Search Results (2,410)

The hydrolase-catalyzed kinetic resolution of fluorinated racemates of 3-arylcarboxylic acids is described. Hydrolysis of ethyl esters of fluorinated acids by esterases and hydrolases in all cases resulted in the formation of hydrolyzed (S)-carboxylic acids and unreacted (R)-esters in high yields and high enantiomeric purity. The influence of separation conditions on the efficiency and enantioselectivity of biocatalytic conversion was also studied. The reactions were carried out under normal conditions (stirring with a magnetic stirrer at room temperature) and microwave irradiation in the presence of hydrolases. Amano PS showed excellent selectivity and good yields in the hydrolysis of fluorinated aromatic compounds. The absolute configuration of the resulting compounds was based on biokinetic studies and the use of chiral HPLC. A molecular modeling of the kinetic resolution of carboxylic acid esters was carried out. Full article

Freshwater, vital for life and ecosystems, accounts for only 2.5% of Earth’s water, and is primarily located in polar caps, underground reservoirs, and surface water. Its quality varies due to environmental interactions, especially in groundwater. Tenerife, located in the Canary Islands, Spain, relies mainly on underground aquifers and tunnels capturing 51.6 cubic hectometers annually. Ensuring safe drinking water is a global challenge due to health risks from poor water quality, including diseases and cancer. Fluoride, sodium, and potassium are essential for health, and are mainly derived from groundwater as fluoride ions (F⁻) and sodium and potassium cations (Na⁺, K⁺). However, excessive F⁻, Na⁺, and K⁺ in drinking water is harmful. The World Health Organization limits F⁻ to 1.5 mg/L, Na⁺ to 8.70 meq/L, and K⁺ to 0.31 meq/L. Geological, climatic, and human factors control the presence and transport of F⁻, Na⁺, and K⁺ in groundwater. Seismic events can impact water quality, with long-term effects linked to aquifer structure and transient effects from gas and fluid expansion during earthquakes. This study was motivated by a 3.8 mbLg earthquake in Tenerife in 2012, which allowed its impact on groundwater quality, specifically F⁻, Na⁺, and K⁻ concentrations, to be examined. Post-earthquake, F⁻ levels alarmingly increased to 8.367 meq/L, while Na⁺ and K⁺ showed no significant changes. This research quantifies the influence of earthquakes on increasing F⁻ levels and evaluates F⁻ reduction during low seismic activity, emphasizing the importance of water management on volcanic islands. Full article

The host kinase casein kinase 2 (CSNK2) has been proposed to be an antiviral target against β-coronaviral infection. To pharmacologically validate CSNK2 as a drug target in vivo, potent and selective CSNK2 inhibitors with good pharmacokinetic properties are required. Inhibitors based on the pyrazolo[1,5-a]pyrimidine scaffold possess outstanding potency and selectivity for CSNK2, but bioavailability and metabolic stability are often challenging. By strategically installing a fluorine atom on an electron-rich phenyl ring of a previously characterized inhibitor 1, we discovered compound 2 as a promising lead compound with improved in vivo metabolic stability. Compound 2 maintained excellent cellular potency against CSNK2, submicromolar antiviral potency, and favorable solubility, and was remarkably selective for CSNK2 when screened against 192 kinases across the human kinome. We additionally present a co-crystal structure to support its on-target binding mode. In vivo, compound 2 was orally bioavailable, and demonstrated modest and transient inhibition of CSNK2, although antiviral activity was not observed, possibly attributed to its lack of prolonged CSNK2 inhibition. Full article

Commercial NH₄-Beta and Na-ZSM-5 zeolites were fluorinated with different amounts of NH₄F and using different procedures (room temperature, conventional refluxing, microwave refluxing). Samples were characterized by XRD, N₂ physisorption, FTIR, ¹H NMR, SEM-EDS, and TGA of adsorbed cyclohexylamine. An increase in the concentration of NH₄F led to fluorinated zeolites with higher surface areas and slightly lower amounts of Brønsted acid sites due to some dealumination. Fluorination by conventional or microwave refluxing at shorter times did not dealuminate ZSM-5, resulting in the formation of higher particle sizes. Ni/fluorinated beta catalysts were more active than Ni/fluorinated ZSM-5 catalysts for the hydrodeoxygenation of guaiacol at 180 °C and 15 bar of H₂ for 1 h due to their higher amount of acid sites. The appropriate proportion of metallic and Brønsted acid centers allowed for the selective obtention of cyclohexane (58%) for the Ni supported on beta fluorinated with NH₄F 0.1 M catalyst. The combination of this fluorinated beta to a Ni/ordered mesoporous carbon catalyst significantly boosted its selectivity to cyclohexane from 0 to 65%. Fluorinated ZSM-5 samples, although having stronger Brønsted acid sites, as observed by ¹H NMR, they had lower amounts, leading to higher selectivity to cyclohexanol when used as catalytic supports. Full article

Fluorinated carbon cathode materials have extremely high theoretical specific energy among known cathode materials of lithium primary batteries. Nevertheless, current fluorinated carbon cannot meet the performance demands of future applications due to the rate performance. This work innovatively applies hollow carbon spheres with a porous structure as carbon sources to prepare fluorinated hollow porous carbon spheres (FHPCS) with high energy density and power density. The porous structure provides more reaction sites for the fluorination process and also shortens the diffusion path of lithium ions during the discharge. Additionally, the hollow porous structure offers more interfacial contact areas and reduces volumetric expansion during discharge reactions. The Li/CF_x primary battery has a maximum specific energy of 2007 Wh kg⁻¹ and a maximum power density of 30,400 W kg⁻¹ and can have a capacity retention rate of 80.8% at a current density of 16 A g⁻¹. In addition, FHPCS also has the highest specific energy of 1999 Wh kg⁻¹ and 1711 Wh kg⁻¹ in Na/CF_x and K/CF_x primary batteries, respectively. The diffusion efficiency of an alkali metal ion is analyzed by the different discharge depths with electrochemical impedance spectroscopy and galvanostatic intermittent titration technique. This effort introduces a new high-performance fluorinated carbon featuring a hollow porous structure and puts forward an innovative approach to designing fluorinated carbon materials. Full article

Iodine and fluorine, as halogen elements, are often coexisting in water environments, with nearly 200 million people suffering from fluorosis globally, and, in 11 countries and territories, adolescents have iodine intakes higher than that required for the prevention of iodine deficiency disorders. It has been suggested that excess iodine and/or fluorine can affect thyroid health and intellectual development, especially in children, but their combined effect has been less studied in this population. This study investigated 399 school-age children in Tianjin, China, collected drinking water samples from areas where the school-age children lived, and grouped the respondents according to iodine and fluorine levels. Thyroid health was measured using thyroid hormone levels, thyroid volume, and the presence of thyroid nodules; intelligence quotient (IQ) was assessed using the Raven’s Progressive Matrices (CRT) test; and monoamine neurotransmitter levels were used to explore the potential relationship between thyroid health and intelligence. Multiple linear regression and restricted cubic spline (RCS) analyses showed that iodine and fluorine were positively correlated with thyroid volume and the incidence of thyroid nodules in school-age children, and negatively correlated with IQ; similar results were obtained in the secondary subgroups based on urinary iodine and urinary fluoride levels. Interaction analyses revealed a synergistic effect of iodine and fluorine. A pathway analysis showed that iodine and fluorine were negatively associated with the secretion of free triiodothyronine (FT3) and free tetraiodothyronine (FT4), which in turn were negatively associated with the secretion of thyroid-stimulating hormone (TSH). Iodine and fluorine may affect IQ in school-aged children through the above pathways that affect thyroid hormone secretion; of these, FT3 and TSH were negatively correlated with IQ, whereas FT4 was positively correlated with IQ. The relationship between thyroid hormones and monoamine neurotransmitters may involve the hypothalamic–pituitary–thyroid axis, with FT4 hormone concentrations positively correlating with dopamine (DA), norepinephrine (NE), and 5-hydroxytryptophan (5-HT) concentrations, and FT3 hormone concentrations positively correlating with DA concentrations. Monoamine neurotransmitters may play a mediating role in the effects of iodine and fluoride on intelligence in schoolchildren. However, this study has some limitations, as the data were derived from a cross-sectional study in Tianjin, China, and no attention was paid to the reciprocal effects of iodine and fluorine at different doses on thyroid health and intelligence in schoolchildren in other regions. Full article

This study focuses on the relationship between U and pyrochlore in the world-class Sn-Nb-Ta (U, Th, REE, Li) Madeira deposit within the Pitinga mining district of northern Brazil. The primary U mineralization is of intrusive-type and early magmatic origin, hosted in the peralkaline albite-enriched granite facies of the A-type Madeira granite (~1820 Ma). U-Pb-LREE-enriched pyrochlore is the only primary U ore and is widely and homogeneously dispersed in two albite-enriched granite subfacies: the albite-enriched granite core (AGC) and the albite-enriched granite border (AGB). In both zones, the pyrochlore crystals underwent strong hydrothermal alteration by F-rich, low-temperature aqueous fluids. During this hypogene alteration process, cations such as LREE, Nb, and F were selectively released, while others like Fe and Si were introduced. This led to the successive formation of various secondary pyrochlore varieties and a relative enrichment of U (up to 13.73 wt.% UO₂). The alteration of pyrochlore eventually resulted in the breakdown of its structure, leading to the formation of U-bearing columbite pseudomorphs and the precipitation of U-rich silicates (up to 34.35 wt.% UO₂), galena, and LREE-rich fluorides within pyrochlore vugs. In contrast to the homogeneous distribution of the primary ore mineralization, the secondary pyrochlore mineralization shows striking zonation, being most intense in the AGB and AGC proximal to a massive cryolite deposit. The U mineralization in the Madeira deposit exhibits grades of 328 ppm UO₂, comparable to the main deposits of this type, with significant reserves of up to 52 kt U. However, it is different from those deposits in four key aspects: homogeneous dispersion of mineralization; pyrochlore as the exclusive primary ore mineral; U and Th mineralizations formed at different stages; and intense hydrothermal alteration. These characteristics are attributed to the special conditions imposed by the fluorine-rich nature of the peralkaline magma. Full article

Four non-fluorinated sulfonimide polyamides (s-PAs) were successfully synthesized and a series of membranes were prepared by blending s-PA with polyvinylidene fluoride (PVDF) to achieve high-methanol-permeation resistivity for direct methanol fuel cell (DMFC) applications. Four membranes were fabricated by blending 50 wt% PVDF with s-PA, named BPD-101, BPD-102, BPD-111 and BPD-211, respectively. The s-PA/PVDF membranes exhibit high methanol resistivity, especially for the BPD-111 membrane with methanol resistivity of 8.13 × 10⁻⁷ cm²/s, which is one order of magnitude smaller than that of the Nafion 117 membrane. The tensile strength of the BPD-111 membrane is 15 MPa, comparable to that of the Nafion 117 membrane. Moreover, the four membranes also show good thermal stability up to 230 °C. The BPD-x membrane exhibits good oxidative stability, and the measured residual weights of the BPD-111 membrane are 97% and 93% after treating in Fenton’s reagent (80 °C) for 1 h and 24 h, respectively. By considering the mechanical, thermal and dimensional properties, the polyamide proton-exchange membrane exhibits promising application potential for direct methanol fuel cells. Full article

Tuning a material’s hydrophobicity is desirable in several industrial applications, such as hydrocarbon storage, separation, selective CO₂ capture, oil spill cleanup, and water purification. The introduction of fluorine into rare-earth (RE) metal–organic frameworks (MOFs) can make them hydrophobic. In this work, the linker bis(trifluoromethyl)terephthalic acid (TTA) was used to make highly fluorinated MOFs. The reaction of the TTA and RE³⁺ (RE: Y, Gd, or Eu) ions resulted in the primitive cubic structure (pcu) exhibiting RE dimer nodes (RE-TTA-pcu). The crystal structure of the RE-TTA-pcu was obtained. The use of the 2-fluorobenzoic acid in the synthesis resulted in fluorinated hexaclusters in the face-centered cubic (fcu) framework (RE-TTA-fcu), analogous to the UiO-66 MOF. The RE-TTA-fcu has fluorine on the linker as well as in the cluster. The MOFs were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and contact angle measurements. Full article

There is a high demand for plasma-resistant coatings that prevent the corrosion of the internal ceramic components of plasma etching equipment, thereby reducing particle contamination and process drift. Yttrium oxyfluoride (YOF) coatings were prepared using atmospheric plasma spraying (APS) with commercially available YOF/YF₃ powder mixtures; namely YOF 3%, YOF 6%, and YOF 9%. The etching behaviour of YOF and yttrium oxide (Y₂O₃) coatings was investigated using an inductively coupled plasma consisting of NF₃/He. X-ray photoelectron spectroscopy (XPS) showed that the YOF 6% coating had the thickest fluorinated layer. The scanning electron microscope (SEM) examination revealed that the YOF 6% coating showed exceptional resistance to erosion and generated a reduced quantity of contaminated particles in comparison to Y₂O₃. Consequently, it is more suitable as a protective material for the inner wall of reactors. The YOF coatings exhibit excellent stability and high resistance to erosion, indicating their appropriateness for use in the semiconductor industry. Full article

To conquer the challenges of charge accumulation and surface flashover in epoxy resin under direct current (DC) electric fields, numerous efforts have been made to research dielectric barrier discharge (DBD) plasma treatments using CF₄/Ar as the medium gas, which has proven effective in improving surface flashover voltage. However, despite being an efficient plasma etching medium, SF₆/Ar has remained largely unexplored. In this work, we constructed a DBD plasma device with an SF₆/Ar gas medium and explored the influence of processing times and gas flow rates on the morphology and surface flashover voltage of epoxy resin. The surface morphology observed by SEM indicates that the degree of plasma etching intensifies with processing time and gas flow rate, and the quantitative characterization of AFM indicates a maximum roughness of 144 nm after 3 min of treatment. Flashover test results show that at 2 min of processing time, the surface flashover voltage reached a maximum of 19.02 kV/mm, which is 25.49% higher than that of the untreated sample and previously reported works. In addition to the effect of surface roughness, charge trap distribution shows that fluorinated groups help to deepen the trap energy levels and density. The optimal modification was achieved at a gas flow rate of 3.5 slm coupled with 2 min of processing time. Furthermore, density functional theory (DFT) calculations reveal that fluorination introduces additional electron traps (0.29 eV) and hole traps (0.38 eV), enhancing the capture of charge carriers and suppressing surface flashover. Full article

Several novel copper (II) complexes of reduced Schiff bases containing fluoride substituents were prepared and structurally characterized by single-crystal X-ray diffraction. The complexes exhibited diverse structures, with the central atom in distorted tetrahedral geometry. The biological effects of the products were evaluated, specifically their cytotoxicity, antimicrobial, and antiurease activities, as well as affinity for albumin (BSA) and DNA (ct-DNA). The complexes showed marked cytotoxic activities in the HepG2 hepatocellular carcinoma cell line, considerably higher than the standard cisplatin. The cytotoxicity depended significantly on the substitution pattern. The best activity was observed in the complex with a trifluoromethyl group in position 4 of the benzene ring—the dichloro[(±)-trans-N,N′-bis-(4-trifluoromethylbenzyl)-cyclohexane-1,2-diamine]copper (II) complex, whose activity (IC₅₀ 28.7 μM) was higher than that of the free ligand and markedly better than the activity of the standard cisplatin (IC₅₀ 336.8 μM). The same complex also showed the highest antimicrobial effect in vitro. The affinity of the complexes towards bovine serum albumin (BSA) and calf thymus DNA (ct-DNA) was established as well, indicating only marginal differences between the complexes. In addition, all complexes were shown to be excellent inhibitors of the enzyme urease, with the IC₅₀ values in the lower micromolar region. Full article

Glioblastoma, a formidable brain tumor characterized by dysregulated NAD metabolism, poses a significant therapeutic challenge. The NAMPT inhibitor FK866, which induces NAD depletion, has shown promise in controlling tumor proliferation and modifying the tumor microenvironment. However, the clinical efficacy of FK866 as a single drug therapy for glioma is limited. In this study, we aim to disrupt NAD metabolism using fluorinated NAD precursors and explore their synergistic effect with FK866 in inducing cytotoxicity in glioblastoma cells. The synthesized analogue of nicotinamide riboside (NR), ara-F nicotinamide riboside (F-NR), inhibits nicotinamide ribose kinase (NRK) activity in vitro, reduces cellular NAD levels, and enhances FK866’s cytotoxicity in U251 glioblastoma cells, indicating a collaborative impact on cell death. Metabolic analyses reveal that F-NR undergoes conversion to fluorinated nicotinamide mononucleotide (F-NMN) and other metabolites, highlighting the intact NAD metabolic pathway in glioma cells. The activation of SARM1 by F-NMN, a potent NAD-consuming enzyme, is supported by the synergistic effect of CZ-48, a cell-permeable SARM1 activator. Temporal analysis underscores the sequential nature of events, establishing NAD depletion as a precursor to ATP depletion and eventual massive cell death. This study not only elucidates the molecular intricacies of glioblastoma cell death but also proposes a promising strategy to enhance FK866 efficacy through fluorinated NAD precursors, offering potential avenues for innovative therapeutic interventions in the challenging landscape of glioblastoma treatment. Full article

PFASs are a variety of ecologically persistent compounds of anthropogenic origin loosely included in many industrial products. In these, the carbon chain can be fully (perfluoroalkyl substances) or partially (polyfluoroalkyl substances) fluorinated. Their ubiquitous presence in many environmental compartments over the years and their long-lasting nature have given rise to concerns about the possible adverse effects of PFASs on ecosystems and human health. Among a number of remediation technologies, adsorption has been demonstrated to be a manageable and cost-effective method for the removal of PFASs in aqueous media. This study tested two novel and eco-friendly adsorbents (pinewood and date seeds biochar) on six different PFASs (PFOS, GenX, PFHxA, PFOA, PFDA, and PFTeDA). Batch sorption tests (24 h) were carried out to evaluate the removal efficiency of each PFAS substance in relation to the two biochars. All samples of liquid phase were analyzed by a developed and then a well-established method: (i) pre-treatment (centrifugation and filtration) and (ii) determination by high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS). The results evidenced a comparable adsorption capacity in both materials but greater in the long-chain PFASs. Such findings may lead to a promising path towards the use of waste-origin materials in the PFAS remediation field. Full article

A variational heteroencoder based on recurrent neural networks, trained with SMILES linear notations of molecular structures, was used to derive the following atomic descriptors: delta latent space vectors (DLSVs) obtained from the original SMILES of the whole molecule and the SMILES of the same molecule with the target atom replaced. Different replacements were explored, namely, changing the atomic element, replacement with a character of the model vocabulary not used in the training set, or the removal of the target atom from the SMILES. Unsupervised mapping of the DLSV descriptors with t-distributed stochastic neighbor embedding (t-SNE) revealed a remarkable clustering according to the atomic element, hybridization, atomic type, and aromaticity. Atomic DLSV descriptors were used to train machine learning (ML) models to predict ¹⁹F NMR chemical shifts. An R² of up to 0.89 and mean absolute errors of up to 5.5 ppm were obtained for an independent test set of 1046 molecules with random forests or a gradient-boosting regressor. Intermediate representations from a Transformer model yielded comparable results. Furthermore, DLSVs were applied as molecular operators in the latent space: the DLSV of a halogenation (H→F substitution) was summed to the LSVs of 4135 new molecules with no fluorine atom and decoded into SMILES, yielding 99% of valid SMILES, with 75% of the SMILES incorporating fluorine and 56% of the structures incorporating fluorine with no other structural change. Full article