Search Results (896)

We present a modular building block strategy for synthesizing phosphonated polyaromatic systems as an alternative to the conventional late-stage phosphonation of prefabricated aromatic scaffolds, which often requires harsh conditions and has limited tolerance for functional groups. A monophosphonated biphenyl building block was obtained via nickel-catalyzed phosphonation of dibromobiphenyl at 170 °C for three hours. This synthesis is more economical and milder than typical high-temperature palladium systems. In parallel, a borated pyrene derivative was prepared by Suzuki–Miyaura borylation. The final palladium-catalyzed Suzuki cross-coupling reaction produced the target compound, octaethyl(pyrene-tetrakis(biphenyl))tetrakis(phosphonate), Et₈-PyTPPE. Single-crystal X-ray diffraction reveals a centrosymmetric molecule that crystallizes in the triclinic space group P–1, with the inversion center located at the central C–C bond of the pyrene core. The pyrene unit is essentially planar, while the biphenylphosphonate arms are highly twisted relative to the core and to each other. The crystal packing is dominated by weak intermolecular interactions, and no significant π–π stacking is observed. Hirshfeld surface analysis shows that H···H (60.5%) and C···H (22.5%) contacts predominate, while O···H interactions (14.4%) with phosphoryl oxygen atoms represent the most relevant directed contacts. From photophysical investigations, Et₈-PyTPPE exhibits blue fluorescence (λ_em. = 452 nm) in solution and aggregation-induced red-shifted emission with nanosecond lifetimes in the solid state, confirming purely fluorescent behavior. Full article

A simple, rapid, and cost-effective method for the determination of benzo[a]pyrene (BaP) in edible oil was developed and validated. Nickel oxide-deposited silica (SiO₂@NiO) was employed as a solid-phase extraction (SPE) adsorbent for the extraction of BaP from edible oil, followed by high-performance liquid chromatography–diode array detector (HPLC-DAD) analysis of BaP. The edible oil was diluted with n-hexane and directly loaded to SiO₂@NiO for SPE. The n-hexane was also used to clean the fat-soluble interference substance in the edible oil, and BaP was selectively captured using SiO₂@NiO through the electron donor–acceptor interaction. The SPE conditions, including the amount of adsorbent, volume of washing solvent, and type and volume of desorption solvent, were optimized. This SiO₂@NiO-based SPE coupled with the HPLC-DAD method demonstrated good linearity within a BaP concentration range of 6–1875 ng/g in edible oils, with a limit of detection of 1.3 ng/g, spiked recovery of 97.4–105.1%, and relative standard deviation (RSD) of <3.0%. The method was applied to the analysis of BaP in 11 real oil samples (soybean oil, olive oil, corn germ oil, flaxseed oil, walnut oil, sunflower kernel oil, peanut oil, unrefined oil, and high-temperature frying oil), and the results show that the unrefined oil and high-temperature frying oil were at risk of BaP exceeding acceptable level. Full article

This investigation was conducted in order to gain a first knowledge of concentrations, distribution patterns, and potential sources of 16 US EPA priority polycyclic aromatic hydrocarbons (PAHs) and organic molecular tracer compounds in deposition dust samples collected in the Valparaiso region, Chile. Dust was sampled in schools (indoor and outdoor) that are located in Puchuncaví and Quintero. Source apportionment analysis using the concentrations of PAHs; glucose, mannitol, sucrose, fructose; di-2-ethylhexyl phthalate; hopanes, and levoglucosan as molecular tracer compounds showed three sources of contribution. The first (46.38%) was related to incomplete combustion processes (Acy, Flu, Ant, Flt, Pyr, and BaA), a second source (20%) represented soil+ biomass burning (levoglucosan, α glucose, β glucose, mannitol, sucrose, and fructose), and a third source (10.26%) was dominated only by 27_norhopane, 27_hopane, which are related to traffic. To assess potential health risks for schoolchildren, the study calculated the benzo[a]pyrene equivalent (BaPE) toxicity and the incremental lifetime cancer risk (ILCR). Toxicity equivalent (TEQ) results showed that the main contributor to overall toxicity in PAHs, especially in schools located in Puchuncaví, was benzo[a]pyrene (BaP), followed by benzo[α]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), indeno[1,2,3-cd] pyrene (IcdP), and dibenzo[a,h]anthracene (DahA). According to the calculated ILCR values, the highest cancer risk was associated with dust ingestion (both indoor and outdoor) for ∑16PAHs, ranging from 1.14 × 10⁻³ to 8.88 × 10⁻⁴. This was followed by dermal contact (1.27 × 10⁻⁵ to 7.27 × 10⁻⁷) and inhalation (1.22 × 10⁻⁸ to 9.99 × 10⁻⁹). Full article

The ovaries are crucial reproductive organs that regulate the menstrual cycle and support pregnancy through the production of steroid hormones. They are highly susceptible to various environmental pollutants, which can lead to ovarian disorders. Luteal phase defect (LPD) and premature ovarian failure (POF) are common ovarian disorders in women. In this study, we integrate network toxicology with molecular docking and molecular dynamics simulations to elucidate the toxicological mechanisms of Benzo(a)pyrene (BaP), a widespread endocrine disruptor, in LPD and POF. Through systematic data mining of the GeneCards and OMIM databases, we identified 1336 targets associated with LPD and 2066 targets related to POF, as well as 220 BaP targets. Venn diagram analysis revealed 36 potential targets for BaP-induced LPD and 43 for BaP-induced POF. GO and KEGG enrichment analyses suggest that BaP-induced LPD and POF may share toxicological mechanisms. PPI network visualization indicated that EGFR, ESR1, and STAT3 are critical common targets for BaP-induced LPD and POF. Molecular docking and molecular dynamics simulations revealed that BaP exhibits strong binding affinity with all three core genes. In KGN cells modeling LPD and POF phenotypes, cellular experiments confirmed that BaP downregulated EGFR and ESR1 expression while upregulating STAT3 expression, thereby supporting the reliability of these targets in BaP-induced ovarian dysfunction. These findings provide insights into BaP-induced reproductive toxicity and offer a foundation for targeted clinical interventions to mitigate the effects of environmental pollutants on women’s reproductive health. Full article

Benzo(a)pyrene (B[a]P) is a pervasive freshwater pollutant, yet its toxicity to the fish gallbladder remains poorly understood. This study investigated the toxicological impacts of 2.5 and 25 μg/L B[a]P on common carp (Cyprinus carpio) using histological, transcriptomic, and single-cell RNA sequencing (scRNA-seq) analyses. Results showed that the gallbladder is a primary site for B[a]P accumulation. High B[a]P concentrations caused vacuolar degeneration of mucosal epithelial cells and nuclear deformities. Transcriptomic analysis revealed that B[a]P stress triggered autoimmune homeostasis imbalance and overinhibited apoptosis. scRNA-seq identified cellular heterogeneity changes, specifically T-cell impairment and epithelial cell (EC) proliferation. Mechanistically, T-cell reduction was linked to the T-cell 2 subset, while EC proliferation involved EC 0 and EC 4 subsets, all participating in the apoptosis pathway. These findings demonstrate that the apoptosis pathway is a key target of B[a]P toxicity in the gallbladder. This work provides a cellular-level framework for assessing environmental polycyclic aromatic hydrocarbon (PAH) risks in aquaculture. Full article

P-glycoprotein (P-gp) is an ATP-dependent efflux transporter that contributes to cellular defense by exporting xenobiotics. While well characterized in mammals, its inducibility and physiological regulation in fish remain poorly understood. This study examined the functional induction of P-gp in juvenile rainbow trout (Oncorhynchus mykiss) hepatocytes following xenobiotic exposure and assessed how energy status (fed vs. fasted) influences both basal and inducible efflux activity. In vivo exposure to clotrimazole, dexamethasone, benzo[a]pyrene, and rifampicin significantly reduced rhodamine 123 (R123) accumulation in hepatocytes, indicating enhanced P-gp activity. Clotrimazole elicited the strongest response, with effects evident by day 3. Induction was dose-dependent and plateaued at doses ≥ 4 mg/kg. A single injection produced transient P-gp activity, while repeated exposures sustained efflux for 28 days. Fasting led to increased R123 accumulation, indicating suppressed basal P-gp function, though inducibility was retained but attenuated. These findings confirm that P-gp is inducible in trout and modulated by nutritional state. This functional plasticity has ecological relevance, as contaminant exposure during energetically limited periods (e.g., migration, overwintering) may compromise chemical defense. Understanding these trade-offs is key to assessing the resilience of wild fish to pollution stressors. Full article

Polymer films and polymer blend films are widely used as functional materials; however, their photophysical behavior cannot be fully explained solely by bulk properties such as relative permittivity or glass transition temperature. In this study, we investigate how local polymer microenvironments regulate fluorescence responses by employing two strongly emissive solvatochromic dyes—FπPCM, a D–π–A-type π-conjugation-extended fluorene dye, and PK, a D–π–A-type pyrene dye—as molecular probes. The photophysical properties of these dyes were systematically examined in a series of transparent polymer matrices, including polystyrene, polycarbonate, poly(methyl methacrylate), poly(vinyl chloride), triacetylcellulose, poly(butyl methacrylate), and poly(2-ethyl-2-oxazoline). Polymer films containing the dyes were prepared by solution casting from homogeneous polymer–dye solutions onto quartz substrates followed by solvent evaporation. Both dyes exhibited polymer-dependent variations in fluorescence wavelength, quantum yield, and lifetime, reflecting not only differences in polymer polarity but also local chain packing and specific dye–polymer interactions. Fluorescence lifetime analysis of PS/POz blend films revealed microscopic heterogeneity even in miscible systems, quantitatively captured using averaged lifetime parameters. Temperature-dependent fluorescence measurements further demonstrated that thermal history and structural relaxation significantly influence local polymer environments. In particular, ratiometric fluorescence analysis of PMMA/PBMA blend films enabled reproducible temperature sensing over a wide range from 30 to 120 °C, despite an overall negative temperature response. These results establish solvatochromic dyes as versatile optical probes for evaluating local polymer microenvironments and highlight their potential for polymer-state monitoring and fluorescence-based temperature-sensing applications. Full article

Polycyclic aromatic hydrocarbons (PAHs) are widely prevalent harmful organic pollutants. Enzymatic activities (such as those of dehydrogenases, catalase, protease and urease), as well as the microbial community structure and assembly (through 16S and ITS amplicon sequencing), were evaluated 90 days after PAH contamination and compared to those in normal soils. Microbial activity, as indicated by soil urease, catalase, and protease activities, was inhibited under PAH stress. Furthermore, PAH stress exerted significant impacts on the soil microbial community structure. Notably, PAH stress reduced soil bacterial and fungal biomass and inhibited the abundance of microbial taxa involved in soil carbon and nitrogen cycling (e.g., Marmoricola, Pedobacter, and Streptomyces), along with the majority of predicted responsive metabolic functions, particularly those related to amino acid and carbohydrate metabolism. PAH stress enriched PAH-degrading microorganisms, including Pseudomonas, Mycobacterium, Bacillus, Cycloclasticus, and Flavobacterium. The niche breadth of bacterial and fungal communities decreased significantly under PAH stress (51.5 and 14.1, respectively) compared to that in normal soil (63.7 and 22.3), which was further supported by Beta Nearest Taxon Index and co-occurrence network analysis. PAH stress increased the contribution of heterogeneous selection to soil microbial assembly (100%) compared to that in normal soil (80%). Thus, the majority of microbial community responses to PAH stress were adversely affected. These results suggest that PAH contamination may profoundly affect the soil quality by restricting the survival space of bacteria and fungi. Full article

Benzo[a]pyrene (BaP), a potent carcinogenic polycyclic aromatic hydrocarbon, is a critical food contaminant originating from environmental deposition and thermal processing, posing a significant threat to public health and driving stringent global regulations. This review critically examines recent advancements in analytical methodologies for BaP determination, giving particular emphasis to sample preparation and detection techniques. The discussion covers the evolution from conventional methods, such as solid-phase extraction, towards more efficient and sustainable approaches, including magnetic, dispersive, and molecularly imprinted solid-phase extraction, as well as microextraction techniques and gel permeation chromatography. For detection, the performance of established chromatographic methods, such as gas chromatography–mass spectrometry (GC-MS) and high-performance liquid chromatography with fluorescence detection (HPLC-FLD), is evaluated against emerging rapid techniques such as sensors, immunoassays, and spectroscopic methods. The analysis reveals that while significant progress has been made in improving sensitivity, selectivity, and throughput, challenges remain in balancing speed with accuracy, managing matrix effects, and translating novel materials from research to routine application. The review concludes by underscoring the necessity for future development to focus on the integration of smart materials, automation, and advanced data science to achieve robust, on-site, and holistic monitoring solutions for ensuring food safety against BaP contamination. Full article

Urban air pollution is a major public health concern, especially in densely populated cities. This problem also includes food safety issues in outdoor retail environments, where fresh products may be exposed to airborne pollutants. This study examines the presence of polycyclic aromatic hydrocarbons (PAHs) on fruits sold at indoor and outdoor locations across Budapest and several Hungarian cities. Results showed higher PAH concentrations on fruit sold outdoors, with benzo[a]pyrene (BAP) exceeding 2 µg/kg in 62% of outdoor samples and in 22% of indoor ones. Washing with water reduced contamination by 40–50% on average, with some samples showing over 65% reduction for BAP. Differences across fruit types were limited overall, though statistically significant for BAP in certain cases, highlighting compound-specific variability. Correlation analysis revealed weak but interpretable associations between PAH levels and ambient air quality indicators, with a moderate correlation for fine particulate matter ≤ 2.5 µm (PM_2.5) (r = 0.4355) and a weaker one for the calculated Air Quality Index (AQI) (r = 0.2148). These findings suggest that while urban microenvironments influence contamination, the general air quality indices may not predict surface PAH burden reliably. The study highlights the role of public wells in enabling citizen-level mitigation through rinsing and calls for integrated urban health strategies considering food exposure alongside infrastructural access. Full article

Transport emissions are a major source of urban polycyclic aromatic hydrocarbons (PAHs), posing risks to human health. While plant leaves and their epiphytic microbes contribute to PAH degradation, how plant traits and environmental factors affect this process remains unclear. This study examined 20 tree species in Beijing’s traffic corridors to explore PAH enrichment on leaves and the structure of phyllospheric bacterial communities. Results show that leaf area, morphology, and sampling height significantly influenced bacterial community assembly. Normalized Stochasticity Ratio (NST) analysis indicated that deterministic processes dominate on medium-sized leaves (11.8–40.1 cm²), simple leaves, and those below 2.3 m or above 3 m in height, whereas stochastic factors prevail on nano leaves, compound leaves, and leaves at low-position (<2.3 m). Although low-molecular-weight PAHs (2–4 rings) were predominant in leaves, Mantel tests revealed significant positive correlations between bacterial communities and high molecular weight PAHs (4–6 rings), such as benz(a)anthracene, benzo[e]pyrene, and picene. Spearman analysis identified 10 dominant bacterial taxa with PAH degradation potential, including Kocuria rosea, Serratia symbiotica, Massilia sp. WG5, and seven unclassified species from Hymenobacter, Sphingomonas, Roseomonas, Curtobacterium, and Deinococcus. Functional Annotation of Prokaryotic Taxa(FAPROTAX) prediction further associated 14 species across six genera, including Acinetobacter, Nocardioides, Gordonia, Rhodococcus, Clostridium_sensu_stricto_18, and Geobacter, with PAH degradation function. This work clarifies the composition and function of phyllospheric PAH-degrading bacteria in an urban traffic environment, offering a theoretical basis for enhancing degradation via bacterial consortia, biosurfactants, and optimized plant selection. Full article

The European Air Quality Directive defines benzo(a)pyrene as the chemical index for polycyclic aromatic hydrocarbon (PAH) carcinogenicity and sets a limit for its concentration in PM₁₀ to address the exposure risk associated with the class. It also mandates monitoring six additional PAHs at a limited number of selected sites to assess the benzo(a)pyrene’s contribution to the class in ambient air. For this aim, as part of the “Reti Speciali” project, benzo(a)pyrene and seven other PAHs were measured at 10 urban sites across Italy in 2016–2019, and the spatial and temporal pattern of these compounds were analyzed to evaluate benzo(a)pyrene’s effectiveness in representing the carcinogenicity of the entire PAH class. Results showed that in Italy, benzo(a)pyrene accounted for 61% ± 4.4% of total carcinogenicity when benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, dibenzo(a-h)anthracene, and indenopyrene were considered, and about 1% less when chrysene and benzo(ghi)perylene were also added. This value varies by site (from 51% ± 11% in Taranto to 66% ± 7.5% in Cosenza) and decreases in summer due to benzo(a)pyrene’s strong photochemical degradation. In Europe, this percentage is generally similar or lower. For instance, in the United Kingdom, across 24 urban sites, it averages 56% ± 2.9%. These findings suggest that benzo(a)pyrene does not represent the overall carcinogenicity of PAHs nor a constant percentage, highlighting the need to further investigate the use of benzo(a)pyrene as the sole marker of PAH toxicity. Full article

Background: Chronic obstructive pulmonary disease (COPD) is a progressive inflammatory lung disorder with limited effective therapies. NRICM102, a traditional multi-herbal formulation originally developed for COVID-19, exhibits anti-inflammatory and immunomodulatory potential. Objectives: The aim of this study was to investigate the therapeutic efficacy of NRICM102 in a COPD-relevant inflammatory lung injury mice model. Methods: Mice were exposed to lipopolysaccharide (LPS) and benzo[a]pyrene (B[a]P) to induce chronic airway inflammation and structural lung damage and treated with NRICM102 (1.5–3.0 g/kg) or dexamethasone. Lung function, histopathology, transcriptomic profiling, and protein expression of key inflammatory markers were assessed. Results: NRICM102 significantly restored LPS+B[a]P-induced enhanced pause (Penh) and arterial oxygen saturation (aO₂%), similar to the effect of dexamethasone. Histological analysis revealed marked alveolar damage, inflammatory cell infiltration, and fibrosis in the model group, all of which were significantly attenuated by NRICM102 in a dose-dependent manner, with high-dose (3.0 g/kg) treatment showing pronounced structural preservation. Transcriptomic profiling revealed that NRICM102, particularly at 3.0 g/kg, partially reversed COPD-associated gene expression patterns, characterized by reduced activation of cytokine signaling, chemokine activity, and antigen presentation pathways. GO, DO, and KEGG enrichment analyses indicated selective modulation of immune-related pathways, with high-dose NRICM102 affecting genes involved in adaptive immunity and cytokine receptor interactions, including a subset of 150 reverted genes. Immunofluorescence analysis confirmed dose-dependent reductions in key inflammatory, immune, and mucus-related markers, including IL-1β, NLRP3, Muc5ac, and MMP12 expression. Conclusions: NRICM102 confers significant protective effects against COPD-relevant inflammatory lung injury by improving pulmonary function, preserving lung architecture, and selectively modulating immune and inflammatory pathways. These results provide preclinical evidence supporting the potential of NRICM102 to modulate inflammation and immune responses associated with COPD-related pathology, although further studies are needed to establish its therapeutic relevance. Full article

Microplastics (MPs) are recognised as emerging vectors for hydrophobic organic contaminants in aquatic environments due to their relatively large surface area and the diversity of their polymer chemistries compositions. This study investigates the sorption behaviour of two priority polycyclic aromatic hydrocarbons (PAHs), pyrene (PYR) and fluoranthene (FLU), onto six common MPs: poly(m-xylene adipamide) (PA-MXD6), high- and low-density polyethylene (HDPE, LDPE), polypropylene (PP), polyethylene terephthalate (PET), and polylactic acid (PLA). Sorption isotherms and kinetics were evaluated under simulated freshwater conditions at environmentally relevant concentrations (1–50 µg·L⁻¹). Despite the low MP concentration used (0.2 g·L⁻¹), over 80% of the initial PAH content was removed by polyolefins, and more than 50% by all other MPs. Sorption capacity was strongly dependent on particle surface area. Langmuir, Henry, and Freundlich isotherms models were fitted, with linear behaviour prevailing at low concentrations. Analysis using the Dubini–-Radushkevich model confirmed that sorption involves chemisorption contributions, mainly through π–π interactions and hydrophobic interactions (polyolefins). Mechanistically, molecular diffusion within the MP matrix was not governing the sorption process, as diffusion coefficients varied with particle size instead of polymer chemistry. Instead, sorption appears to be governed by PAH diffusion through the hydrodynamic boundary layer and subsequent retention on the MP surface. Empirically, kinetic data fitted the pseudo-second-order model, further supporting that the sorption process involves chemisorption. These findings highlight the role of MPs as vectors for PAHs in freshwater systems and their potential application in contaminant removal. Expressing sorption per unit surface area is recommended for accurate assessment. This work contributes to understanding the environmental behaviour of MPs and their implications for pollutant transport and toxicity. Full article

The widespread use of antibiotics, combined with pervasive exposure to diverse environmental media, has intensified the global challenge of antibiotic resistance. Accumulating evidence reveals that beyond direct antibiotic pressure, residual non-antibiotic chemicals—despite lacking intrinsic antibacterial activity—can significantly promote the enrichment and spread of antibiotic resistance genes (ARGs) in farmland soils through indirect mechanisms such as inducing oxidative stress, altering microbial community structure, and enhancing both vertical and horizontal gene transfer. To address this issue, the present study investigates the influence of representative non-antibiotic contaminants commonly detected in agricultural environments—including pesticides (e.g., Omethoate, imidacloprid, and atrazine), industrial pollutants (e.g., PCB138, BDE47, benzo [a] pyrene, 2,3,7,8-tetrachlorodibenzo-p-dioxin [TCDD], and benzene), plastic-associated compounds (e.g., Polyethylene trimer, phthalates, and tributyl acetylcitrate), and ingredients from personal care products (e.g., triclosan and bisphenol A)—on ARG transmission dynamics. Leveraging bioinformatics resources such as the CARD database, PDB, AlphaFold, and molecular sequence analysis tools, we identified relevant small-molecule ligands and macromolecular receptors to construct a simulation system modeling ARG transfer pathways. Molecular docking and molecular dynamics (MD) simulations were then implemented, guided by a Plackett–Burman experimental design, to systematically evaluate the impact of individual and co-occurring pollutants. The resulting data were processed using advanced analytical tools, and MD trajectories were interpreted at the molecular level across three scenarios: an unperturbed (blank) system, single-pollutant exposures, and dual-pollutant combinations. By integrating computational simulations with machine learning approaches, this work uncovers the “co-selection” effect exerted by non-antibiotic chemical residues in shaping the environmental resistome, thereby providing a mechanistic and scientific basis for comprehensive risk assessment of agricultural non-point source pollution and the development of effective soil health management and antimicrobial resistance containment strategies. Full article