Search Results (12,875)

Fragmentation Resilience Energy Mass Spectrometry (FREMS) builds on the field of energy-resolved mass spectrometry and previously used methods, e.g., Survival Yield. It exploits breakdown energies at near “continuous” ramp (0.2% NCE increments) to offer higher resolution and a reliable method for compound differentiation, contaminant identification and structural elucidation. Implementation of FREMS involves acquiring ion breakdown/formation curves as collision energy is incrementally increased. These curves themselves can be analyzed by several means to give a single metric—Fragmentation Resilience (FR₅₀). This value has been shown to be experimentally interchangeable with the modified-Survival Yield (m-SY₅₀) and the Cross-Intersect (C-I). A full panel of testing on an LTQ-Orbitrap revealed that breakdown energies depend only on three controllable parameters—number of ions inside the ion trap, Maximum Inject time and Activation Time. A fairly linear relationship (R² > 0.95) with proposed FR₅₀, m-SY₅₀ and C-I metrics provides reliable adjustment mechanisms for these variables via calibrations. Consequently, this technique can be applied to ions produced by any atmospheric pressure ionization processes and treated as exclusively in vacuo experiments. Applications of FREMS to 4-chlorobenzylpyridinium ion revealed that under collisional activated dissociation (CAD) conditions, the rate of decomposition of precursor ion is equivalent to the rate of formation of its fragments, i.e., normalized breakdown and formation curves intersect at inflection points. Full article

Background: Trypanosoma cruzi, the causative agent of Chagas disease, remains a major public health concern, and there is a continued need for new antitrypanosomal agents. Thiosemicarbazone (TSC) derivatives have emerged as a promising class of compounds with potential antiparasitic activity. Objectives: This study aimed to report the synthesis, characterization, and biological profiling of a novel series of thiosemicarbazone derivatives as antitrypanosomal agents against Trypanosoma cruzi. Methods: Fourteen new compounds and six previously described analogues were prepared and characterized by ¹H/¹³C nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). As a preliminary in vitro screen, activity was assessed by direct parasite counting in epimastigote and bloodstream trypomastigote forms, as tractable models of replicative and infective stages sharing core metabolic targets with intracellular amastigotes. Epimastigote potency was quantified as half-maximal effective concentrations (EC₅₀) derived from dose–response curves, whereas trypomastigote response was evaluated as percent viability after treatment at a fixed concentration of 20 µM. Mechanistic profiling included inhibition assays against the cysteine protease cruzipain (CZP) and selected redox defense enzymes, complemented by in silico similarity clustering and binding-pose affinity scoring. Results: A nitro-methoxy-substituted TSC showed potent CZP inhibition but limited trypomastigote efficacy, whereas brominated analogues displayed dual-stage activity independent of CZP inhibition. Tanimoto similarity analysis identified distinct structure–activity clusters, linking nitro-methoxy substitution to epimastigote selectivity and brominated scaffolds to broader antiparasitic profiles, with hydrophobicity and steric complementarity as key determinants. Enzymatic assays revealed no significant inhibition of cytosolic tryparedoxin peroxidase (cTXNPx) or glutathione peroxidase type I (TcGPx-I), suggesting redox disruption is not a primary mode of action. In vitro and in silico analyses showed low or no non-specific cytotoxicity under the tested conditions, supporting further optimization of these derivatives as antitrypanosomal preliminary hits. Key hits included derivative 3e (epimastigote EC₅₀ = 0.36 ± 0.02 µM) and brominated analogues 2c and 2e (epimastigote EC₅₀ = 3.92 ± 0.13 and 4.36 ± 0.10 µM, respectively), while docking supported favorable binding-pose affinity (e.g., ΔG_S-pose = −20.78 ± 2.47 kcal/mol for 3e). Conclusions: These results support further optimization of the identified thiosemicarbazone derivatives as preliminary antitrypanosomal hits and provide insight into structure–activity relationships and potential mechanisms of action. Full article

The mineral-mapping capability of three spaceborne sensors with different spatial and spectral resolutions, the Environmental Mapping and Analysis Program (EnMap), Sentinel-2, and World View-3 (WV3), is assessed regarding bauxite mining wastes in Amphissa, Greece, with validation based on ground samples. We applied the well-established Linear Spectral Unmixing (LSU) and Spectral Angle Mapping (SAM) classification techniques utilizing endmembers of two established spectral libraries and incorporated ground data through geochemical and mineralogical analyses, X-ray fluorescence (XRF), Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), and X-ray Diffraction (XRD), to assess classification performance. The main lithologies in this area are bauxites and limestones; therefore, aluminum oxyhydroxides, calcite, and iron oxide minerals were the dominant phases as indicated by the XRF/XRD results. Almost all target minerals were mapped with the three sensors and both methods. The performance of EnMap is affected by its coarser spatial resolution despite its higher spectral resolution using these methods. Sentinel-2 is most effective for mapping iron-bearing minerals, particularly hematite, due to its higher spatial resolution and the presence of diagnostic iron oxide absorption features in the VNIR. World View 3 Shortwave Infrared (WV3-SWIR) performs better when mapping calcite, benefiting from its eight SWIR spectral bands and very high spatial resolution (3.7 m). Hematite and calcite yield the highest accuracy, especially with SAM, indicating 0.80 for Sentinel-2 (10 m) for hematite and 0.87 for WV3-SWIR (3.7 m) for calcite. AlOOH shows higher accuracy with SAM, ranging from 0.57 to 0.80 across the sensors, while LSU shows lower accuracy, ranging from 0.20 to 0.73 across the sensors. This study showcases each sensor’s ability to map minerals while also demonstrating that spectral coverage and the spatial and spectral resolution, as well as the characteristics of the selected endmembers, exert a critical influence on the accuracy of mineral mapping in mine waste. Full article

Ramaria flavobrunnescens is an ectomycorrhizal coral mushroom that is often found growing in eucalyptus forests. The mushroom has been linked to accidental ingestion-associated livestock poisonings in South America, though the toxicological agent has not yet been described. Mushroom samples identified as R. flavobrunnescens were analyzed by liquid chromatography high-resolution mass spectrometry (LC–MS/MS) to determine the potential source of the toxicity, and to provide a metabolomic profile of the species. Previously reported Ramaria secondary metabolites were detected, including ramarins, ramariolides, pistillarin and arsenic-containing compounds. A number of bacterial species were isolated from R. flavobrunnescens that produced iron-chelating cyclic peptides, which were detected in the mushroom samples. Interestingly, we detected a series of eucalyptus tree secondary metabolites in abundance from R. flavobrunnescens fruiting bodies, some of which have reported toxicities and bioactivities. To our knowledge, this is the first report of eucalyptus secondary metabolites in a mushroom. The diversity of secondary metabolites identified in the mushroom extracts provides insight into the potential complex ecological interactions between R. flavobrunnescens, its associated microbiota, and its mycorrhizal interaction with eucalyptus trees. Full article

Leaves of Cucumis callosus, traditionally employed in Ayurvedic medicine for the treatment of urinary disorders, were investigated in depth for their therapeutic potential against bacterially induced urinary tract infection (UTI) for the first time. The present work is the first to explore the antibacterial activity of C. callosus leaf fractions with an integrative in silico, in vitro, and in vivo approach. Through bioassay-guided fractionation, the chloroform fraction (F1) was identified as the most active, exhibiting potent activity against Uropathogenic Escherichia spp. species. Liquid chromatography–mass spectrometry (LC-MS) analysis of F1 revealed the presence of bioactive compounds, including stigmasterol, 1,2,3,4-tetrahydroisoquinoline, lactose, hydroxy(mesityl)acetic acid, and 2,4-di-tert-butylphenol. Molecular docking studies validated the strong binding affinities of these compounds for bacterial resistance enzymes, including AmpC β-lactamase and carbapenemases, thereby providing plausible mechanisms of antimicrobial action. In vivo studies carried out on female rats infected with Escherichia spp. species revealed a dose-dependent reduction in bacterial load, with a significant decrease in urinary tract inflammation upon F1 administration. Histopathological evaluation confirmed the protective effect, with reduced epithelial damage and inflammation in bladder tissues. These findings indicate significant antibacterial and tissue-protective effects of the C. callosus leaf fraction F1, supporting its ethnomedicinal use and establishing it as a promising phytotherapeutic agent for the treatment of urinary tract infections. Full article

Eugenia pyriformis Cambess., popularly known as uvaia, is a native Brazilian species belonging to the Myrtaceae family that has attracted pharmacological interest due to its richness in bioactive secondary metabolites. Previous studies have reported antimicrobial and antioxidant activities of the essential oil obtained from its leaves, reinforcing its therapeutic potential. In this context, the present study aimed to extract and characterize the essential oil from E. pyriformis leaves cultivated in the mountainous region of Rio de Janeiro, Brazil, and to evaluate its anti-inflammatory potential through in vitro and in vivo models. Gas chromatography mass spectrometry (GC–MS) analysis revealed a predominance of sesquiterpene hydrocarbons, mainly γ-muurolene, δ-cadinene, and β-caryophyllene. The oil exhibited significant anti-edematogenic activity in carrageenan-, prostaglandin E₂-, and bradykinin-induced paw edema models in adult female Swiss mice, suggesting modulation of inflammatory mediators, possibly through inhibition of the cyclooxygenase (COX) pathway. Conversely, no effect was observed in the compound 48/80-induced model, indicating the absence of activity on histamine- and serotonin-mediated processes. In vitro assays demonstrated that the oil reduced TNF-α and IL-1β gene expression in RAW 264.7 macrophages, confirming its ability to modulate pro-inflammatory cytokines. Taken together, these findings demonstrate that the essential oil of E. pyriformis exerts anti-inflammatory activity through multiple targets. Full article

In recent years, the development of new diagnostic technologies, such as tandem mass spectrometry (MS/MS) and next-generation sequencing (NGS), has caused a veritable revolution in the diagnosis of genetic diseases, reducing time, cost, and invasiveness associated with prior diagnostic techniques. While MS/MS laid the foundation for the development of numerous, usually institutionally based, neonatal screening programs, NGS has gained traction in newborn screening (NBS), primarily through pilot projects and private funding across different countries. As a result, the traditional Wilson and Jungner criteria have been supplemented by additional criteria, including considerations of equity and access, in response to emerging technologies. This review aims to provide an up-to-date overview of the global landscape of metabolic screening panels, highlight the major ongoing genomic screening projects, and outline the current models for integrating these two screening systems. Substantial differences exist across countries in the numbers and types of diseases included in national NBS programmes. In this context, Italy represents a prominent case, as its neonatal screening framework has seen significant expansion and development in recent years, reaching a particularly comprehensive metabolic screening panel. Nonetheless, a number of initiatives to incorporate genomic technologies into the NBS pathway are currently underway, primarily involving high-income countries. Nonetheless, unlike metabolomic-based NBS programs, no country has a government-mandated NGS program as first-tier testing for newborns. New evidence is emerging from ongoing models of integration of multi-omics approaches into NBS, including the use of AI and machine learning. Identifying the most appropriate system for this integration to reduce the false-positive and false-negative rates associated with both screening types, ensure more equitable access to screening, and facilitate faster access to treatment may represent a useful and foresightful way to conceptualize NBS in the future. This transitional phase should promote rigorous improvements before full-scale adoption. Full article

Titanium dioxide (TiO₂) nano- and submicrometric particles’ widespread use in different sectors raised concerns about human and environmental exposure. The validation of analytical methods is essential to ensure reliability in risk assessment studies. In this study, a single-particle inductively coupled plasma mass spectrometry (spICP-MS) method was validated for the detection, quantification, and dimensional characterization of TiO₂ particles in biological tissues. Tissue samples collected after exposure to TiO₂ particles underwent mild acidic digestion using a HNO₃/H₂O₂ mixture to achieve complete matrix decomposition while preserving particle integrity. The resulting digests were analyzed by ICP-MS operated in single-particle mode to quantify and size TiO₂ particles. Method validation was conducted according to ISO/IEC 17025:2017 and included linearity, repeatability, recovery, and detection limit assessments. The limit of detection for TiO₂ particles was 0.04 µg/g, and 55.7 nm was the size the detection limit. Repeatability was within 0.5–11.5% for both TiO₂ mass concentrations and particle size determination. The validated method was applied to tissues from inhalation-exposed subjects, showing TiO₂ levels of 80 ± 20 µg TiO₂/g and particle number concentrations of 5.0 × 10⁵ ± 1.2 × 10⁵ part. TiO₂/mg. Detected TiO₂ particles’ mean diameter ranged from 230 to 330 nm. The developed and validated spICP-MS method provides robust and sensitive quantification of TiO₂ particles in biological matrices, supporting its use in human biomonitoring and exposure assessment studies. Full article

Background: Plasticisers with endocrine-disrupting potential are ubiquitous and associate with obesity and type-2 diabetes (T2D), with higher levels reported in the Middle East. However, no data exist on plasticiser exposure in Bahrain where T2D affects 15% of the national population. Methods: An observational exploratory study in T2D (n = 60) and controls (n = 96), analysed for 24 h urinary plasticiser levels (liquid chromatography tandem mass spectrometry (LC-MS/MS)). Correlation and generalised linear model (GLM) analyses were employed to examine associations. Results: T2D were older (p < 0.001), had higher body mass index (BMI) (p < 0.001), body weight (p < 0.001) and glycosylated haemoglobin A1c (HbA1c) (p < 0.001). Correlation analysis revealed differences in inter-plasticiser, and plasticiser and biomarker relationships, with loss or reversal in T2D compared to controls. Mono-n-butyl phthalate (MnBP) levels were higher in T2D (p = 0.04); however, regression analysis revealed significant association with age. The GLM analyses demonstrated marked differences in the levels of mono(3-carboxypropyl) phthalate (MCPP), mono(2-ethyl-5-carboxypentyl) phthalate (MECPP), monoethyl phthalate (MEP) and bisphenol S (BPS), with lower levels in T2D versus controls (B = −3.41, p = 0.01; B = −5.28, p < 0.001; B = −8.94, p < 0.001; B = −6.09, p = 0.006, respectively); however, these contrasts appeared to be substantially confounded by BMI and/or age. Positive influence of age and negative influence of BMI when observed across the full dataset were generally reversed in T2D. Levels were complementary to those previously reported for the Middle East. Conclusions: The study indicates the phthalate levels in Bahrain are elevated though complementary to studies of phthalates in the Middle East; within those levels, the study indicates differential exposure–response relationships with plasticisers, influenced by age and BMI, in those with T2D compared to healthy controls. Full article

Lung cancer (LC) remains the leading cause of cancer-related death worldwide, largely due to late-stage diagnosis and the limited performance of current screening strategies. In this preliminary study, headspace solid-phase microextraction coupled with gas chromatography–mass spectrometry (HS-SPME/GC-MS) was used to comprehensively characterize the urinary volatilome of LC patients and healthy controls (HCs), with the dual aim of defining an LC-associated volatilomic signature and identifying volatile organic metabolites (VOMs) with discriminatory potential. A total of 56 VOMs spanning multiple chemical classes were identified, revealing a distinct metabolic footprint between groups. LC patients exhibited markedly increased levels of terpenoids and aldehydes, consistent with heightened oxidative stress, including lipid peroxidation, and perturbed metabolic pathways, whereas HCs showed a predominance of sulphur-containing compounds and volatile phenols, likely reflecting active sulphur amino acid metabolism and/or microbial-derived processes. Multivariate modelling using partial least squares-discriminant analysis (PLS-DA, R² = 0.961; Q² = 0.941; p < 0.001), supported by hierarchical clustering, demonstrated robust and clearly separated group stratification. Among the detected VOMs, octanal, dehydro-p-cymene, 2,6-dimethyl-7-octen-2-ol and 3,7-dimethyl-3-octanol displayed the highest discriminative power, emerging as promising candidate urinary biomarkers of LC. These findings provide proof-of-concept that HS-SPME/GC-MS-based urinary volatilomic profiling can capture disease-specific molecular signatures and may serve as a non-invasive approach to support the early detection of LC, warranting validation in independent cohorts and integration within future multi-omics diagnostic frameworks. Full article

Background: Persistent liver pathology despite a sustained virologic response (SVR) to hepatitis C virus (HCV) therapy is a major clinical concern. This is particularly relevant for people with HIV (PWH) with HCV coinfection, a population prone to accelerated liver disease progression. This study aimed to characterize the plasma miRNA profile in PWH with cirrhosis one year after successful completion of HCV therapy, and to explore their relationship with metabolite alterations. Methods: This cross-sectional study enrolled 47 PWH who achieved HCV clearance with antiviral therapy. Using plasma samples collected approximately one year after completion of HCV therapy, participants were stratified into two groups based on liver stiffness measurement (LSM): compensated cirrhosis (n = 32, LSM ≥ 12.5 kPa) and non-cirrhosis (n = 15, LSM < 12.5 kPa). Plasma miRNAs and metabolites were determined using small RNA sequencing and untargeted capillary electrophoresis-mass spectrometry (CE-MS), respectively. Significantly differentially expressed (SDE) miRNAs were identified using generalized linear models (GLM) with a negative binomial distribution, and their correlation with metabolite levels was quantified using Spearman’s correlation. Results: In the cirrhosis group (n = 32), we identified a distinct signature of 15 SDE miRNAs (9 upregulated, 6 downregulated) compared to the non-cirrhotic group (n = 15), showing hsa-miR-10401-3p, hsa-miR-548ak, hsa-miR-141-3p, and hsa-miR-3940-3p the largest expression changes. miRNA-gene interaction and pathway enrichment analysis suggested that these 15 SDE miRNAs potentially regulate multiple genes involved in immune response and amino acid metabolism. In addition, correlation analyses with our metabolomic data revealed significant associations between specific SDE miRNAs and amino acids and their derivatives. Specifically, the expression of upregulated miRNAs (e.g., hsa-miR-10401-3p and hsa-miR-16-5p) was positively correlated with plasma levels of L-methionine and its derivatives, while downregulated miRNAs (e.g., hsa-miR-625-5p) were inversely correlated with L-tryptophan. Conclusions: In cirrhotic PWH with history of HCV coinfection, a distinct plasma miRNA signature linked to dysregulated amino acid metabolism is found one year after completion of HCV therapy. This underscores that the HCV cure does not equate to complete hepatic recovery, highlighting the critical need for long-term monitoring in this high-risk population. Full article

Allium tuberosum, commonly known as garlic chives, is a promising species with significant antioxidant and anti-inflammatory properties, useful both fresh and dried as a spice. This study analyzed the chlorophyll, carotenoid, polyphenol content, and antioxidant activity in various parts of two- and three-year-old garlic chives, including green stems, inflorescences, and flowering shoots. The research found that flowering shoots had higher levels of chlorophylls and carotenoids, while inflorescences were rich in total polyphenols and exhibited the highest antioxidant activity. Essential oils extracted from different parts of the plant were analyzed using gas chromatography–mass spectrometry (GC–MS), revealing distinct chemical profiles. The oils contained unique compounds, with oxygenated monoterpenes predominant in green stems and stems with flower buds, and aliphatic hydrocarbons more prevalent in inflorescences. This study highlights the high antioxidant potential of Allium tuberosum and suggests further research due to its varied chemical composition across different plant parts. Full article

The fall armyworm (FAW), Spodoptera frugiperda, poses a major threat to global maize production. Reliance on synthetic pesticides has contributed to pest resistance and environmental degradation, underscoring the need for sustainable alternatives. In this study, ethanolic extracts of neem (Azadirachta indica) and moringa (Moringa oleifera), together with maize-associated bacterial isolates, were evaluated for their biocontrol potential against fall armyworm. Gas chromatography-mass spectrometry (GC-MS) analysis for bioextract identification revealed tissue-specific chemical diversity, identifying eight key phytochemicals, including octadecanoic acid, trimethyl fluorosilane, and hexadecanoic acid in neem, and trimethyl fluorosilane, ethyl oleate, ethyl (9Z,12Z), octadecanoic acid, and benzenedicarboxylic acid in moringa extracts. Eighty-nine bacterial isolates were screened for extracellular enzyme activities (cellulase, chitinase, glucanase, and protease) and siderophore production, among which four strains, DR-55 (Bacillus subtilis), HL-7 (Bacillus cereus), HL-37 (Bacillus cereus), and DR-63 (Enterobacter sp.), exhibited >50% biocontrol efficacy under greenhouse conditions. A strong correlation (r = 0.88) was observed between in vitro antagonistic activity and greenhouse performance, validating the screening approach. Fall armyworm mortality was the highest in larvae (up to 80%), moderate in pupae (15–17%), and the lowest in adults (6–7%), respectively. Overall, plant bio-extracts and maize-associated microbial isolates represent a promising, non-hazardous strategy for sustainable fall armyworm management while preserving maize plant health. Full article

To investigate the treatment performance of a CuTiO₃ photocatalytic system for organic peroxide production wastewater under visible light, CuTiO₃ powder prepared through the hydrothermal method was used for this experiment. The light absorption properties of the CuTiO₃ catalyst were analyzed using UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effects of the initial pH, photocatalyst dosage, light intensity, and reaction duration on the photocatalytic reaction were examined. Before and after the reaction, the changes in pollutant components in water were characterized via three-dimensional excitation–emission matrix fluorescence spectrometry (3D-EEM) and gas chromatography–mass spectrometry (GC-MS); the changes in the concentrations of some pollutants were analyzed via wavelength scanning. The results indicated that CuTiO₃ has a good response to visible light. Under the optimized conditions (initial pH = 5, CuTiO₃ dosage = 1.2 g/L, light intensity = 1300 W/m², duration = 4 h), the COD removal rate reached 58%, and the B/C (BOD₅/COD) ratio of wastewater increased from 0.112 to 0.221, demonstrating a good pretreatment effect. GC-MS analysis demonstrated significant degradation effects on amide and hydride substances. Radical capture experiments verified hydroxyl radicals as the dominant species in CuTiO₃ photocatalysis. Visible-light photocatalysis using CuTiO₃ provides an efficient pretreatment pathway for organic peroxide production wastewater. Full article

Gold nanoparticles (Au-NP) are frequently used as model nanomaterials to study nanoparticle behavior in plants due to their analytical detectability and negligible natural background in plant tissues. However, the feasibility of visualizing the spatial distribution of foliar-applied Au-NP at low exposure levels using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains insufficiently explored. In this study, commercially sourced Au-NP were applied to lentil leaves (Lens culinaris var. Beluga) at a low concentration of 0.5 mg·L⁻¹ using a controlled leaf submersion approach. Leaves were sampled at 1 h, 24 h, and 96 h post-exposure and analyzed by LA-ICP-MS imaging to assess time-dependent changes in gold-associated spatial signals, and to compare elemental distribution patterns with non-exposed controls. Untreated control leaves showed no detectable gold at any sampling time point, confirming negligible native Au background. In treated leaves, LA-ICP-MS imaging revealed an initially localized Au hotspot at 1 h, followed by progressive Au redistribution toward the leaf margins and petiole region by 24 h and 96 h. Gold signals persisted over the full 96 h period, indicating stable association of Au-NP with leaf tissue. Comparative elemental mapping of Ca, Mg, K, P, Fe, Zn, and Cu showed no persistent differences in spatial distribution patterns between treated and control leaves as detectable by LA-ICP-MS. This study demonstrates the feasibility of LA-ICP-MS imaging for visualizing the deposition and temporal spatial redistribution of low-dose foliar-applied nanoparticles in intact leaves. The results provide a methodological reference for future hypothesis-driven studies that apply nanoparticles under more controlled conditions, include increased replication, and combine multiple analytical techniques. Full article