Search Results (57)

This study employed computational methods to investigate the basicity of a series of polyfluorinated phosphanes. Results revealed an exceptionally low basicity, with the computed pK_aH values in acetonitrile approaching −30, a value significantly lower than anticipated. The good agreement between the SMD and COSMO-RS methods provided confidence in the reliability of these values. This unexpected behavior challenges conventional perceptions of phosphane basicity and deepens our understanding of the electronic effects of fluorination. The findings hold important implications for catalysis, ligand design, and main-group chemistry, where a precise comprehension of phosphane electronic properties is crucial. pK_aH(MeCN) values, gas-phase basicities, and steric parameters are reported for 14 phosphanes. Full article

Background and Objectives: The imminent threat of antibiotic resistance has spurred studies of nonconventional antimicrobial approaches. Gallium utilization is a promising and emerging approach to treating a variety of resistant bacteria using “Trojan horse” strategies to disrupt iron-dependent processes and biofilms. This study utilized experimental evolution to test the evolvability of gallium resistance in Staphylococcus aureus and resistance traits potentially correlated with metals, antibiotics and polyfluorinated compounds, as well as its genomics foundations. Methods: Whole-genome sequencing was utilized to reveal functional networks of mutations associated with gallium resistance. Additionally, scanning electron microscopy (SEM) observation was utilized to visualize distinct morphological changes on the surface of gallium-resistant populations and compare with the control populations. Results: As demonstrated by these studies, S. aureus evolved resistance to gallium after 20 days of selection. Furthermore, these populations displayed resistance traits correlated with heavy metals and polyfluorinated compounds. In contrast, the gallium-resistant populations were very sensitive to antibiotics. Whole-genome analysis revealed significant polymorphisms in the gallium (III)-resistant populations for example, polymorphisms in staphyloferrinA export MFS transporter/D ornithine citrate ligase (sfaA/sfaD), teichoic acid D Ala esterase (fmtA), DUF3169 family protein (KQ76_RS01520) and adenine phosphoribosyltransferase (KQ76_RS08360), while polymorphisms in the ABC transporter permease subunit (pstC) and acyltransferase family protein (KQ76_RS04365) were unique to the control populations. The polymorphisms directly affected the cells’ morphology. SEM images showed significant external ultrastructural changes in the gallium-selected bacterial cells compared to the control cells. Conclusions: Our study confirmed that using gallium as an antimicrobial can have significant health and environmental implications. Full article

Chemicals in personal care and consumer products are suspected to disrupt endocrine function and affect reproductive health. However, the link between mixed exposure and long-term amenorrhea is not well understood. This study analyzed data from 684 women (2013–2018 National Health and Nutrition Examination Survey) to assess exposure to eight polyfluorinated alkyl substances (PFASs), 15 phthalates (PAEs), six phenols, and four parabens. Various statistical models for robustness tests and mediation analysis were used to explore associations with long-term amenorrhea and the role of serum globulin. Biological mechanisms were identified through an integrated strategy involving target analysis of key chemicals and long-term amenorrhea intersections, pathway analysis, and target validation. Results showed that women with long-term amenorrhea had higher exposure levels of Perfluorodecanoic acid, Perfluorohexane sulfonic acid (PFHxS), Perfluorononanoic acid, n-perfluorooctanoic acid (n_PFOA), n-perfluorooctane sulfonic acid, and Perfluoromethylheptane sulfonic acid isomers. Logistic regression with different adjustments consistently found significant associations between elevated PFAS concentrations and increased long-term amenorrhea risk, confirmed by Partial Least Squares Discriminant Analysis. Mediation analysis revealed that serum globulin partially mediated the relationship between PFAS exposure and long-term amenorrhea. Network and target analysis suggested that PFHxS and n_PFOA may interact with Signal Transducer and Activator of Transcription 3 (STAT3). This study highlights significant associations between PFAS exposure, particularly PFHxS and n_PFOA, and long-term amenorrhea, with serum globulin and STAT3 serving as mediators in the underlying mechanisms. Full article

The carbonylation at the benzyl C-Hal bonds (Hal = F, Cl) of a number of polyfluorinated alkylbenzenes and benzocycloalkenes using carbon monoxide in the presence of SbF₅ is described. The reaction provided the corresponding α-arylcarboxylic acids or their methyl esters following aqueous or methanol treatment. The products of double carbonylation were obtained from bis(chloromethyl)tetrafluorobenzenes and benzal fluorides. For benzal chloride derivatives, the possibility of selective mono- or dicarbonylation was shown to depend on the amount of antimony pentafluoride. In the case of polyfluorinated secondary benzyl halides with a hydrogen atom at the α-carbon atom and vicinal fluorine atoms, the addition of CO was found to be accompanied by the elimination of HF, resulting in α,β-unsaturated α-arylcarboxylic acids. The double elimination of HF during the carbonylation of 1,4-dichloro-2,2,3,3,5,6,7,8-octafluorotetralin yielded dimethyl perfluoronaphthalene-1,4-dicarboxylate. Full article

This comprehensive review reports on concentrations, sources, emissions, and potential health effects from Semi-Volatile Organic Compounds (SVOCs) identified in the internal home environment in European residences. A total of 84 studies were identified, and concentrations were collated for inhalation exposure from dust, air and aerosol. A total of 298 individual SVOCs were identified and 67 compounds belonging to eight chemical classes: phthalates, flame retardants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), per- and polyfluorinated alkyl substances (PFAS), biocides, bisphenols and musks were prioritised. Phthalates are the most abundant SVOCs with DEHP being the most abundant in both the dust and aerosol phases (WAGMs 426.4 μg g⁻¹ and 52.2 ng m⁻³, respectively) followed by DBP for dust (WAGMs are 95.9 μg g⁻¹). In the air, the most abundant SVOCs are DiBP (284.1 ng m⁻³), DBP (179.5 ng m⁻³), DEHP (106.2 ng m⁻³) and DMP (27.79 ng m⁻³). Chemicals from all SVOC categories are emitted from building and construction materials, furnishings and consumer products, especially phthalates. Both legacy chemicals and their alternatives were detected. Complexities of reporting on SVOCs included differing sampling methodologies, multiple standards in their definition, lack of industry data, and toxicological data focused primarily on ingestion not inhalation exposures. Further research is recommended to develop the evidence base for potential health effects including via inhalation, reporting of emission rates and undertaking future monitoring studies. Full article

Per- and polyfluoroalkyl substances (PFAS) are contaminants that can lead to adverse health effects in aquatic organisms, including reproductive toxicity and developmental abnormalities. To assess the ecological health risk of PFAS in Pennsylvania stream surface water, we conducted a comprehensive analysis that included both measured and predicted estimates. The potential combined exposure effects of 14 individual PFAS to aquatic biota were estimated using the sum of exposure-activity ratios ($\Sigma$EARs) in 280 streams. Additionally, machine learning techniques were utilized to predict potential PFAS exposure effects in unmonitored stream reaches, considering factors such as land use, climate, and geology. Leveraging a tailored convolutional neural network (CNN), a validation accuracy of 78% was achieved, directly outperforming traditional methods that were also used, such as logistic regression and gradient boosting (accuracies of ~65%). Feature importance analysis highlighted key variables that contributed to the CNN’s predictive power. The most influential features highlighted the complex interplay of anthropogenic and environmental factors contributing to PFAS contamination in surface waters. Industrial and urban land cover, rainfall intensity, underlying geology, agricultural factors, and their interactions emerged as key determinants. These findings may help to inform biotic sampling strategies, water quality monitoring efforts, and policy decisions aimed to mitigate the ecological impacts of PFAS in surface waters. Full article

Anesthetic gases represent a small but significant portion of the environmental impact of health care in many countries. These compounds include several fluorocarbons commonly referred to as “fluranes”. The fluranes are greenhouse gases (GHG) with global warming potentials in the hundreds to thousands and are also PFAS compounds (per- and polyfluorinated alkyl substances) according to at least one definition. Nitrous oxide (N₂O) is sometimes used as an adjunct in anesthesia, or for sedation, but has a significant stratospheric ozone depletion potential as well as GHG effects. Reducing emissions of these compounds into the environment is, therefore, a growing priority in the health care sector. Elimination or substitution of the highest impact fluranes with alternatives has been pursued with some success but limitations remain. Several emission control strategies have been developed for fluranes including adsorption onto solids, which has shown commercial promise. Catalytic decomposition methods have been pursued for N₂O emission control, although mixtures of fluranes and N₂O are potentially problematic for this technology. All such emission control technologies require the effective scavenging and containment of the anesthetics during use, but the limited available information suggests that fugitive emissions into the operating room may be a significant route for unmitigated losses of approximately 50% of the used fluranes into the environment. A better understanding and quantification of such fugitive emissions is needed to help minimize these releases. Further cost–benefit and techno-economic analyses are also needed to identify strategies and best practices for the future. Full article

In this work, a novel optical–chemical sensor for the detection of per- and polyfluorinated substances (PFASs) in a real scenario is presented. The proposed sensing approach exploits the multimode characteristics of plastic optical fibers (POFs) to achieve unconventional sensors via surface plasmon resonance (SPR) phenomena. The sensor is realized by the coupling of an SPR-POF platform with a novel chemical chip based on different polymeric nanolayers over the core of a D-shaped POF, one made up of an optical adhesive and one of a molecularly imprinted polymer (MIP) for PFAS. The chemical chip is used to launch the light into the SPR D-shaped POF platform, so the interaction between the analyte and the MIP’s sites can be used to modulate the propagated light in the POFs and the SPR phenomena. Selectivity tests and dose–response curves by standard PFOA water solutions were carried out to characterize the detection range sensor response, obtaining a wide PFAS response range, from 1 ppt to 1000 ppt. Then, tests performed on river water samples collected from the Bormida river paved the way for the applicability of the proposed approach to a real scenario. Full article

Concerns over the life cycle impacts of fluoropolymers have led to their inclusion in broad product restriction proposals for per- and poly-fluorinated alkyl substances (PFAS), despite their non-bioavailable properties and low exposure potential in complex, durable goods such as non-consumer electrical products. Based on the hypothesis that manufacturers are most able to manage the environmental impacts of their products, practical engineering approaches to implementing life cycle fluoropolymer stewardship are evaluated to bridge the ongoing debate between precautionary and risk-based approaches to PFAS management. A life cycle thinking approach is followed that considers product design and alternatives, as well as the product life cycle stages of material sourcing, manufacturing, field deployment, and end-of-life. Over the product life cycle, the material sourcing and end-of-life stages are most impactful in minimizing potential life cycle PFAS emissions. Sourcing fluoropolymers from suppliers with fluorosurfactant emissions control and replacement minimizes the potential emissions of bio-available PFAS substances. A stack-as-service approach to electrolyzer operations ensures a takeback mechanism for the recycling of end-of-life fluoropolymer materials. Retaining electrolytic hydrogen’s license to operate results in over USD 2 of environmental and health benefits per kilogram of hydrogen produced from reduced greenhouse gas and air pollutant emissions compared to conventional hydrogen production via steam methane reforming. Full article

6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) exhibits pronounced estrogenic effects, potentially influencing the etiology of lung cancer. This study assessed the potential associations between serum concentrations of 6:2 Cl-PFESA and lung cancer risk at the population level. Odds ratios (ORs) for lung cancer across serum 6:2 Cl-PFESA quartiles were assessed using conditional logistic regression. Additionally, we investigated potential effect modification by various confounding factors. Elevated serum levels of 6:2 Cl-PFESA were consistently associated with an increased risk of lung cancer in both the crude model (OR = 1.62, 95% CI: 1.08–2.42, p = 0.018) and the adjusted model (OR = 1.59, 95% CI: 1.06–2.39, p = 0.026). Stratified analyses revealed that elevated serum levels of 6:2 Cl-PFESA were associated with increased risk estimates of lung cancer among males (adjusted OR = 2.04, 95% CI: 1.19–3.51, p = 0.006), smokers (adjusted OR = 2.48, 95% CI: 1.25–4.89, p = 0.003), and drinkers (adjusted OR = 2.20, 95% CI: 0.94–5.16, p = 0.049). The results of this study imply that exposure to 6:2 Cl-PFESA at levels considered environmentally relevant may be linked to an elevated risk of developing lung cancer. Full article

Immunomodulatory imide drugs (IMiDs) play a crucial role in the treatment landscape across various stages of multiple myeloma. Despite their evident efficacy, some patients may exhibit primary resistance to IMiD therapy, and acquired resistance commonly arises over time leading to inevitable relapse. It is critical to develop novel therapeutic options to add to the treatment arsenal to overcome IMiD resistance. We designed, synthesized, and screened a new class of polyfluorinated thalidomide analogs and investigated their anti-cancer, anti-angiogenic, and anti-inflammatory activity using in vitro and ex vivo biological assays. We identified four lead compounds that exhibit potent anti-myeloma, anti-angiogenic, anti-inflammatory properties using three-dimensional tumor spheroid models, in vitro tube formation, and ex vivo human saphenous vein angiogenesis assays, as well as the THP-1 inflammatory assay. Western blot analyses investigating the expression of proteins downstream of cereblon (CRBN) reveal that Gu1215, our primary lead candidate, exerts its activity through a CRBN-independent mechanism. Our findings demonstrate that the lead compound Gu1215 is a promising candidate for further preclinical development to overcome intrinsic and acquired IMiD resistance in multiple myeloma. Full article

This study introduces an innovative approach to enhancing membrane distillation (MD) performance by developing bead-containing superhydrophobic sulfonated polyethersulfone (SPES) nanofibers with S-MWCNTs. By leveraging SPES’s inherent hydrophobicity and thermal stability, combined with a nanostructured fibrous configuration, we engineered beads designed to optimize the MD process for water purification applications. Here, oxidized hydrophobic S-MWCNTs were dispersed in a SPES solution at concentrations of 0.5% and 1.0% by weight. These bead membranes are fabricated using a novel electrospinning technique, followed by a post-treatment with the hydrophobic polyfluorinated grafting agent to augment nanofiber membrane surface properties, thereby achieving superhydrophobicity with a water contact angle (WCA) of 145 ± 2° and a higher surface roughness of 512 nm. The enhanced membrane demonstrated a water flux of 87.3 Lm⁻² h⁻¹ and achieved nearly 99% salt rejection efficiency at room temperature, using a 3 wt% sodium chloride (NaCl) solution as the feed. The results highlight the potential of superhydrophobic SPES nanofiber beads in revolutionizing MD technology, offering a scalable, efficient, and robust membrane for salt rejection. Full article

Per- and polyfluorinated alkyl substances (PFASs) are a group of anthropogenic chemicals used in a range of industrial processes and consumer products. Recently, their ubiquitous presence in the environment as well as their toxicological effects in humans have gained relevant attention. Although the occurrence of PFASs is widely investigated in scientific community, the standardization of analytical method for all matrices still remains an important issue. In this review, we discussed extraction and detection methods in depth to evaluate the best procedures of PFAS identification in terms of analytical parameters (e.g., limits of detection (LODs), limits of quantification (LOQs), recoveries). Extraction approaches based on liquid–liquid extraction (LLE), alkaline digestion, and solid phase extraction (SPE), followed by liquid chromatography–mass spectrometry (LC-MS) and gas chromatography–mass spectrometry (GC-MS) analysis are the main analytical methods applied in the literature. The results showed detectable recoveries of PFOA and PFOS in meat, milk, vegetables, eggs products (90.6–101.2% and of 89.2–98.4%), and fish (96–108%). Furthermore, the low LOD and LOQ values obtained for meat (0.00592–0.01907 ng g⁻¹; 0.050 ng g⁻¹), milk (0.003–0.009 ng g⁻¹; 0.010–0.027 ng g⁻¹), fruit (0.002–0.009 ng g⁻¹; 0.006–0.024 ng g⁻¹), and fish (0.00369–0.017.33 ng g⁻¹; 0.05 ng g⁻¹) also confirmed the effectiveness of the recent quick, easy, cheap, effective, rugged, and safe method (QuEChERS) for simple, speedy, and sensitive ultra-trace PFAS analysis. Full article

In this study, particle loading, polyfluorinated alkyl silanes (PFAS or FAS) content, superhydrophobicity, and crack formation for nanocomposite coatings created by the spray coating process were investigated. The formulations comprised hydrophobic silica, epoxy resin, and fluorine-free or FAS constituents. The effect of FAS content and FAS-free compositions on the silica and epoxy coatings’ chemistry, topography, and wetting properties was also studied. All higher particle loadings (~30 wt.%) showed superhydrophobicity, while lower particle loading formulations did not show superhydrophobic behavior until 13% wt. FAS content. The improved water repellency of coatings with increased FAS (low particle loadings) was attributed to a combination of chemistry and topography as described by the Cassie state. X-ray photoelectron spectroscopy (XPS) spectra showed fluorine enrichment on the coating surface, which increases the intrinsic contact angle. However, increasing the wt.% of FAS in the final coating resulted in severe crack formation for higher particle loadings (~30 wt.%). The results show that fluorine-free and crack-free coatings exhibiting superhydrophobicity can be created. Full article

The widespread use and impervious nature of per- and polyfluorinated alkyl substances (PFASs) is leading to potentially harmful exposure in numerous environments. One avenue to explore remediation of PFAS-contaminated environments involves investigating how well PFASs adsorb onto various substrates. In the current review, we focus on summarizing recent computational research, largely involving density functional theory (DFT) and molecular dynamics (MD), into the adsorption and interaction of PFASs with a variety of substrates with an aim to provide insight and inspire further research that may lead to solutions to this critical problem that impacts the environment and human health. Full article