Search Results (216)

Three fluorophenyl-substituted cyclometalated Ir(III) complexes (Ir1–Ir3) have been synthesized by changing the position of the fluorine atom. All complexes exhibit distinct aggregation-induced phosphorescence emission (AIPE) characteristics in CH₃CN/H₂O and demonstrate satisfactory detection performance for 2,4,6-trinitrophenols (TNPs) with limits of detection of 124 nM, 101 nM, and 127 nM, respectively. In addition, Ir1–Ir3 possess excellent selectivity and anti-interference capability for TNP detection, showing outstanding performance even in different common water samples. The ultraviolet–visible absorption spectra and luminescence lifetimes of the complexes show that their quenching processes include both a static process and dynamic process, and the detection mechanism may be assigned to a combination of photo-induced electron transfer and an inner-filter effect. Full article

The rocks of the Burpala alkaline intrusion contain a wide range of rare minerals that concentrate rare earth elements (REEs), Nb, Th, Li, and other incompatible elements. One of the examples of the occurrence of such mineralization is albite–aegirine rocks located at the contact zone between the intrusion and the host terrigenous–sedimentary rock. In albite–aegirine rocks, cubic crystals of “metaloparite”, partially or completely substituted by bastnäsite-(Ce) and polymorphic TiO₂ phases (anatase and rutile) mainly represent the rare metal minerals. In albite–aegirine rocks, trace element minerals are predominantly represented by cubic crystals of “metaloparite”, which are partially or completely replaced by bastnäsite-(Ce) and polymorphic TiO₂ phases such as anatase and rutile. Additionally, Th-bearing zircon (up to 17.7 wt% ThO₂) and a variety of unidentified minerals containing REEs, Th, and Nb were detected. The obtained data indicate that bastnäsite-(Ce) is the result of the recrystallization of “metaloparite” accompanied by the formation of Th-bearing zircon and Nb-bearing rutile (up to 9.9 wt% Nb₂O₅) and the separation of various undiagnosed, unidentified LREE phases. Our studies show that remobilization of LREEs, HFSEs, and local enrichment of rocks in these elements occurred due to the effects of residual fluid enriched in fluorine and carbon dioxide. Full article

We report the first syntheses—from commercially available 3-chloro-2-fluoroprop-1-ene (9)—of key garlic-derived compounds containing sp²-fluorine. We also report synthesis of fluoro-5,6-dihydrothiopyrans by trapping 2-fluorothioacrolein (15). Thus, difluoroallicin (12, S-(2-fluoro-2-propenyl) 2-fluoroprop-2-ene-1-sulfinothioate) is prepared by peracid oxidation of 1,2-bis(2-fluoro-2-propenyl)disulfane (11). S-2-Fluoro-2-propenyl-l-cysteine (2-fluorodeoxyalliin, 13), synthesized from cysteine and characterized by X-ray crystallography, is oxidized to its S-oxide, 2-fluoroalliin (22). The latter, with alliinase-containing powdered fresh garlic, gives a mixture of 12, allicin (1), and isomers of monofluoroallicin (23), indicating that 22 serves as a substrate for garlic alliinase. Upon heating, 12 generates transient 15, which dimerizes giving difluoro vinyl dithiins 6 and 7. Ethyl acrylate trapping of 15 affords 5- and 6-substituted 3-fluoro-5,6-dihydro-4H-thiopyrans (19 and 20). In 1,1,1,3,3,3-hexafluoro-2-propanol (HEFP) as solvent, 12 is converted into trifluoroajoene ((E,Z)-1-(2-fluoro-3-((2-fluoro-2-propenyl)sulfinyl)prop-1-en-1-yl)-2-(2-fluoro-2-propenyl)disulfane; 18). Liquid sulfur converts 11 to a (CH₂=CFCH₂)₂S_n mixture (n = 4–15), characterized by UPLC-(Ag⁺)-coordination ion spray-mass spectrometry. Full article

To mitigate the serious environmental impact caused by the persistent accumulation of plastics, replacing conventional plastics with paper-based alternatives has emerged as a promising trend. In response to the environmental and health concerns associated with petrochemical-based plastic meal boxes and fluorinated water- and oil-repellent agents, this study proposes a sustainable, fluorine-free coating technology based on chitosan to enhance the water and oil resistance of molded-paper pulp meal boxes. By adjusting the degree of deacetylation and the solution concentration of chitosan, coated meal boxes were fabricated via a spraying method. The results demonstrate that coatings prepared with highly deacetylated (>95%) and concentrated (4% w/v) chitosan significantly improve barrier properties, achieving a water contact angle of 114.9° ± 3°, the highest oil-resistance rating (12/12) according to TAPPI standards, and stable resistance to 95 °C hot oil for up to 30 min without leakage. In addition, the coated samples exhibit enhanced mechanical strength (21.26 MPa) and excellent biodegradability. This work provides a cost-efficient and eco-friendly disposable food packaging solution, facilitating the sustainable substitution of petrochemical-based plastics. Full article

Excessive intake of fluorine (F) over time can lead to acute or chronic fluorosis. In this study, a novel Fe^III–Ce^IV-based layered hydroxide composite (DD-LHC) was synthesized and applied in both batch and column modes to develop new adsorbent materials and to obtain efficient removal of fluorine (F) anions from wastewater. DD-LHC achieved better adsorption results and material stability compared to green rusts (GR, Fe^II–Fe^III hydroxide). The maximum adsorption capacity of DD-LHC for F⁻ was 44.68 mmol·g⁻¹, obtained at an initial pH of 5 and initial concentration of 80 mM. The substitution of Ce^IV for Fe^II in the intercalated layered structure of GR potentially changed the reaction pathways for F⁻ removal, which are typically dominant in the layered double hydroxides (LDHs) of Fe^II–Fe^III. The molecular structure of layered hydroxides combined with the three-dimensional (3D) metal frame of Fe-O-Ce was integrated into DD-LHC, resulting in nanoscale particle morphologies distinct from those of GR. The pseudo-first-order kinetic model effectively described the whole adsorption process of DD-LHC for F⁻. DD-LHC exhibited notable selectivity for F⁻ across a wide pH range. The removal process of F⁻ by DD-LHC was dominated by Ce–F coordination bonds, with additional influences from auxiliary pathways to different extents. Full article

Anode-free lithium-ion batteries offer a volumetric energy density approximately 60% higher than that of conventional lithium-ion cells. Despite this advantage, they often experience rapid capacity degradation and a limited cycle life. Optimizing electrolyte formulations—particularly through the use of specific additives, solvents, and lithium salts—is essential to improving these systems. This study explores electrolytes composed of fluorinated and carbonate-based solvents applied in anode-free lithium-ion cells featuring copper as the anode substrate and Li_1.05Ni_0.33Mn_0.33Co_0.33O₂ as the cathode. In the present work, the ionic conductivity of electrolytes was studied by impedance spectroscopy, and the electrochemical parameters of anode-free lithium-ion cells were compared using these electrolyte solutions: lithium difluoro(oxalato)borat (LIDFOB) salts were used in a mixture of solvents such as fluoroethylene carbonate (FEC) and dimethoxyethane (DME) in a ratio of 3:7 and in a mixture of propylene carbonate (PC) and dimethoxyethane in a ratio of 3:7. Enhanced performance was observed upon the substitution of conventional carbonates with fluorinated co-solvents. The findings suggest that LiDFOB is a thermostable salt, and its high conductivity contributes to the formation and stabilization of the interface of solid electrolytes. The results indicate that at low temperature conditions, a double salt should be used for lithium current sources, for example, 0.4 M LiDFOB and 0.6 M LiBF₄, as well as electrolyte additives such as fluoroethylene carbonate and lithium nitrate. Full article

Background/Objectives: Pancreatic cancer is the seventh most lethal type of cancer in the world, and its treatment, which is largely inefficient, is based on surgery and/or non-specific chemotherapy. Its malignant features are characterized by complex cell signaling pathways, which can be used as targets for new drugs. Methods: In this study, glucal-based compounds were synthetized, with substitution based on fluorine, nitrogen and aromatic ring addition. The compounds were tested in the pancreatic cell culture Mia-PaCa-2 and cell viability was assessed, with further IC50 calculation, stability and selectivity. Molecular docking was performed to evaluate the probable molecular target for 5b and in silico physicochemical properties were determined. Results: One molecule, named 5b, with two fluorine atoms inserted in the aromatic ring, exerted potent inhibitory activity on cell growth (IC50 = 1.39 µM), which was selective for pancreatic cells. Through molecular docking studies, the compound was found to be positioned in the active site of JAK3, indicating inhibition of such protein, which has a role in tumoral cell growth. Moreover, 5b was stable for 24 months and had physicochemical properties to permeate cell membranes, good oral absorption, and low potential to cause toxicity. Conclusions: These data suggest that 5b can be druggable and can be considered as a prototype for a new course of treatment in pancreatic cancer. Full article

In this work, a density functional theory (DFT) with Hubbard correction (U) approaches implemented through the Quantum ESPRESSO code is utilized to investigate the effects of fluorine (F) doping on the structural, electronic, and optical properties of rutile TiO₂. Rutile TiO₂ is a promising material for renewable energy production and environmental remediation, but its wide bandgap limits its application to the UV spectrum, which is narrow and expensive. To extend the absorption edge of TiO₂ into the visible light range, different concentrations of F were substituted at oxygen atom sites. The structural analysis reveals that the lattice constants and bond lengths of TiO₂ increased with F concentrations. Ab initio molecular dynamics simulations (AIMD) at 1000 K confirm that both pristine and F-doped rutile TiO₂ maintains structural integrity, indicating excellent thermal stability essential for high-temperature photocatalytic applications. Band structure calculations show that pure rutile TiO₂ has a bandgap of 3.0 eV, which increases as the F concentration rises, with the 0.25 F-doped structures exhibiting an even larger bandgap, preventing it from responding to visible light. The absorption edge of doped TiO₂ shifts towards the visible region, as shown by the imaginary part of the dielectric function. This research provides valuable insights for experimentalists, helping them understand how varying F concentrations influence the properties of rutile TiO₂ for photocatalytic applications. Full article

The semiconductor industry is essential to information technology and the ongoing artificial intelligence transformation but also poses significant environmental challenges, including greenhouse gas emissions, air pollution, solid waste, and high water and energy consumption. This review identifies key emission sources in semiconductor manufacturing, focusing on the release of fluorinated gases from chemical-intensive processes and the sector’s substantial energy demands. We evaluate the effectiveness and limitations of current mitigation strategies, such as process optimization, clean energy adoption, and material substitution. We also examine supply chain interventions, including green procurement, logistics optimization, and intelligent management systems. While technological innovation is crucial for the sustainable transition of the global semiconductor industry, the high cost of upgrading to greener production processes remains a major obstacle. Despite progress in clean energy integration and material alternatives, significant challenges persist in reducing emissions across the entire value chain. This review underscores an urgent need for collaborative, integrated approaches to drive the sustainable transition of the semiconductor sector and its upstream supply chain. Full article

The complex of hypofluorous acid with acetonitrile—HOF•CH₃CN—is the only substance possessing a truly electrophilic oxygen. This fact makes it the only tool suitable for transferring oxygen atoms to sites that are not accessible to this vital element. We will review here most of the known organic reactions with this complex, which is easily made by bubbling dilute fluorine through aqueous acetonitrile. The reactions of HOF•CH₃CN with double bonds produce epoxides in a matter of minutes at room temperature, even when the olefin is electron-depleted and cannot be epoxidized by any other means. The electrophilic oxygen can also substitute deactivated tertiary C-H bonds via electrophilic substitution, proceeding with full retention of configuration. Using this complex enables transferring oxygen atoms to a carbonyl and oxidizing alcohols and ethers to ketones. The latter could be oxidized to esters via the Baeyer–Villiger reaction, proving once again the validity of the original Baeyer mechanism. Azines are usually avoided as protecting groups for carbonyl since their removal is problematic. HOF•CH₃CN solves this problem, as it is very effective in recreating carbonyls from the respective azines. A bonus of the last reaction is the ability to replace the common ¹⁶O isotope of the carbonyl with the heavier ¹⁷O or ¹⁸O in the simplest and cheapest possible way. The reagent can transfer oxygen to most nitrogen-containing molecules. Thus, it turns practically any azide or amine into nitro compounds, including amino acids. This helps to produce novel α-alkylamino acids. It also attaches oxygen atoms to most tertiary nitrogen atoms, including certain aromatic ones, which could not be obtained before. HOF•CH₃CN was also used to make five-member cyclic poly-NO derivatives, many of them intended to be highly energetic materials. The nucleophilic sulfur atom also reacts very smoothly with the reagent in a wide range of compounds to form sulfone derivatives. While common sulfides are easily converted to sulfones by many orthodox reagents, electron-depleted ones, such as R_f-S-Ar, can be oxidized to R_f-SO₂-Ar only with this reagent. The mild reaction conditions also make it possible to synthesize a whole range of novel episulfones and offer, as a bonus, a very easy way to make S^xO₂, x being any isotope variation of oxygen. These mild conditions also helped to oxidize thiophene to thiophen-S,S-dioxide without the Diels–Alder dimerizations, which usually follow such dioxide formation. The latter reaction was a prelude to a series of preparations of [all]-S,S-dioxo-oligothiophenes, which are important for the efficient preparation of active layers in field-effect transistors (FETs), as such oligomers are considered to be important for organic semiconductors for light-emitting diodes (LEDs). Several types of these oligothiophenes were prepared, including partly or fully oxygenated ones, star-oligothiophenes, and fused ones. Several [all]-S,S-dioxo-oligo-thienylenevinylenes were also successfully prepared despite the fact that they also possess carbon–carbon p centers in their molecules. All oxygenated derivatives have been prepared for the first time and have lower HOMO-LUMO gaps compared to their parent compounds. HOF•CH₃CN was also used to oxidize the surface of the nanoparticles of oligothiophenes, leaving the core of the nanoparticle unchanged. Several highly interesting features have been detected, including their ability to photostimulate the retinal neurons, especially the inner retinal ones. HOF•CH₃CN was also used on elements other than carbon, such as selenium and phosphor. Various selenides were oxidized to the respective selenodioxide derivatives (not a trivial task), while various phosphines were converted efficiently to the corresponding phosphine oxides. Full article

6-Aryl-2-picolinic acid herbicides are an important subclass of auxin herbicides, characterized by their good absorption and conductivity, broad weed control spectrum, and excellent herbicidal activity against some resistant weeds. Based on previous studies from our group and the distinct characteristics of physico-chemical properties and biological activities of active skeleton structure containing fluorine atoms, this paper introduces the design and synthesis of 41 novel 4-amino-6-(5-aryl-substituted-1-pyrazolyl)-3-chloro-5-fluoro-2-picolinic acid compounds. The test of inhibiting A. thaliana roots growth showed that most of the S-series compounds exhibited superior inhibitory effects compared to picloram, with six compounds demonstrated even better inhibitory capability than the new herbicidal molecule florpyrauxifen. For example, compound S202, at a concentration of 0.5 µmol/L, exhibited a 78.4% inhibition of A. thaliana root growth, whereas florpyrauxifen showed only a 33.8% inhibition. Root growth inhibition tests on weeds showed that 28 compounds, at a concentration of 250 µM, demonstrated a greater than 80% inhibition of Brassica napus (BN) root growth. Post-emergence herbicidal activity tests showed that most compounds exhibited good inhibitory effects on broadleaf weeds, with 10 compounds achieving a 100% inhibition of the growth of Amaranthus retroflexus L (AL). These results demonstrate that some of the 4-amino-6-(5-aryl-substituted-1-pyrazolyl)-3-chloro-5-fluoro-2-picolinic acid compounds could be used as potential lead structures in the discovery of novel synthetic auxin herbicides. Full article

Fluorination of carbohydrates is a promising strategy to produce glycomimetics with improved pharmacological properties, such as increased metabolic stability, bioavailability and protein-binding affinity. Fluoroglycans are not only of interest as inhibitors and chemical probes but are increasingly being used to develop potential synthetic vaccine candidates for cancer, HIV and bacterial infections. Despite their attractiveness, the synthesis of fluorinated oligosaccharides is still challenging, emphasizing the need for efficient protocols that allow for the site-specific incorporation of fluorine atoms (especially at late stages of the synthesis). This is particularly true for the development of fully synthetic vaccine candidates, whose (modified) carbohydrate antigen structures (glycotopes) per se comprise multistep synthesis routes. Based on a known minimal protective epitope from the capsular polysaccharide of S. pneumoniae serotype 8, a panel of six novel F-glycotope mimetics was synthesized, equipped with amine linkers for subsequent conjugation to immunogens. Next to the stepwise assembly via fluorinated building blocks, the corresponding 6F-substituted derivatives could be obtained by microwave-assisted, nucleophilic late-stage fluorination of tri- and tetrasaccharidic precursors in high yields. The described synthetic strategy allowed for preparation of the targeted fluorinated oligosaccharides in sufficient quantities for future immunological studies. Full article

Synthesis of organometallic compounds has had an enormous impact on medicine. In this context, gold complexes are gaining much interest since the discovery of the cytotoxic effect of cisplatin. On the other hand, in the last two decades, the mechanochemical synthetic approaches have been developed considerably demonstrating that they could also be a powerful tool enabling environmentally benign and sustainable synthesis of metal complexes. The present work focuses on mechanochemical synthesis of precursors and gold–NHC complexes of type NHCAuCl and [AubisNHC]⁺. The mechanochemical approach has been studied to afford four substituted imidazoles, eight imidazolium salts and six NHCAuCl and one [AubisNHC]⁺. Substituted imidazoles were obtained with yields varying between 29–99%. Five imidazolium salts bearing aliphatic carbon atoms were obtained, with yields from 46–81%. It is important to notice that the reaction can follow the aging process giving rise to imidazolium salts in very good yields. Concerning the gold(I) complexes, for the first time, six mono NHC complexes of type NHCAuCl have been synthesized, five of them with yields varying between 41–83%. Finally, compound 19 [AubisNHC]⁺ has been obtained not only by transmetallation, but most gratifyingly through direct metalation in 73% yield. Full article

Fluorinated nitriles have been proposed as low-global-warming-potential substitutes for industrial applications such as plasma etching and as dielectric materials in high-voltage equipment. FT-IR spectroscopy was used to measure the radiative efficiency of CH₂FCN and its reactivity towards Cl and OH radicals, and to determine products from the Cl reaction. Relative rate experiments yielded rate constants for Cl and OH reactions of (2.1 ± 0.3) × 10⁻¹⁴ and (7.0 ± 1.0) × 10⁻¹⁴ cm³ molecule⁻¹ s⁻¹, respectively. The estimated atmospheric lifetime of CH₂FCN with respect to radical attack was estimated to be 0.45 years, which, combined with the radiative efficiency of 0.042 W m⁻² ppb⁻¹, implies a 100-year global warming potential of 20. FCOCN was observed as the only organic product of the Cl-atom reaction in air, consistent with a dominant role for H-abstraction. Absolute infrared cross-sections for FCOCN were determined, to assist future experiments where this molecule may be formed. Quantum calculations at the CBS-APNO//B2PLYP-D3/cc-pVTZ level indicate similar energy barriers to addition and abstraction for OH radical attack, but the looser transition state and greater opportunity for tunneling also favor abstraction in this case. Full article

Fluorine accounts for 0.3 g/kg of the Earth’s crust, being widely distributed in the environment as fluoride. The toxic effects of this anion in humans and other organisms have been known for a long time. Fluoride has been reported to alter several cellular processes although the mechanisms involved are largely unknown. Inorganic pyrophosphatases (PPases) are ubiquitous enzymes that hydrolyze inorganic pyrophosphate (PPi), a metabolite generated from ATP. In Saccharomyces cerevisiae, the enzyme responsible for PPi hydrolysis in the cytosol (IPP1) is strongly inhibited by fluoride in vitro. The essentiality of IPP1 for growth has been previously demonstrated using YPC3, a yeast mutant with conditional expression of the corresponding gene. Here, YPC3 was used to generate cells that tolerate high concentrations of fluoride by (a) the overexpression of IPP1 or its human ortholog, or (b) the substitution of IPP1 by the fluoride-insensitive PPase from Streptococcus mutans. The results obtained suggest that maintaining appropriate levels of PPase activity in the cytosol is essential for the adaptation of S. cerevisiae to high fluoride concentrations. The increase in fluoride tolerance allows YPC3 cells transformed with suitable plasmids to be selected on rich non-selective medium supplemented with this anion. Full article