Search

In view of the inherent pseudocapacitance, rich redox pairs (Nb5+/Nb4+ and Nb4+/Nb3+), and high lithiation potential (1.0–3.0 V vs Li/Li+), Nb2O5 is considered a promising anode material. However, the inherent low electronic conductivity of Nb2O5 limits its lithium storage performance, and the rate performance after carbon modification is still unsatisfactory because the intrinsic conductivity of Nb2O5 has not been substantially improved. In this experiment, taking the improvement of the intrinsic electrical conductivity of Nb2O5 as the guiding ideology, we prepared F-doped Nb2O5@fluorocarbon composites (F–Nb2O5@FC) with a large number of oxygen vacancies by one-step annealing. As the anode electrode of lithium-ion batteries, the reversible specific capacity of F–Nb2O5@FC reaches 150 mA g−1 at 5 A g−1 after 1100 cycles, and the rate performance is particularly outstanding, with a capacity up to 130 mA g−1 at 16 A g−1, which is far superior to other Nb2O5@carbon-based anode electrodes. Compared with other single conductivity sources of Nb2O5@carbon-based composites, the electrical conductivity of F–Nb2O5@FC composites is greatly improved in many aspects, including the introduction of free electrons by F− doping, the generation of oxygen vacancies, and the provision of a three-dimensional conductive network by FC. Through analytical chemistry (work function, UV–Vis diffuse reflectance spectroscopy, and EIS) and theoretical calculations, it is proved that F–Nb2O5@FC has high electrical conductivity and realizes rapid electron transfer. [ABSTRACT FROM AUTHOR]

Fluorination of two-dimensional (2D) antimonene hexagons synthesized through a colloidal bottom-up approach has been explored using microwave-induced plasma and reactive ion etching fluorination strategies through the generation of CF4. The stability of the fluorine bond has been corroborated through DFT calculations. This work paves the way for further halogen-derivative modifications of heavy 2D pnictogens. [ABSTRACT FROM AUTHOR]

Among optimization strategies for solving the poor ion transport ability and electrolyte/electrode interface compatibility problems of lithium (Li)‐based batteries, halogen elements, such as fluorine (F) and iodine (I), have gradually occupied an important position because of their superb electronegativity, oxidizability, ionic radius, and other properties. The study commences by outlining the shared mechanism by which F and I enhance solid‐state lithium metal batteries' electrochemical performance. In particular, F and I can considerably improve ion transport capacity through chemical means such as intermolecular interactions and halogenation reactions. Furthermore, the utilization of F and I significantly enhances the stability of the electrolyte/electrode interface via physical strategies, encompassing doping techniques, the application of surface coatings, and the fabrication of synthetic intermediate layers. Subsequently, the characteristics of F and I used in Li‐based batteries are elaborated in detail, focusing on the fact that F can provide additional energy density as an anode material but by different mechanisms. Additionally, I can considerably activate dead lithium at the negative electrode, and F can act as a new carrier. Finally, a rational concept of the synergistic effect of F and I is proposed and the feasibility of F–I bihalide solid electrolytes is explored. [ABSTRACT FROM AUTHOR]

Fluorine, the most electronegative element, is currently used extensively in medicine, agrochemistry, and material science. Fluorinated compounds are expected to account for 30–50% of all active components now under development. It is difficult for medicinal chemists to discover new active compounds with higher efficacy, decreased mammalian toxicity, a better environmental profile, and a cheaper cost; yet, fluorinated pyrazole fits all of these criteria. The current review will provide an overview of the synthesis of pyrazoles with novel fluorinated substituents that have important uses in pharmaceutical and agricultural chemistry, with a focus on data published between 2011 and 2023. A concise table with the relevant literature references helped the reader to understand each derivative of fluorinated pyrazoles according to their biological activity. [ABSTRACT FROM AUTHOR]

Gelation of sulfolane-based highly concentrated electrolytes using a partially fluorinated polymer enhances the Li-ion transference number of the electrolytes because acidic protons surrounded by fluorine atoms in the polymer network trap anions, and the high Li+ transference number is effective in suppressing the concentration polarization in Li batteries. [ABSTRACT FROM AUTHOR]

Settling the structure stacking of graphene (G) nanosheets to maintain the high dispersity has been an intense issue to facilitate their practical application in the microelectronics‐related devices. Herein, the co‐doping of the highest electronegative fluorine (F) and large atomic radius chlorine (Cl) into G via a one‐step electrochemical exfoliation protocol is engineered to actualize the ultralong cycling stability for flexible micro‐supercapacitors (MSCs). Density functional theoretical calculations unveiled that the F into G can form the "ionic" C─F bond to increase the repulsive force between nanosheets, and the introduction of Cl can enlarge the layer spacing of G as well as increase active sites by accumulating the charge on pore defects. The co‐doping of F and Cl generates the strong synergy to achieve high reversible capacitance and sturdy structure stability for G. The as‐constructed aqueous gel‐based MSC exhibited the superb cycling stability for 500,000 cycles with no capacitance loss and structure stacking. Furthermore, the ionic liquid gel‐based MSC demonstrated a high energy density of 113.9 mW h cm−3 under high voltage of up to 3.5 V. The current work enlightens deep insights into the design and scalable preparation of high‐performance co‐doped G electrode candidate in the field of flexible microelectronics. [ABSTRACT FROM AUTHOR]

Perovskite solar cells (PSCs) are usually modified and passivated to improve their performance and stability. The interface modification and bulk doping are the two basic strategies. Fluorine (F)‐containing materials are highly favored because of their unique hydrophobicity and coordination ability. This review discusses the basic characteristics of F, and the basic principles of improving the photovoltaic performance and stability of PSC devices using F‐containing materials. We systematically summarized the latest progress in the application of F‐containing materials to achieve efficient and stable PSCs on several key interface layers. It is believed that this work will afford significant understanding and inspirations toward the future application directions of F‐containing materials in PSCs, and provide profound insights for the development of efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

Paracetamol‐based bis 1,2,3‐triazole analogues were synthesized involving copper‐catalyzed click chemistry protocol. The new compounds were characterized by 1H NMR, 13C NMR, and mass spectral techniques. All the compounds were evaluated for their in vitro anti‐inflammatory properties using diclofenac as standard reference. The compound 6b with chlorine and fluorine functions displayed outstanding activity with IC50 values of 7.34 ± 0.45 µM and 7.84 ± 0.47 µM, respectively. Compound 6g with methyl and fluorine functions displayed best activity with IC50 values of 9.34 ± 0.22 µM and 9.40 ± 0.35 µM, respectively. Compound 6i, 6k, 6f, 6a, 6e, 6h, 6j, and 6l exhibited promising activity with respect to diclofenac. Using PyRx tool, the molecular docking study against crystal structure of COX‐2 proved the binding efficacies with notable binding interactions. [ABSTRACT FROM AUTHOR]

Three non-fullerene acceptors (NFAs) with varying alkyl chain sizes and lengths but constant fluorine atoms were synthesized. BO-17F and HD-17F, with optimal fluorination, exhibit improved molecular packing and morphology, achieving efficiencies of 14.2% and 14.4%. This work highlights the importance of fine-tuning alkyl chains and fluorination levels in organic solar cells. [ABSTRACT FROM AUTHOR]

Branch‐connected dimerized acceptors can take full advantages of four end units in enhancing molecular packing comparing to that of terminal‐connected ones, thus potentially reaching the best balance between stability and power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, two branch‐connected dimerized acceptors, namely D1 and D2, are developed by employing bithiophene and difluorinated bithiophene as linker groups, respectively. Induced by the fluorine atoms on linker group, D2 affords a larger molar extinction coefficient, more importantly, the optimized nanoscale film morphology and superior charge transport behavior comparing to D1. Consequently, D2‐based binary OSCs render a good PCE of 16.66%, outperforming that of 15.08% for D1‐based ones. This work highlights the great significance of linker group screening in designing high‐performance branch‐connected dimerized acceptors. [ABSTRACT FROM AUTHOR]

The study proposes the utilization of microwave-assisted methods for converting neutralization slag (NS) into hydroxyapatite (HAP), offering an alternative to the conventional hydrothermal method. The microwave-assisted approach addresses the challenges encountered in hydrothermal reactions, such as particle agglomeration, reduced specific surface area, prolonged reaction time, high temperature requirements, and inadequate saturation adsorption capacity. By employing the response surface methodology with a Box-Behnken design, the study found that the microwave-assisted method significantly reduced the synthesis time from 90 to 25 min and the temperature from 120 °C to 56 °C. Furthermore, the microwave method consumed only 1/43 of the energy utilized in hydrothermal synthesis. To assess the performance of the synthesized HAP, various detection methods were utilized, including XRD, SEM-EDS, FTIR, Zeta potential, and ICP, which analyzed the crystal structure, crystallinity, morphology, chemical composition, and surface charge of HAP. The BET method was used to measure the specific surface area, further confirming the successful synthesis of HAP. The HAP synthesized through this microwave-assisted method exhibited a saturation adsorption capacity of up to 98.4 mg/g of fluoride ions from vanadium industrial raffinate. This study demonstrates that the microwave-assisted method provides a viable solution for reducing energy consumption and enhancing HAP synthesis efficiency for wastewater treatment in the vanadium industry. [Display omitted] [ABSTRACT FROM AUTHOR]

Visible light‐mediated photocatalytic approach for the radical functionalization of alkenes bearing the fluorinated aryl sulfide fragment is described. The process occurs in the presence of organic photocatalyst using sulfinates as sources of radicals. The key step of the reaction is the intramolecular 1,4‐migration of the polyfluoroaryl group. In the reaction, three new bonds are formed (two C−C and one C−S bond). The decisive role of fluorine atoms in the reaction efficiency was confirmed by DFT calculations. [ABSTRACT FROM AUTHOR]

In this work, we present our improved protocols for the single batch syntheses of approximately 32 g of [NHMe3][CB11H12] and 10 g of Na[CHB11F11] as well as salt metathesis reactions, granting access to useful starting materials to introduce the [CHB11F11]− anion. This includes the trityl cation [Ph3C]+ and the bis‐1,2‐difluorobenzene‐silver(I)‐complex [Ag(odfb)2]+, as well as some applications of the shown compounds. The described methodology allows the synthesis of large amounts of both the [CB11H12]− and the [CHB11F11]− anion and therefore making them accessible for further reactions. To facilitate the reproducibility, we present video tutorials of the synthetic steps towards Na[CHB11F11]. [ABSTRACT FROM AUTHOR]

The gas phase reaction of fluorine atoms with carbonyl sulfide, F + OCS → SF + CO (1), has been investigated over a wide temperature range, T = 220–960 K, in a discharge-flow system combined with mass spectrometry for the analysis of the reactive mixture. The reaction rate coefficient was determined as a function of temperature using both absolute (under pseudo-first-order conditions using an excess of F atoms) and relative rate methods: k1 = (8.95 ± 0.52) × 10−11 exp((102 ± 20)/T) cm3 molecule−1 s−1 (with an estimated total uncertainty of 15% independent of temperature). The SF radical was observed as the main primary reaction product. The experimental results are supported by theoretical calculations, which evidence that the reaction is exothermic with a weak negative temperature dependence. [ABSTRACT FROM AUTHOR]

Herein, fluorinated thioureas with various substituents (F1-F3) were synthesized and characterized spectroscopically and analytically to investigate their properties as antibacterial agents. Prior to experimental studies, Density Functional Theory (DFT) modeling was performed at B3LYP/6-31G (d,p) to complement and offer comparative overview with the experimental findings. With regards to all theoretical analyses, the Frontier Molecular Orbital (FMO) demonstrated a desirable low HOMO-LUMO gap for all three designated derivatives, particularly F1 (1.60 eV), which is consistent with its GCRDs values, namely its high electronegativity and low hardness values that corresponds to low LUMO energy, suggesting higher bacterial activity. Agar diffusion assay was used for the preliminary screening of in-vitro antibacterial activity against pathogenic Gram-positive and Gram-negative bacteria. All three derivates successfully inhibit at least two bacterial strains (B. cereus, S. aureus), but none were able to penetrate into E. coli. The highest inhibition rate was exhibited by F3 at 33.33 ± 0.71% against S. aureus, whilst F1 only managed to gain 29.63 ± 0.00% of inhibition rate for the same bacterium. Meanwhile, the lowest penetration rate was recorded at 1.53 ± 0.35% by F2 against B. cereus. [ABSTRACT FROM AUTHOR]

An expedient and easy-to-handle synthetic platform has been established for the constructing of 2 H -thiophenes carrying fluorine atoms through [4+1] cyclization of enaminothiones with fluorinated carbene precursors. This simple reaction system is well compatible with a wide range of substrates under completely metal-free conditions. The resulting 2 H -thiophenes can undergo further late-stage modifications to yield a wide range of fluorine-substituted heterocycles. [ABSTRACT FROM AUTHOR]

With environmental and health issues being raised, researchers have shifted their study from fluorinated to fluorine-free waterproof agents. However, most of the reported fluorine-free water repellents exhibit a significant drawback in their poor stability and durability of water repellency. In addition, the use of higher concentrations in these repellents results in the fabric becoming stiff, which negatively impacts the hand of the treated fabrics. To address these issues, dendrimer-like waterborne polyurethane prepolymers were initially synthesized using isophorone diisocyanate, polytetrahydrofuran, N -methyldiethanolamine, and trimethylolpropane as the primary materials. In this synthesis, sorbitan tristearate served as the dendrimer-like blocking agent, while single-ended bis-hydroxypropyl silicone oil was employed as functional monomers to enhance the hand and water repellency of the prepolymers. Then, dendrimer-like waterborne polyurethane was finished on the cotton fabric using a pad–dry–cure procedure. The test results showed that the water contact angle of dendrimer-like waterborne polyurethane film increased from 104.28° to 107.00° with the content of single-ended bis-hydroxypropyl silicone oil increasing, and the water contact angle of dendrimer-like waterborne polyurethane-finished fabrics reached 148.6° alone with a standard spray test rating of 90–95. In addition, the water contact angle of dendrimer-like waterborne polyurethane-finished fabrics was still greater than 140° even after five standard washes. The single-ended bis-hydroxypropyl silicone oil addition facilitated similar hand to the original fabric in dendrimer-like waterborne polyurethane-finished fabrics with high concentrations, surpassing market water repellents. This work is of great significance for improving the stability and durability of water repellency, and the hand of waterborne polyurethane fluorine-free water repellents in the textile industry. [ABSTRACT FROM AUTHOR]

Fluorosilicone rubber is essential for sealing in extreme temperatures and non‐polar environments due to its exceptional adaptability. However, achieving a high yield of fluorosilicone polymers with medium and high fluorine content remains a challenge. Herein, a facile gradient strategy is developed that involves modifying the method of cyclic monomer addition based on the rate of ring‐opening polymerization (ROP), to improve yield and adjust fluorine content precisely. The polymerization process is designed and tailored based on the reaction rates of anionic ring‐opening polymerization (AROP) and cationic ring‐opening polymerization (CROP) via an efficient gradient strategy. The effects of the polymerization process on the viscosity and yield of vinyl fluorosilicone polymers and hydrofluorosilicone polymers are investigated and optimized. Notably, the as‐prepared vinyl‐terminated fluoromethylsilane with 60% fluorine content (FMS‐Vi‐60F) has a high yield (86.6%) and high viscosity (150 000 mPa·s) in a short reaction time, which is superior to previous methods. Clearly, the gradient ring‐opening method developed in this work provides a facile and efficient synthesis for fabricating fluorosilicone polymers with a high yield and tunable fluorine content. [ABSTRACT FROM AUTHOR]

Addressing the environmental impact of SF6, we synthesized a fluorine-functionalized triphenylamine-based nanoporous organic polymer, ANOP-8, at room temperature using N,N,N′,N′-tetraphenylbenzidine and 2,3,4,5,6-pentafluorobenzaldehyde. ANOP-8, which incorporates 14.86% fluorine, has a BET surface area of 694 m2 g−1 and a robust C–C structure. It achieves SF6/N2 selectivities of 65 and 51 at 298 K and 1 bar through ideal adsorbed and breakthrough experiments, respectively. Molecular simulations have revealed the adsorption mechanisms, underscoring the potential of fluorinated polymers in developing future adsorbents for toxic gases. [ABSTRACT FROM AUTHOR]

A strategy to access fluorinated spiroindolenines has been developed, involving a selective functionalization of indoles with fluorinated moieties and subsequent catalytic dearomatization. Trifluomethylthio (SCF3), diethyl phosphono(difluoromethyl)thio (SCF2P(O)(OEt)2) and (phenylsulfonyl)difluoromethyl (CF2SO2Ph) groups were embedded at the C2 position of indole derivatives substituted with alkynes, allenes, and allyl carbonate moieties at the C3 position. A gold‐catalyzed cycloisomerization gave access to five spiroindolenines, and an enantioselective palladium catalyzed cyclization provided 10 fluorinated spirocyclic products with up to 77% ee. [ABSTRACT FROM AUTHOR]

Experimental evidence for hypervalent compounds of second‐row elements is still scarce in literature. Here, we present the first report of the long‐sought binary, hypervalent trifluorooxygenate anion [OF3]−. It was isolated in solid Ne matrices under cryogenic conditions after reacting oxygen difluoride with free fluoride ions from laser ablation of alkali metal fluorides MF (M=Li−Cs). VSEPR theory and calculations at the CCSD(T) level predict a C2v‐symmetric T‐shape structure with one short and two long O−F bond lengths in [OF3]−. This is confirmed experimentally by FTIR spectroscopy in combination with isotopic labeling. Analysis of the natural local molecular orbitals shows the presence of one 2c–2e and one 3c–4e bond each. Natural resonance theory indicates the importance of the stability of [OF2]⋅− for the stability of [OF3]−. Although free [OF2]⋅− was not detected, the species MOF2 (M=Na−Cs) could be observed in the same experiments, which are best described as contact ion pairs of M+[OF2]⋅−. [ABSTRACT FROM AUTHOR]

Alternating copolymers are crucial for diverse applications. While dispersity (Ð, also known as molecular weight distribution, MWD) influences the properties of polymers, achieving low dispersities in alternating copolymers poses a notable challenge via free radical polymerizations (FRPs). In this work, we demonstrated an unexpected discovery that dispersities are affected by the participation of charge transfer complexes (CTCs) formed between monomer pairs during free radical alternating copolymerization, which have inspired the successful synthesis of various alternating copolymers with low dispersities (>30 examples, Ð=1.13–1.39) under visible‐light irradiation. The synthetic method is compatible with binary, ternary and quaternary alternating copolymerizations and is expandable for both fluorinated and non‐fluorinated monomer pairs. DFT calculations combined with model experiments indicated that CTC‐absent reaction exhibits higher propagation rates and affords fewer radical terminations, which could contribute to low dispersities. Based on the integration of Monte Carlo simulation and Bayesian optimization, we established the relationship map between FRP parameter space and dispersity, further suggested the correlation between low dispersities and higher propagation rates. Our research sheds light on dispersity control via FRPs and creates a novel platform to investigate polymer dispersity through machine learning. [ABSTRACT FROM AUTHOR]

Due to the increasing fluoride concentrations in water bodies, significant environmental concerns have arisen. This study focuses on aluminum-based materials with a high affinity for fluorine, specifically enhancing metal–organic frameworks (MOFs) with amino groups to improve their adsorption and defluorination performance. We systematically investigate the factors influencing and mechanisms governing the adsorption and defluorination behavior of amino-functionalized aluminum-based MOF materials in aqueous environments. An SEM, XRD, and FT-IR characterization confirms the successful preparation of NH2-MIL-101 (Al). In a 10 mg/L fluoride ion solution at pH 7.0, fluoride ion removal efficiency increases with the dosage of NH2-MIL-101 (Al), although the marginal improvement decreases beyond 0.015 g/L. Under identical conditions, the fluoride adsorption capacity of NH2-MIL-101 (Al) is seven times greater than that of NH2-MIL-101 (Fe). NH2-MIL-101 (Al) demonstrates effective fluoride ion adsorption across a broad pH range, with superior fluoride uptake in acidic conditions. At a fluoride ion concentration of 7 mg/L, with 0.015 g of NH2-MIL-101 (Al) at pH 3.0, adsorption equilibrium is achieved within 60 min, with a capacity of 31.2 mg/g. An analysis using adsorption isotherm models reveals that the fluoride ion adsorption on NH2-MIL-101 (Al) follows a monolayer adsorption model, while kinetic studies indicate that the predominant adsorption mechanism is chemical adsorption. This research provides a scientific basis for the advanced treatment of fluoride-containing wastewater, offering significant theoretical and practical contributions. [ABSTRACT FROM AUTHOR]

A route is developed to (γ,γ',γ"'‐trifluoro)neopentyl (TFNP) aryl ethers to extend the methods for the introduction of the tert‐butyl group, carrying a fluorine on each of the methyl substituents. The route combines neopentyltosylate 3 with phenols and thiophenols to give efficient substitution reactions to the corresponding TFNP aryl ethers. The three C−F bonds adopt a helical propeller conformation as revealed by computation and single crystal X‐ray structure analysis. The LogPs of TFNP ethers are lower (more hydrophilic) than their neopentyl analogues. The metabolism of selected TFNP ethers was explored in the fungus Cunninghamella elegans. [ABSTRACT FROM AUTHOR]

Helicenes, with their unique helical structures, have long captured the interest of synthetic chemists, not only as end products, but also as versatile platforms for further chemical transformations. However, transforming [6]helicene into planar coronene typically requires harsh conditions and poses significant challenges. Herein, we demonstrate that replacing the terminal benzene ring of [6]helicene with a thiophene ring enables its photochemical transformation into coronene. Sulfur oxidation of the thiophene ring enables the corresponding thermal transformation, and the terminal tetrafluorination of the opposite benzene ring further accelerates this process, yielding 1,2‐difluorocoronene, as confirmed by X‐ray crystallography. The transformation begins with an intramolecular Diels–Alder reaction, whose activation energy is significantly lowered by these structural changes. Our findings underscore the utility of strategic modifications such as sulfur oxidation and fluorination in promoting this "helix‐to‐disc" conversion and opening new avenues for synthesizing functional polycyclic aromatics. [ABSTRACT FROM AUTHOR]

Sulfur based deoxyfluorination reagents are usually derived from the corrosive gas SF4. Herein, we report the synthesis and properties of an easily accessible phosphonium salt [(tmg)3PF]+SF5− (1) which was obtained from the reaction of sulfur hexafluoride (SF6) with tris(tetramethylguanidinyl)phosphine. The performance of this crystalline SF5− salt as a reagent in deoxyfluorination reactions was investigated together with a second SF5− salt [(R1)3PF]+SF5− (2) containing bulky substituents (R1=1,3‐di‐tert‐butylimidazolidin‐2‐ylidenamino). Both reagents proved to be effective for the deoxyfluorination of various functional groups including alcohols, anhydrides, and amides. [ABSTRACT FROM AUTHOR]

A metal‐free hypervalent iodine‐mediated C3‐trifluoropropionyloxylation of N‐substituted indoles was developed. (Bis‐trifluoropropanoate)iodobenzene was used as both the oxidant and fluorine source. The reaction was sensitive to the N‐protecting groups of the indoles. N‐acylated indoles provided 3‐trifluoropropionyloxylated indoles, while 3‐trifluoropropionyloxylated oxindoles were generated from indoles bearing N‐alkyl groups. [ABSTRACT FROM AUTHOR]

Fluorine's high electronegativity, lipophilicity, and metabolic stability make it a valuable element for drug design and development. Consequently, significant synthetic efforts have focused on introducing fluorine and fluorinated motifs into organic molecules, with the synthesis of trifluoromethyl ketones (TFMKs) recently attracting considerable attention. Building on our ongoing research on radical organofluorine chemistry, we present herein the divergent synthesis of trifluoromethyl ketones directly from olefins using readily available chloro‐ and bromotrifluoroacetone as synthetic precursors of the trifluoroacetonyl radical under photoredox catalysis. Mechanistic studies revealed that the divergence is attained through radical polar crossover (RPC) and hydrogen atom transfer (HAT) mechanisms. [ABSTRACT FROM AUTHOR]

Optically transparent polyimide (PI) films with good atomic oxygen (AO) resistance have been paid extensive attention as thermal controls, optical substrates for solar cells or other components for low Earth orbit (LEO) space applications. However, for common PI films, it is usually quite difficult to achieve both high optical transparency and AO resistance and maintain the intrinsic thermal stability of the PI films at the same time. In the current work, we aimed to achieve the target by using the copolymerization methodology using the fluorinated dianhydride 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), the fluorinated diamine 2,2-bis [4-(4-aminophenoxy)phenyl]hexafluoropropane (BDAF) and the polyhedral oligomeric silsesquioxane (POSS)-containing diamine N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) as the starting materials. The fluoro-containing monomers were used to endow the PI films with good optical and thermal properties, while the silicon-containing monomer was used to improve the AO resistance of the afforded PI films. Thus, the 6FCDA-based PI copolymers, including 6FCPI-1, 6FCPI-2 and 6FCPI-3, were prepared using a two-step chemical imidization procedure, respectively. For comparison, the analogous PIs, including 6FPI-1, 6FPI-2 and 6FPI-3, were correspondingly developed according to the same procedure except that 6FCDA was replaced by 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Two referenced PI homopolymers were prepared from BDAF and 6FDA (PI-ref1) and 6FCDA (PI-ref2), respectively. The experimental results indicated that a good balance among thermal stability, optical transparency, and AO resistance was achieved by the 6FCDA-PI films. For example, the 6FCDA-PI films exhibited good thermal stability with glass transition temperatures (Tg) up to 297.3 °C, good optical transparency with an optical transmittance at a wavelength of 450 nm (T450) higher than 62% and good AO resistance with the erosion yield (Ey) as low as 1.7 × 10−25 cm3/atom at an AO irradiation fluence of 5.0 × 1020 atoms/cm2. The developed 6FCDA-PI films might find various applications in aerospace as solar sails, thermal control blankets, optical components and other functional materials. [ABSTRACT FROM AUTHOR]

For the first time, the possibility of using hexafluoro‐1,4‐naphthoquinone for the construction of condensed heterocyclic system was demonstrated. As a result, two‐step synthesis of previously unknown 5,6,7,8‐tetrafluoro‐1H‐benzo[f]indol‐4,9‐dione derivatives was elaborated. The suggested method includes initial interaction of hexafluoro‐1,4‐naphthoquinone with various methyl 3‐aminocrotonates and subsequent intramolecular cyclization into the target fluorinated benzo[f]indole‐4,9‐diones. The distinctive feature of considered protocol is regiospecific reaction of fluorine atoms in quinone fragment. Advantages of the presented approach are simple synthetic procedure avoiding chromatographic purification, atom economy and readily available starting materials. The structure of one of the synthesized compounds was established by x‐ray analysis. [ABSTRACT FROM AUTHOR]

Fluorinated, manganese‐redox cation‐disordered rocksalts are promising candidates for high‐performance cobalt‐free Li‐ion cathode active material. A need for reactive fluorinated precursors was however identified. While manganese oxyfluorides are promising precursor candidates, none stable at room temperature was reported prior to 2023. The key to their recent synthesis by reacting molecular fluorine with MnO was a procedure to continuously scan the temperature axis in search of activation temperatures. In line with this philosophy of continuous exploration of the chemical space, two experimental procedures are reported to scan the stoichiometry axis of a gas‐solid phase diagram in search of transitions and intermediate compounds. Their application to F2 ‐ Mn3O4 and F2 ‐ Mn2O3 phase diagrams resulted in the discovery of two new ranges of stable manganese oxyfluorides of respective compositions MnO1.33‐0.13xFx with x<0.5 and MnO1.5‐0.22xFx with x<1. [ABSTRACT FROM AUTHOR]

We present a comprehensive study on the conformational behavior of diversely substituted 4‐fluorotetrahydrothiopyran derivatives. Through quantum chemical simulations including DFT as well as NBO and NPA analysis, we elucidate the pivotal role of electrostatic interactions, occasionally complemented by hyperconjugative interactions, in stabilizing axial fluorine conformers. Less polar conformers were occasionally obtained, attributed to the interplay of electrostatic and hyperconjugative interactions. Experimental validation through NMR spectroscopy aligns with the computational analysis, thus providing a coherent understanding of the structural dynamics of these compounds. [ABSTRACT FROM AUTHOR]

The 2,2‐difluoroethyl group is an important lipophilic hydrogen bond donor in medicinal chemistry, but its incorporation into small molecules is often challenging. Herein, we demonstrate electrophilic 2,2‐difluoroethylation of thiol, amine and alcohol nucleophiles with a hypervalent iodine reagent, (2,2‐difluoro‐ethyl)(aryl)iodonium triflate, via a proposed ligand coupling mechanism. This transformation offers a complementary strategy to existing 2,2‐difluoroethylation methods and allows access to a wide range of 2,2‐difluoroethylated nucleophiles, including the drugs Captopril, Normorphine and Mefloquine. [ABSTRACT FROM AUTHOR]

Skeletal fluorosis is a chronic metabolic bone disease caused by long-term excessive fluoride intake. Abnormal differentiation of osteoblasts plays an important role in disease progression. Research on the mechanism of fluoride-mediated bone differentiation is necessary for the prevention and treatment of skeletal fluorosis. In the present study, a rat model of fluorosis was established by exposing it to drinking water containing 50 mg/L F−. We found that fluoride promoted Runt-related transcription factor 2 (RUNX2) as well as superoxide dismutase 2 (SOD2) and sirtuin 3 (SIRT3) expression in osteoblasts of rat bone tissue. In vitro, we also found that 4 mg/L sodium fluoride promoted osteogenesis-related indicators as well as SOD2 and SIRT3 expression in MG-63 and Saos-2 cells. In addition, we unexpectedly discovered that fluoride suppressed the levels of reactive oxygen species (ROS) and mitochondrial reactive oxygen species (mtROS) in osteoblasts. When SOD2 or SIRT3 was inhibited in MG-63 cells, fluoride-decreased ROS and mtROS were alleviated, which in turn inhibited fluoride-promoted osteogenic differentiation. In conclusion, our results suggest that SIRT3/SOD2 mediates fluoride-promoted osteoblastic differentiation by down-regulating reactive oxygen species. [ABSTRACT FROM AUTHOR]

Fluorine-Doped Tin Oxide (FTO) thin films were deposited on a glass substrate using the spin coating technique and then annealed in both open air and nitrogen environments at temperatures between 500°C and 600°C. This study examined how annealing temperature affects the structural and electrical properties of the films. X-ray diffraction (XRD) analysis showed that the films had a polycrystalline structure, predominantly with the (110) plane. As the annealing temperature is increased, the crystal size also increased, leading to lower dislocation density and higher electron mobility. The resistivity of the films decreased with higher annealing temperatures, reaching its lowest value at 600°C. These findings indicate that annealing temperature is crucial for optimizing the structural and electrical properties of FTO thin films made via spin coating. The optimal annealing conditions were found to be 600°C in open air, resulting in a resistivity of 2.47x10-3 Ω-cm, sheet resistance of 1.08x10-2 Ω/square, the largest grain size of 18.41 nm, and the lowest values for dislocation density (2.95x1015 lines/cm²) and micro-strain (1.97x10-3). [ABSTRACT FROM AUTHOR]

Fluorinated sludge, as the main byproduct of refined production in the semiconductor industry, is a hazardous solid waste. In the process of co-treating fluorine-containing sludge in cement kilns, the fluorine, phosphate, and various heavy metal ions contained in the fluorinated sludge will inevitably be introduced into the cement raw material at the same time. These ions will significantly affect and change the calcination process and properties of cement raw material minerals. However, there are few studies on the impact of their coexistence on the properties of cement clinker. Therefore, this paper systematically studied the synergistic influence mechanism of fluorine, phosphate, and heavy metal ions co-doping on the calcination process, microstructure, and hydration characteristics of tricalcium silicate ( C3 S). The results show that compared with the single doping of phosphorus, the co-doping of phosphate and heavy metal ions is not conducive to the firing of C3 S, while the co-doping of fluorine, phosphate, and heavy metal ions has a significant synergistic promoting effect on the firing of C3 S, while significantly improving the symmetry of C3 S crystal structure, resulting in more defects of different types on the surface of C3 S minerals. Compared with the single doping of phosphorus, the co-doping of phosphate and heavy metal ions is beneficial for improving the initial and later hydration rates of C3 S, reducing the aspect ratio of rod- shaped hydrated calcium silicate (C-S-H). The effect of co-doping of fluorine, phosphate, and heavy metal ions on the hydration performance of C3 S depends on the doping ratio of each ion. However, as the doping amount of each ion increases, the acceleration period of C3 S hydration will be continuously delayed, and the co-doping of the three ions will promote the increase of the aspect ratio of rod-shaped C-S-H. [ABSTRACT FROM AUTHOR]

Soil naturally contains fluorine, but concerns arise when its levels or bioavailability are increased by human activities or specific compounds. South Korea faces challenges in regulating soil fluorine pollution despite implementing stricter total fluorine standards (e.g., 400 mg/kg for residential areas) than many developed countries (e.g., 4000 mg/kg for all land uses in Japan). Moreover, a recent national soil survey in Korea revealed widespread exceedance (15.2% of samples) of the Soil Worrisome Level, even in areas with naturally low background levels of fluoride. This highlights the limitations of regulations based solely on total fluorine content. This review explores the global landscape of soil fluorine management strategies and examines potential solutions that reconcile environmental protection with economic concerns. We recommend a shift towards regulating specific and hazardous fluorine compounds rather than total content and prioritizing remediation efforts based on assessments of bioavailable fluorine. This approach may help Korea establish a more effective and sustainable strategy for managing soil fluorine pollution. [ABSTRACT FROM AUTHOR]

ABSTRACT For the first time, the interaction of perfluoro‐1,4‐naphthoquinone with various 5‐aminopyrazoles was investigated. It was shown that three types of products can be obtained depending on the structure of starting aminopyrazole. For all examples, the substitution of one fluorine atom in quinone moiety was observed. Wherein, in most cases, the starting aminopyrazoles act as a C‐nucleophile leading to 2‐(5‐aminopyrazol‐4‐yl)‐3,5,6,7,8‐pentafluoronaphthalene‐1,4‐diones. At the same time substrates unsubstituted at ring nitrogen atom regiospecifically react at aminogroup resulting in the formation of 2,5,6,7,8‐pentafluoro‐3‐((pyrazol‐5‐yl)amino)naphthalene‐1,4‐diones. Besides that, the absence of steric hindrance in the pyrazole unit allowed us to direct the process at nitrogen atom in Position 2 and synthesize zwitter‐ionic 3‐(5‐aminopyrazol‐2‐ium‐2‐yl)‐5,6,7,8‐tetrafluoro‐1,4‐dioxo‐1,4‐dihydronaphthalen‐2‐olates. The structures of two types of obtained products were confirmed by x‐ray analysis. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The present work prepared a copper N‐heterocyclic carbene complex that could be used in catalyzing the homogeneous hydrogenation of carboxylic acid with ammonia borane (hydrogen source) to synthesize primary alcohols. Various aromatic and aliphatic carboxylic acids with diverse functional groups were transformed to respective alcohols in moderate to high yields. The process can be easily scaled up (TON up to 14545) and exhibits a high compatibility with different sensitive functional groups, including fluorine, chlorine, bromine, iodine, hydroxyl, cyano and nitro groups. IMesCuCl/NH3·BH3 combination can selectively reduce aromatic and aliphatic esters. Mechanistic studies indicate that Cu‐H species produced in situ are the active intermediates. [ABSTRACT FROM AUTHOR]

Background: Excessive subchronic fluoride exposure can cause severe damage to detoxification organs, including the liver. Sodium butyrate has anti-inflammatory, antitumor, antioxidant and immunomodulatory properties. However, relatively few studies have investigated the effects of sodium butyrate on liver injury caused by subchronic fluoride exposure. The purpose of this research was to investigate the effect and mechanism of sodium butyrate on fluoride-induced hepatic inflammatory injury via the expression of nod-like receptor protein 3 (NLRP3). Methods: Mice were subjected to randomization into four groups, control group (C), fluorosis group (F), sodium butyrate alone group (S), and treatment group (Y). The mice in groups F and F + S drank 100 mg/L sodium fluoride-containing distilled water freely every day. After fluoride exposure lasted for 3 months, the mice in group S and F + S were gavaged with sodium butyrate daily at a concentration of 1000 mg/kg. Following the treatment regimen, liver specimens were collected for analysis. The mRNA and protein expression levels of inflammatory factors and NLRP3 and its downstream gene were measured by RT-qPCR and western blotting. Results: The histological hematoxylin and eosin (H&E) staining of liver showed that the subchronic fluoride-exposed group were chronic inflammation. The liver of treatment group were less vacuolar degeneration and inflammatory infiltration. The results of the biochemical assay showed that the subchronic fluoride-exposed group were liver injury. In addition, the detection of oxidative stress indicators showed that chronic subchronic fluoride exposure could lead to an increase in the level of oxidative stress in the liver, and the treatment alleviated this increase. RT-qPCR results showed that compared with those in the control group, the mRNA levels of the inflammatory factors TNF-α, IL-6 and IL-1β, the NLRP3 inflammasome and its downstream factors NLRP3, caspase-1, gasdermin D (GSDMD) and IL-18 increased in the liver tissue of mice in the subchronic fluoride-exposed group. Sodium butyrate released inflammatory factors during subchronic fluoride exposure and inhibited the protein expression of activated NLRP3 to a certain extent. Conclusions: Sodium butyrate may play a protective role by antagonizing the production of activated inflammasomes and their downstream inflammatory factors in the livers of subchronic fluoride-exposed mice. [ABSTRACT FROM AUTHOR]

A practical and efficient trifluoromethylation of readily available and bench stable N‐Thiophthalimides and N‐Thioimides with Ruppert‐Prakash reagent (TMS‐CF3) is described. The reaction proceeds at room temperature and only requires NaOAc as the mild promoter to prepare a series of trifluoromethyl thioethers in good to excellent yields. Both aryl and alkyl derivates are well trifluoromethylated under transition‐metal‐free reaction conditions. Moreover, the reaction features with scale‐up synthesis and late‐stage modification of bioactive molecule. [ABSTRACT FROM AUTHOR]

Functional group (FG) is one of the cornerstone concepts in organic chemistry and related areas. The wide spread of bioisosterism ideas in medicinal chemistry and beyond caused a striking rise in demand for novel FGs with a defined impact on the developed compound properties. In this work, the evaluation of the 3,3‐difluorooxetane unit (3,3‐diFox) as a functional group for bioisosteric replacements is disclosed. A comprehensive experimental study (including multigram building block synthesis, quantification of steric and electronic properties, measurements of pKa, LogP, chemical stability, and biological evaluation of the 3,3‐diFox‐derived bioisostere of a drug candidate) revealed a prominent behavior of the 3,3‐diFox fragment as a versatile substituent for early drug discovery programs. [ABSTRACT FROM AUTHOR]

As great potential recycling strategy, the direct regeneration of spent LiCoO2 (LCO) is beneficial for lowering environmental pollutions and promoting global sustainability. However, owing to the using of binder and electrolyte, some fluorine impurities would be remained into spent materials. Considering the doping behaviors of F‐elements, their suitable content introducing would facilitate the energy‐storage abilities of regenerated LCO. Herein, through the tailored introduction of F‐elements, spent LCO are successfully regenerated with physical‐chemical evolutions. Benefitting from the existed oxygen vacancies, the diffusion energy‐barrier of F‐elements is reduced from 1.73 eV to 0.61 eV, facilitating the establishment of gradient F‐doped subsurface, along with the formation of rigid CoO5F. Meanwhile, excess F‐elements (1 wt %, as a threshold) lead to the formation of LiF passivation layer on the surface. Thus, the as‐optimized sample displays a considerable capacity of 154.4 mAh g−1 even at 5.0 C, with retention rate (88.3 %) in 3.0–4.5 V. Supported by detailed electrochemical and kinetic analysis, the structural advantages are confirmed to boost the improved redox activity of Co‐ions and the alleviating of irreversible oxygen‐release. Give this, the work is anticipated to reveal the evolutions of regenerated LCO with the introduced F‐elements, whilst providing the practical regeneration strategies toward excellent high‐voltage properties. [ABSTRACT FROM AUTHOR]

The human colon is home to trillions of microorganisms that modulate gastrointestinal physiology. The understanding of how this gut ecosystem impacts human health, although evolving, is slowed by the lack of accessible tools suitable to studying complex host‐mucus‐microbe interactions. Here, a synthetic gel‐like material capable of recapitulating the varied structural, mechanical, and biochemical profiles of native human colonic mucus is reported to develop compositionally simple microbiome screening platforms with utility in microbiology and drug discovery. The viscous fibrillar material is realized through templated assembly of a fluorine‐rich amino acid at liquid‐liquid interphases. The fluorine‐assisted mucus surrogate (FAMS) can be decorated with mucins to serve as a habitat for microbial colonization and integrated with human colorectal cells to generate artificial mucosae, referred to as a microbiome organoid. Notably, FAMS are made with inexpensive and commercially available materials and can be generated using simple protocols and standard laboratory hardware. As a result, this platform can be broadly incorporated into various laboratory settings to advance probiotic research and inform in vivo approaches. If implemented into high throughput screening approaches, FAMS may represent a valuable tool to study compound metabolism and gut permeability, with an exemplary demonstration of this utility presented here. [ABSTRACT FROM AUTHOR]

Dermatomycoses are the most widespread fungal skin infections worldwide and directly affect patients' quality of life. They are challenging to manage because of the need for prolonged treatment and the development of resistance to antifungal agents. This article studies the antifungal activity of trifluoromethylthiolated cinnamate derivatives on Candida species and dermatophytes as well as possible mechanisms of action, irritability, and cytotoxicity tests. These molecules show activity against dermatophyte fungi with minimum inhibitory concentrations (MIC) as low as 0.39 μg mL−1. In particular, chloroaromatic derivatives demonstrated the best inhibition profile (1.56–6.25 μg mL−1). Importantly, our series of molecules were not active against Candida spp., being selective for dermatophytes. A study of the mechanism of action suggests that our SCF3 cinnamates do not bind directly to ergosterol or the cell wall. The physicochemical parameters and the absence of irritability resulting from the HET‐CAM test demonstrate that compound 8 can be considered a future candidate for the therapy of dermatophytosis. [ABSTRACT FROM AUTHOR]

Novel tetrafluoro-λ6-sulfanyl-containing oligomers prepared by visible light-promoted addition of 1,4-(bis-chlorotetrafluoro-λ6-sulfanyl) benzene or 1,3-(bis-chlorotetrafluoro-λ6-sulfanyl) benzene to either 1,4-diethynyl benzene or the 1,3-diethynyl isomers form hard, stress resistant thin films on spin casting. The isomeric oligomers were utilized to establish a structure-function relationship for the mechanical properties of films prepared from the oligomers. The Young's moduli of 145-nm-thick cured films could reach 60 GPa. The measured hardnesses, between 1.57 and 2.77 GPa, were more than double those of polymethyl methacrylate (PMMA) films. Curing of the tetrafluoro-λ6-sulfanyl-containing polymer films by UV irradiation resulted in coatings that exhibited remarkable hardness and modulus with good surface adhesion to silicon. [ABSTRACT FROM AUTHOR]

A modular synthesis of sulfondiimidoyl fluorides—the double aza‐analogues of sulfonyl fluorides—allowing variation of the carbon and both nitrogen‐substituents is reported. The chemistry uses readily available organometallic reagents, commercial sulfinylamines, simple electrophiles, and N‐fluorobenzenesulfonimide (NFSI), as the starting materials. The reactions are broad in scope, efficient, and scalable. We show that the sulfondiimidoyl fluoride products can be combined with amines to provide sulfondiimidamides, and with organolithium reagents to provide sulfondiimines, and that reactivity in these transformations can be modulated by variation of the N‐substituents. [ABSTRACT FROM AUTHOR]

Controlled radical copolymerizations present attractive avenues to obtain polymers with complicated compositions and sequences. In this work, we report the development of a visible‐light‐driven organocatalyzed controlled copolymerization of fluoroalkenes and acyclic N‐vinylamides for the first time. The approach enables the on‐demand synthesis of a broad scope of amide‐functionalized main‐chain fluoropolymers via novel fluorinated thiocarbamates, facilitating regulations over chemical compositions and alternating fractions by rationally selecting comonomer pairs and ratios. This method allows temporally controlled chain‐growth by external light, and maintains high chain‐end fidelity that promotes facile preparation of block sequences. Notably, the obtained F/N hybrid polymers, upon hydrolysis, afford free amino‐substituted fluoropolymers versatile for post modifications toward various functionalities (e.g. amide, sulfonamide, carbamide, thiocarbamide). We further demonstrate the in situ formation of polymer networks with desirable properties as protective layers on lithium metal anodes, presenting a promising avenue for advancing lithium metal batteries. [ABSTRACT FROM AUTHOR]

Ligand binding hotspots are regions of protein surfaces that form particularly favourable interactions with small molecule pharmacophores. Targeting interactions with these hotspots maximises the efficiency of ligand binding. Existing methods are capable of identifying hotspots but often lack assays to quantify ligand binding and direct elaboration at these sites. Herein, we describe a fragment‐based competitive 19F Ligand Based NMR (LB‐NMR) screening platform that enables routine, quantitative ligand profiling focused at ligand‐binding hotspots. As a proof of concept, the method was applied to 4′‐phosphopantetheine adenylyltransferase (PPAT) from Mycobacterium abscessus (Mabs). X‐ray crystallographic characterisation of the hits from a 960‐member fragment screen identified three ligand‐binding hotspots across the PPAT active site. From the fragment hits a collection of 19F reporter candidates were designed and synthesised. By rigorous prioritisation and use of optimisation workflows, a single 19F reporter molecule was generated for each hotspot. Profiling the binding of a set of structurally characterised ligands by competitive 19F LB‐NMR with this suite of 19F reporters recapitulated the binding affinity and site ID assignments made by ITC and X‐ray crystallography. This quantitative mapping of ligand binding events at hotspot level resolution establishes the utility of the fragment‐based competitive 19F LB‐NMR screening platform for hotspot‐directed ligand profiling [ABSTRACT FROM AUTHOR]

Symmetry-forming closest approaches of aromatic rings; 'Symthons', are usually the strongest interactions in halobenzene crystal structures. Where they combine to create π–π stacking, they are as strong as hydrogen bonds. This π–π stacking is disrupted when fluorine is present, as revealed in this analysis of all 290 closest aromatic approaches in the crystal structures of halobenzenes. Closest aromatic approaches involving fluorine show fewer examples of 'Symthon I' π–π stacking, and more examples of offset translations with larger displacements. Edge⋯face approaches are also more common in the presence of fluorine, frequently accommodating fluorine atoms in the 'edges'. Some edge⋯face approaches do not embody any symmetry. These findings are consistent with lower melting points and favourable connections between fluorine and positively charged carbon atoms. [ABSTRACT FROM AUTHOR]