires more tedious and complex sample processing but allows for a more accurate quantification of a broader range of pesticides. Full article

The formation of polycyclic aromatic hydrocarbons (PAHs) during catagenesis does not exclusively lead to planar structures. The inclusion of five-ring elements increases the curvature of PAHs and yields bent molecules. These bowl-like configurations may end in the formation of spherical carbon allotropes as fullerenes or nanotubes, as recently shown. The presence of fullerenes in crude oil raises the question of why the reaction is feasible under catagenic conditions although the laboratory synthesis of fullerenes commonly requires high-energy environments. This study focuses on the feasibility of the simulation of catagenesis under laboratory conditions and the question of which building blocks may lead to spherical structures. Possible educts, reaction mechanisms, and conditions such as temperature are discussed and related to experimental outcomes. For the simulation under laboratory conditions, a light gas condensate was fractionated by distillation in order to reduce the number of compounds per fraction and make them distinguishable. The characterization of the resulting fractions was performed through GC-MS and GC-FID measurements before heat application in a closed reactor. High-resolution mass spectrometry (HRMS) measurements of the products indicated PAH growth and, more importantly, the formation of fullerenes. Interestingly, the characterized fullerenes mostly comprised the range of non-IPR (isolated pentagon rule) fullerenes. Full article

Two main adenoviral diseases have been described in pigeons: pigeon adenovirus type 1 (PiAdV-1) and pigeon adenovirus type 2 (PiAdV-2), which belong to the genus Aviadenovirus under the family Adenoviridae. PiAdV-1 and PiAdV-2 are highly pathogenic to pigeons, leading to considerable losses worldwide. To date, there is little information on the epidemiological distribution of PiAdV-1 and PiAdV-2 in pigeons due to the lack of detection and differentiation platforms for these two viruses. High-resolution melting technology (HRM) has been widely used for developing detection and differentiation platforms, with the melting profile based on the GC content in the real-time PCR (qPCR-HRM) system. This study designed and synthesized a pair of specific primers on the basis of the characteristic variations of the 52K genes of PiAdV-1 and PiAdV-2, then the detection and differentiation qPCR-HRM platform was established after conditional optimization. The results showed that this method had good specificity; it could only specifically detect PiAdV-1 and PiAdV-2, with no cross-reaction with other pigeon-origin pathogens that occur in pigeons. This method had high sensitivity, with the lowest detection limits at 57 copies/µL (for PiAdV-1) and 56 copies/µL (for PiAdV-2). This method had good intra-group and inter-group coefficients of variation, both of which were less than 1.5%. Field samples for the epidemiological surveillance and investigation data of PiAdV-1 and PiAdV-2 were checked. We found only PiAdV-2-positive samples in meat pigeons, but the percentages of PiAdV-1-positive, PiAdV-2-positive, and coinfection-positive samples among the racing pigeons were 5.71%, 14.29%, and 2.86%, respectively. To our knowledge, this is the first report for the simultaneous detection and differentiation of PiAdV-1 and PiAdV-2 using the qPCR-HRM platform. Our study also provided evidence of PiAdV-1 and PiAdV-2 coinfection in racing pigeons, but further studies are needed. Full article

Microalgae are a sustainable source of bioactive compounds and nutrients that do not compete with crops for arable land. Lobosphaera sp. was used to produce biodegradable films. Bioactive compounds, polysaccharides, and proteins were extracted from this microalga. The total phenolic content (TPC) and antioxidant activity (ABTS, DPPH, and ORAC) of the bioactive-rich extract were determined, and its composition was analyzed for phenolics using LC-ESI-QqTOF-HRMS and for lipids using GC-FID. The cytotoxicity of this extract on Caco-2 cells was also assessed. Different types of films were produced based on alginate (2%) (film A) and alginate with polysaccharides-rich (PS-rich) extract (0.5%) (film B); PS-rich extract and bioactive-rich extract (0.25%) (film C); protein-rich (P-rich) extract (0.5%) (film D); and P-rich extract and bioactive-rich extract (film E). The antioxidant activity and physical parameters of the films, such as thickness, color, water vapor permeability, solubility, tensile strength (TS), and elongation at break (EAB), were determined. The TPC of the bioactive-rich extract was 1.07 ± 0.05 mg GAE/100 mg DW, and its antioxidant activity was 2.44 ± 0.27, 1.67 ± 0.15, and 11.90 ± 1.22 µmol TE/100 mg DW for ABTS, DPPH, and ORAC, respectively. The extract showed no cytotoxicity to gut cells at concentrations equal to or below 1.0 mg/mL. Film E obtained the best results for the antioxidant activity, 451.06 ± 14.68 and 212.81 ± 39.12 µM TE/mg film for ABTS and DPPH, respectively. In addition, the films enriched with the bioactive-rich extract (films C and E) presented antimicrobial activity against Listeria monocytogenes. These films controlled the mold and yeast growth in strawberries during a four-day storage at 25 °C. All films were completely soluble in water and hydroethanolic solutions but only partially solubilized in acetic acid (3%). TS and EAB were not significantly different among the films. It was possible to produce biodegradable films using microalga Lobosphaera sp. with good bioactivity and physical characteristics. Full article

Cathinones, a class of synthetic new psychoactive substances (NPSs), continue to emerge and pose public threats. Government control efforts often lead to the emergence of new isomers, which have adverse repercussions on NPSs identification and risk prediction. This work reports on the synthesis and structural characterization of twenty chloro-cathinones, including different isomers, to create analytical data to facilitate their identification in forensic and clinical contexts. Additionally, the potential of these cathinones to cause neuronal damage was evaluated. In vitro cytotoxicity was assessed using a differentiated human neuroblastoma cell line (SH-SY5Y) as a dopaminergic neuronal model. The tested cathinones showed LC₅₀ values from 0.6 to 2.5 mM, with 4-CBC being the most cytotoxic. The most toxic cathinones increase reactive oxygen species levels and/or cause mitochondrial membrane potential depolarization. Furthermore, this study explored, for the first time, the effect of cathinones on the cholinergic system through acetylcholinesterase (AChE) inhibition. All tested cathinones inhibited AChE with IC₅₀ values between 0.1 and 2 mM. Molecular docking analysis revealed that the most inhibitory cathinones interacted with the CASs and PASs in AChE’s active gorge. These findings provide valuable insights into the effects of cathinones, highlighting potential health risks and structural features that may influence their toxicity towards the cholinergic system and neuronal damage. Full article

The extraction processes for medicinal plants, particularly the distillation of aromatic plants, generate significant quantities of by-products, consisting of fibrous biomass and hydrosols. These by-products pose challenges for disposal and recovery. Consequently, it is imperative to make the entire highly energy-intensive process more sustainable by valorizing all derivatives. This study aims to recover polyphenols from the exhausted biomasses of Artemisia dracunculus, Echinacea purpurea, Helichrysum italicum (from the Asteraceae family), and Lavandula angustifolia, Lavandula × intermedia, Melissa officinalis, Salvia officinalis, Salvia sclarea, and Salvia rosmarinus (from the Lamiaceae family) after steam distillation. The residual biomasses were extracted using ethanol (conventional solvent) and different natural deep eutectic solvents (NADES) composed of choline chloride in combination with citric and lactic acids at different molar ratios. The NADES containing choline chloride and lactic acid at the molar ratio 1:1 (CLA11) exhibited the highest recovery of representative phenols of the plants, namely chicoric and rosmarinic acids. The CLA11 solvent demonstrated a stronger extractive capacity compared to ethanol in all the biomasses belonging to the Asteraceae and Lamiaceae families. Specifically, CLA11 extracts showed a higher number of compounds in UHPLC-HRMS and greater concentrations of chicoric and rosmarinic acids determined by HPLC-DAD than ethanol extracts. In conclusion, NADES were demonstrated to be a viable alternative system for the recovery of bioactive compounds that could be used to formulate new products for the food, pharmaceutical, and cosmetic industries. Moreover, the use of NADES can enhance the sustainability of the whole production chain of essential oils being environmentally friendly. Full article

Stable isotope ratio analysis of carbon (δ¹³C) and hydrogen (δ²H) in vanillin has become a valuable tool for differentiating natural vanilla from synthetic or biosynthetic alternatives and for tracing its geographical origins. However, increasingly sophisticated fraud techniques necessitate ongoing refinement of analytical methods to ensure accurate detection. This study advanced the field by investigating minor volatile organic compounds as potential biomarkers for identifying botanical and geographical origins of vanilla products. Vanilla pods from the two main vanilla species, V. planifolia and V. tahitensis, were investigated using GC-MS/MS to analyze their aromatic profile and GC-C/Py-IRMS to determine compound-specific isotope ratios, providing, for the first time, detailed and authentic isotopic and aromatic profiles. Additionally, the potential natural presence of ethyl vanillin and its corresponding glucoside precursors—molecules commonly used as synthetic vanilla-scented fragrance agents in various foods and industrial products—was explored using UHPLC-HRMS. These findings contribute to robust methods for verifying vanilla authenticity, addressing flavor complexity and isotopic composition, and enhancing the detection of adulteration in vanilla-flavored products. Full article

This study critically examines the workflow for untargeted analysis of volatile organic compounds (VOCs) in ambient air, from sampling strategies to data interpretation by using GC-HRMS. While untargeted approaches are well-established in liquid chromatography (LC) due to advanced-deconvolution tools and extensive metabolomic libraries, their application in gas chromatography (GC) remains less developed, particularly for VOCs. The high structural isomerism of VOCs and the relative novelty of GC-based untargeted methodologies present unique challenges, including limited software tools and reference libraries. Air samples from suburban and rural sites in central Italy were analyzed to explore chemical diversity and address methodological gaps. This study evaluates critical decisions, such as sampling strategies, extraction techniques, and data-processing workflows, highlighting the limitations of automated deconvolution tools and the need for manual validation. Results revealed distinct source contributions, with suburban areas showing higher levels of anthropogenic compounds and rural areas dominated by biogenic emissions. This work underscores the potential of GC-HRMS untargeted analysis to advance environmental chemistry, while addressing key pitfalls and providing practical recommendations for reliable application. By bridging methodological gaps, it offers a roadmap for future studies aiming to integrate untargeted and targeted approaches in air quality research. Full article

Emerging contaminants (ECs), encompassing pharmaceuticals, personal care products, pesticides, and industrial chemicals, represent a growing threat to ecosystems and human health due to their persistence, bioaccumulation potential, and often-unknown toxicological profiles. Addressing these challenges necessitates advanced analytical tools capable of detecting and quantifying trace levels of ECs in complex environmental matrices. This review highlights the pivotal role of mass spectrometry (MS) in monitoring ECs, emphasizing its high sensitivity, specificity, and versatility across various techniques such as Gas Chromatography-Mass Spectrometry (GC-MS), Liquid Chromatography-Mass Spectrometry (LC-MS), and High-Resolution Mass Spectrometry (HR-MS). The application of MS has facilitated the real-time detection of volatile organic compounds, the comprehensive non-targeted screening of unknown contaminants, and accurate quantification in diverse matrices including water, soil, and air. Despite its effectiveness, challenges such as matrix interferences, a lack of standardized methodologies, and limited spectral libraries persist. However, recent advancements, including hybrid MS systems and the integration of artificial intelligence (AI), are paving the way for more efficient environmental monitoring and predictive modeling of contaminant behavior. Continued innovation in MS technologies and collaborative efforts are essential to overcome existing challenges and ensure sustainable solutions for mitigating the risks associated with emerging contaminants. Full article

Stingless bees are vital pollinators in tropical and neotropical regions, emphasizing the need to conserve these species. However, resource scarcity, particularly pollen, during certain periods negatively impacts bee health and pollination efficiency. To address this, we developed a fermented protein feed using microorganisms from pollen of Melipona quadrifasciata, a species commonly found in the Brazilian Atlantic Forest. The fermented feed consisted of a protein bran mixture, sugar syrup, and an inoculant derived from species’ fermented pollen. To assess the feed quality, nutritional evaluation and metabolomic analyses were conducted (UHPLC/DAD-HRMS/MS and GC-MS). The metabolomic analysis identified 85 compounds in positive and 102 in negative ionization modes. Shared metabolites, such as isoquercetin and palatinose, highlighted similarities between the feed and natural fermented pollen. Laboratory tests with caged bees showed comparable consumption between the feed and fermented pollen with no statistical difference (mean: 0.067 g vs. 0.060 g; p = 0.53). The feed exhibited a favorable pH transition (5.30 pre-fermentation to 4.41 after the fermentation process) and remained stable for six months at ±2 °C. These findings demonstrate a biotechnological advance in stingless bee nutrition, offering a viable solution during resource scarcity and promoting the health of M. quadrifasciata. Full article

Glucocorticoids (GCs) are routinely used to treat hematological malignancies; however, long-term treatment with GCs can lead to atrophic and metabolic adverse effects. Selective glucocorticoid receptor agonists (SEGRAs) with reduced side effects may act as a superior alternative to GCs. More than 30 SEGRAs have been described so far, yet none of them reached clinical trials for anti-cancer treatment. In the present work, we propose a novel approach to increase the number of potential SEGRAs by obtaining derivatives of synephrine, a molecule of natural origin. We synthesized 26 novel compounds from the class of synephrine derivatives and characterized them by HRMS, and ¹H and ¹³C NMR. We evaluated in vitro anti-cancer effects in leukemia K562 and lymphoma Granta cells using the MTT assay and studied their potential affinity for the glucocorticoid receptor (GR) in silico using the molecular docking approach. The novel derivative 1-[4-(benzyloxy)phenyl]-2-(hexylamino)ethanol (10S-E2) with the highest GR affinity in silico exhibited cytotoxic activity against K562 and Granta cells after 24 h of treatment at the concentration of approximately 13 µM which correlated with its highest MolDock Score. The other compound with high GR affinity, 2-(hexylamino)-1-(4-nitrophenyl)ethanol (13S-G2), demonstrated cytotoxicity in both cell lines at concentrations of 50–70 µM. Overall, our results may provide a solid rationale for developing and further investigating synephrine derivatives as SEGRAs with anti-cancer activity. Full article

The stem bark of black locust (Robinia pseudoacacia L.) was extracted, and nine antioxidant compounds (R1–R9) were detected by high-performance thin-layer chromatography combined with the radical scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH•) assay, multi-detection, and heated electrospray high-resolution mass spectrometry. For structure elucidation, the methanolic crude extract was fractionated by solid-phase extraction, and the compounds were isolated by reversed-phase high-performance liquid chromatography with diode array detection. The structures of isolated compounds were elucidated by nuclear magnetic resonance and attenuated total reflectance Fourier-transform infrared spectroscopy as well as gas chromatography-mass spectrometry to determine the double bond position. 3-O-Caffeoyl oleanolic acid (R1), oleyl (R2), octadecyl (R3), gadoleyl (R4), eicosanyl (R5), (Z)-9-docosenyl (R6), docosyl (R7), tetracosyl (R8), and hexacosanyl (R9) caffeates were identified. While R1 has been reported in R. pseudoacacia stem bark, the known R3, R5, R7, R8, and R9 are described for the first time in this species, and the R2, R4, and R6 are new natural compounds. All nine caffeates demonstrated antioxidant activity. The antioxidant effects of the isolated compounds R1–R8 were quantified by a microplate DPPH• assay, with values ranging from 0.29 to 1.20 mol of caffeic acid equivalents per mole of isolate. Full article

Type-2 diabetes affects an increasing percentage of the world’s population and its control through dietary management, involving the consumption of health-promoting foods or their derived supplements, is a common strategy. Several mushroom species have been demonstrated to be endowed with antidiabetic properties, resulting from their ability in improving insulin sensitivity and production, or inhibiting the carbohydrate-hydrolyzing enzymes α-amylase and α-glucosidase. This study aimed to investigate for the first time the hypoglycemic properties of the edible mushroom Leccinum scabrum (Bull.) Gray. Mushroom extracts were prepared through the microwave-assisted extraction (MAE) technique using green solvents with different polarity degrees. The inhibition activity of all the obtained extracts on both α-glucosidase and α-amylase was evaluated and the highest activity was observed for the EtOAc extract which showed an IC₅₀ value about 60-fold lower than the reference compound 1-deoxynojirimycin (DNJ) on α-glucosidase (0.42 ± 0.02 and 25.4 ± 0.6 µg/mL, respectively). As expected on the basis of the literature data concerning both α-glucosidase and α-amylase inhibition, a milder inhibition activity on pancreatic α-amylase was observed. Preliminary in vivo tests on Drosophila melanogaster carried out on the most active obtained extract (EtOAc) confirmed the in vitro observed hypoglycemic activity. Finally, the EtOAc extract metabolic profile was determined through GC-MS and HRMS analyses. Full article