A copper-catalyzed fluoroalkylation of lithium aryl n butyl borates with electrophilic fluoroalkylating reagent YlideFluor for the preparation of di-, trifluoromethyl-, and monofluoroalkyl-substituted (hetero)arenes under mild conditions was described. Control experiments indicated that a fluoroalkyl radical, rather than a difluorocarbene intermediate, is involved in the catalytic process. In addition, stoichiometric reactions demonstrated that transmetalation of copper catalyst with lithium aryl n butyl borate takes place before the single-electron-transfer (SET) oxidation of an ate-type Cu(I) intermediate [CuI(Ar)(SCN)]- by YlideFluor. Based on these mechanistic results, a reasonable catalytic cycle for the copper-catalyzed fluoroalkylation of lithium aryl n butyl borates was proposed.

alpha-Sulfanyl carbonyl moieties are common structural features in bioactive molecules. Herein, a copper(I)-catalyzed enantioselective alkylation of alpha-sulfanyl acetamides is disclosed, affording a broad array of chiral alpha,alpha-disubstituted amides in high yields with high enantioselectivity. Benzyl bromides, allyl bromides, propargyl bromide, and non-activated alkyl iodides serve as suitable alkylation electrophiles. Furthermore, structurally diversified amides are well tolerated. Control experiments and NMR studies indicate that alpha-phenylthioacetamide coordinates to the copper(I) catalyst through chelation, leading to activation of the alpha-protons, facile deprotonation, and subsequent formation of stabilized copper(I)-enolate. Finally, various transformations based on the amide moiety, especially the Weinreb amide, demonstrate synthetic utilities of the present method, together with the formal synthesis of a presynaptic cholinergic modulator (11).

The SF5O group has been less explored as a highly fluorinated substituent on an organic framework. In fact, only a few SF5O-containing compounds have been reported, and the preparation of SF5O-containing compounds relied on hazardous reagents and special apparatuses. Herein we describe safe and efficient access to various pentafluoro(aryloxy)-lambda 6-sulfanes (ArOSF5) through the reaction of hypervalent lambda 3-chlor(brom)anes with [Et3MeN]+[OSF5]-. The synthetic and application potentials of ArOSF5 moieties were demonstrated by the inertness of OSF5 moieties in the presence of palladium catalysts, alkalis, and nucleophiles.

A divergent synthesis of spiroindenes through a palladium catalyzed cycloaddition between zwitterionic pi-propargyl palladium species and benzofulvenes in moderate to good yields has been disclosed along with good functional group compatibility and a broad substrate universality. This protocol features a highly regioselective switchable process between [3+2] and [4+2] cycloadditions controlled by phosphine ligands with different bite angles. The reaction mechanism has been clarified by mechanistic studies and DFT calculations, rendering that the coordination modes of the ligands with the substrates and the bite angle of the ligands play critical roles in the product regioselectivity.

Organic long persistent luminescence (OLPL) materials exhibit afterglow lasting several hours. However, current strategies for constructing OLPL materials remain limited, necessitating further exploration. Herein, a difluoroboron beta-diketonate (BF2bdk) luminophore was designed, featuring high molar absorptivity, abundant intersystem crossing and reverse intersystem crossing (RISC) pathways, and an enhanced photoluminescence quantum yield (PLQY). The BF2bdk was doped into an optimal crystalline matrix, 4-methoxyphenyl benzoate (MeOPhB), which serves to protect excitons while also acting as electron acceptors. The resulting BF2bdk-MeOPhB materials possess moderate k RISC, exhibiting bright thermally activated delayed fluorescence (TADF) afterglow with 1.5 s duration and 73.1% PLQY. Under intense excitation, this two-component system demonstrated two-photon-ionization-triggered OLPL. Furthermore, the addition of a third component, N,N,N ',N '-tetramethylbenzidine (TMB), acts as an electron donor, promoting charge separation. Following the slow charge recombination, high-performance BF2bdk-MeOPhB-TMB OLPL materials based on TADF-type afterglow emitters were achieved with 2 h afterglow duration, showing promising applications in anticounterfeiting and data encryption.

The development of efficient detection technology for dairy allergens represents a crucial concern for public health. In this study, a strategy utilizing sinapinic acid salt (SAS) for analyzing allergen proteins through MALDITOF MS is presented. SAS has proven to be a superior matrix compared to solid matrices, as it inhibits aggregation and prevents fragmentation, thereby yielding more reliable molecular mass values of intact allergen proteins. Furthermore, our results indicate that SAS offers higher sensitivity than solid matrices for milk protein analysis. The use of SAS also results in excellent repeatability and a strong linear relationship. By directly analyzing commercially available dairy products, this method has been confirmed to accurately differentiate allergen proteins across various types and brands of dairy products, and it is promising as a novel tool for detecting dairy allergen proteins in the future.

Exosomes derived from hypoxic endometrial epithelial cells are pivotal in cellular communication and tissue repair, offering new perspectives on reproductive health. This manuscript highlights the study by Zhang et al, which investigates the effects of miR-214-5p and miR-21-5p in hypoxic cell-derived exosomes on human umbilical cord mesenchymal stem cells. The study reveals that low levels of these microRNAs activate the signal transducer and activator of transcription 3 signaling pathway, enhancing human umbilical cord mesenchymal stem cell migration and differentiation. These findings provide novel insights into therapeutic strategies for improving endometrial health and addressing infertility linked to thin endometrium.

Two fluorinated monomers M1 and M2 based on pentafluorostyrene, are synthesized via an aromatic nucleophilic substitution reaction (SNAr) at room temperature, with high yields of up to 90%. Subsequently, M1 and M2 are converted to fluorinated poly(aryl ether)s through thermo-crosslinking. Among the two polymers, cured M2 possessing higher fluorine content, demonstrates superior overall performance with a 5% weight loss temperature (T5d) of 465 degrees C, a low water uptake of 0.17% (after immersing in boiling water for 72 h), a low dielectric constant (Dk) of 2.46 and dielectric loss (Df) of 3.65 x 10-3 at 10 GHz. These properties outperform those of numerous poly(aryl ether)s and commercially available low-dielectric materials. This study provides a facile and effective method for preparing fluorinated poly(aryl ether)s tailored specifically for high-frequency communication applications.

A highly enantioselective electrophilic selenylation/semipinacol rearrangement of allenols has been developed, which is enabled by the cooperative catalysis of a chiral sulfide and an achiral sulfonic acid. The designed and synthesized chiral sulfide catalyst and selenylating reagent play a crucial role in enhancing both enantioselectivity and reactivity. This approach exhibits excellent regio-, chemo-, and enantioselectivity, providing access to diverse enantioenriched cyclopentanones featuring an arylselenovinyl-substituted quaternary carbon stereocenter. Furthermore, these products can be transformed into synthetically valuable alkyne, vinyl bromide, and aniline derivatives. Mechanistic studies reveal that the combination of a chiral sulfide and an achiral sulfonic acid not only facilitates the formation of catalytically active species, but also governs the enantioselectivity of the reaction. Meanwhile, density functional theory calculations disclose that four hydrogen bond interactions and a pi...pi interaction are responsible for the observed enantioselectivity.

Tumor necrosis factor (TNF)-induced receptor-interacting serine/threonine protein kinase 1 (RIPK1)-mediated cell death, including apoptosis and necroptosis, is increasingly recognized as a major driver of inflammatory diseases. Cell death checkpoints normally suppress RIPK1 kinase to safeguard the organism from its detrimental consequences. However, the mechanisms licensing RIPK1 kinase activity when a protective checkpoint is disabled remain unclear. Here, we identified S-palmitoylation as a licensing modification for RIPK1 kinase. TNF induces RIPK1 palmitoylation, mediated by DHHC5 and dependent on K63-linked ubiquitination of RIPK1, which enhances RIPK1 kinase activity by promoting the homo-interaction of its kinase domain and promotes cell death upon cell death checkpoint blockade. Furthermore, DHHC5 is amplified by fatty acid in the livers of mice with metabolic dysfunction-associated steatohepatitis, contributing to increased RIPK1 cytotoxicity observed in this condition. Our findings reveal that ubiquitination-dependent palmitoylation licenses RIPK1 kinase activity to induce downstream cell death signaling and suggest RIPK1 palmitoylation as a feasible target for inflammatory diseases.

An efficient palladium-catalyzed intramolecular annulation of 1-acylamino-o-carboranes has been achieved for the synthesis of o-carboranoxazoles with good to excellent yields across a wide range of substrates. Chlorobenzene, acting as an external oxidant, plays a crucial role in this intramolecular dehydrogenative cross-coupling reaction.

Metabolic dysregulation and altered metabolite concentrations are widely recognized as key characteristics of aging. Comprehensive exploration of endogenous metabolites that drive aging remains insufficient. Here, we conducted an untargeted metabolomics analysis of aging mice, revealing citrulline as a consistently down-regulated metabolite associated with aging. Systematic investigations demonstrated that citrulline exhibited antiaging effects by reducing cellular senescence, protecting against DNA damage, preventing cell cycle arrest, modulating macrophage metabolism, and mitigating inflammaging. Long-term citrulline supplementation in aged mice yielded beneficial effects and ameliorated age-associated phenotypes. We further elucidated that citrulline acts as an endogenous metabolite antagonist to inflammation, suppressing proinflammatory responses in macrophages. Mechanistically, citrulline served as a potential inhibitor of mammalian target of rapamycin (mTOR) activation in macrophage and regulated the mTOR-hypoxia-inducible factor 1 alpha-glycolysis signaling pathway to counter inflammation and aging. These findings underscore the significance of citrulline deficiency as a driver of aging, highlighting citrulline supplementation as a promising therapeutic intervention to counteract aging-related changes.

CF3CCl2-containing compounds are of significant synthetic value but are typically synthesized from environmentally harmful hydrochlorofluorocarbons (CFCs). Herein, we report the use of a well-defined Cu(I) complex, [(bpy)Cu(CF3)], as an efficient trifluoromethylating reagent for the direct trifluoromethylation of trichloroalkanes under mild conditions, affording CF3CCl2-containing products with excellent chemoselectivity. This protocol also enabled the gram-scale synthesis of cyhalothric acid ester, which is a key intermediate in the production of pyrethroid pesticides.