The purpose of this Special Issue is to showcase the latest findings in fluorine chemistry [...].

Building blocks have been identified that can be functionalised by sequential nucleophilic aromatic substitution. Some examples are reported that involve the formation of cyclic benzodioxin and phenoxathiine derivatives from 4,5-difluoro-1,2-dinitrobenzene, racemic quinoxaline thioethers, and sulfones from 2,3-dichloroquinoxaline and (2-aminophenylethane)-2,5-dithiophenyl-4-nitrobenzene from 1-(2-aminophenylethane)-2-fluoro-4,5-dinitrobenzene. Four X-ray single-crystal structure determinations are reported, two of which show short intermolecular N-O…N \"π hole\" contacts.

The kinetics of the F2 reaction with thiirane (C2H4S) was studied for the first time in a flow reactor combined with mass spectrometry at a total helium pressure of 2 Torr and in the temperature range of 220 to 800 K. The rate constant of the title reaction was determined under pseudo-first-order conditions, either monitoring the kinetics of F2 or C2H4S consumption in excess of thiirane or of F2, respectively: k1 = (5.79 ± 0.17) × 10-12 exp(-(16 ± 10)/T) cm3 molecule-1 s-1 (the uncertainties represent precision of the fit at the 2σ level, with the total 2σ relative uncertainty, including statistical and systematic errors on the rate constant being 15% at all temperatures). HF and CH2CHSF were identified as primary products of the title reaction. The yield of HF was measured to be 100% (with an accuracy of 10%) across the entire temperature range of the study. Quantum computations revealed reaction enthalpies ranging from -409.9 to -509.1 kJ mol-1 for all the isomers/conformers of the products, indicating a strong exothermicity. Boltzmann relative populations were then established for different temperatures.

Fluorine possesses distinctive chemical characteristics, such as its strong electron-withdrawing ability and small atomic size, which render it an invaluable asset in the design and optimization of pharmaceuticals. The utilization of fluorine-enriched medications for combating cancer has emerged as a prominent approach in medicinal chemistry and drug discovery, offering improved clinical outcomes and enhanced pharmacological properties. This comprehensive review explores the synthetic approaches and clinical applications of approved 22 representative fluorinated anti-cancer drugs from 2019 to present, shedding light on their historical development, brand names, drug target activity, mechanism of action, preclinical pharmacodynamics, clinical efficacy, and toxicity. Additionally, the review provides an extensive analysis of the representative synthetic techniques employed. Overall, this review emphasizes the significance of incorporating fluorine chemistry into anti-cancer drug research while highlighting promising future prospects for exploring compounds enriched with fluorine in the battle against cancer.

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This research aimed to introduce a novel method for the valorization of mineral waste, focusing on the development of hydroxyapatite (HAP) as an effective and economical adsorbent for immobilizing fluoride ions (F-) in soil. Hydroxyapatites were produced through the reaction between potassium dihydrogen phosphate (KH2PO4) and calcium-abundant limestone soil (CLS). X-ray diffraction analyses revealed that the primary phases in HAPCLS were brushite (CaHPO5·2H2O) and hydroxyapatite (Ca10(PO4)6(OH)2). The FTIR spectra exhibited characteristics akin to natural HAP, including the presence of orthophosphate groups (PO43-), hydroxyl groups (OH-), and both A/B types of carbonates in the apatite structure. The morphology of the synthesized HAP, as observed through SEM-EDS, was consistent with that of phosphocalcic hydroxyapatite crystals. The EDS results indicated a Ca/P atomic ratio of 1.7 for HAPCLS, aligning closely with the typical hydroxyapatite stoichiometry (Ca/P = 1.67). The application of HAP to reduce fluoride (F-) levels in soil proved to be successful; introducing 1% of various HAP formulations reduced the fluoride concentration from 51.4 mg/kg in untreated soil to levels below the IWSI limit (10 mg/kg), achieving a reduction to 8.1 mg/kg for HAPCLS. The sequential extraction of fluoride demonstrated that after soil treatment, fluoride was predominantly removed from the residual fraction (Fraction 4) and was effectively sequestered by the hydroxyapatites (Ca10(PO4)6(OH)2) through anionic exchange with hydroxide ions (OH-), resulting in the formation of stable and insoluble fluorapatite (Ca10(PO4)6F2).

The approved anthelmintic salicylanilide drug niclosamide has shown promising anticancer and antimicrobial activities. In this study, new niclosamide derivatives with trifluoromethyl, trifluoromethylsulfanyl, and pentafluorosulfanyl substituents replacing the nitro group of niclosamide were prepared (including the ethanolamine salts of two promising salicylanilides) and tested for their anticancer activities against esophageal adenocarcinoma (EAC) cells. In addition, antifungal activity against a panel of Madurella mycetomatis strains, the most abundant causative agent of the neglected tropical disease eumycetoma, was evaluated. The new compounds revealed higher activities against EAC and fungal cells than the parent compound niclosamide. The ethanolamine salt 3a was the most active compound against EAC cells (IC50 = 0.8-1.0 µM), and its anticancer effects were mediated by the downregulation of anti-apoptotic proteins (BCL2 and MCL1) and by decreasing levels of β-catenin and the phosphorylation of STAT3. The plausibility of binding to the latter factors was confirmed by molecular docking. The compounds 2a and 2b showed high in vitro antifungal activity against M. mycetomatis (IC50 = 0.2-0.3 µM) and were not toxic to Galleria mellonella larvae. Slight improvements in the survival rate of G. mellonella larvae infected with M. mycetomatis were observed. Thus, salicylanilides such as 2a and 3a can become new anticancer and antifungal drugs.

Alternating copolymers are crucial for diverse applications. While dispersity (Ɖ, 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, Ɖ = 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.

The impact of cadmium (Cd) and fluorine (F) on plant and human health has provoked significant public concern; however, their combined effects on plant and soil bacterial communities have yet to be determined. Here, a pot experiment was conducted to evaluate the effects of exogenous F, Cd, and their combination (FCd) on lettuce growth and soil bacterial communities. The results revealed that F and Cd concentrations in lettuce ranged from 63.69 to 219.45 mg kg-1 and 1.85 to 33.08 mg kg-1, respectively, presenting lower values in shoots than in the roots. Moreover, low contamination levels had no discernable influence on lettuce growth, but showed a synergistic negative on plant biomass when exogenous F and Cd exceeds 300 and 1.0 mg kg-1, respectively. The results of 16S rRNA gene sequencing indicated that the most abundant bacterial community at the phylum level was Proteobacteria, with the relative abundance ranging from 33.42% to 44.10% across all the treatments. The contaminants had little effect on bacterial richness but impacted the structure of bacterial communities. The PCoA showed that compartment and contaminants were the primary contributors to the largest source of community variation, while the VPA indicated that F and Cd synergistically affected the bacterial communities. In turn, lettuce plants could enhance the resistance to the combined stress by increasing the relative abundance of Oxyphotobacteria, Subgroup 6, Thermoleophilia, and TK10 classes in the rhizosphere.

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.