Organic long persistent luminescence (OLPL) materials, which feature minutes or hours long afterglow durations and power-law emission decay profiles, have shown numerous potential applications, whereas the access to such materials usually relies on high-temperature melt-casting or time-consuming solvent evaporation. Here we report the fabrication of OLPL materials via photopolymerization of N-vinylcarbazole catalyzed by pyrylium salt. The polymerization is conducted at 80 degrees C (above the melting point of N-vinylcarbazole, 64 degrees C), which avoid the use of organic solvents and can be completed in 5 s. The resultant OLPL materials are p-type with charge recombination mechanism of hole transporting character, which are tolerate with ambient oxygen and exhibit powerlaw decay with afterglow intensity being proportional to t-m (m = 1.1-1.3). By incorporating a third component that is a red fluorescence dye into the photopolymerization system, the obtained three-component materials display red and enhanced OLPL property because of the excited state energy transfer from OLPL donor to fluorescence acceptor. The present study provides an ultra-fast and solvent-free method for OLPL materials, which pave the way for their wide-spread applications.

We previously discovered that crosslinkable fluorene derivatives with alkyl side chains exhibit excellent dielectric properties at a high frequency of 10 GHz. To further explore the impact of alkyl side chains on the dielectric properties of aromatic polymers, we have designed and synthesized four alkyl benzenes incorporating crosslinkable benzocyclobutene groups. The properties of their cured products are presented in this study. The results indicate that the cured resins exhibit the dielectric constant (Dk) ranging from 2.44 to 2.52 with the dielectric loss (Df) from 5.0 x 10-4 to 7.8 x 10-4 at a frequency of 10 GHz, meaning that alkyl side chains have a big effect on the improvement of dielectric properties of aromatic polymers. Moreover, the Dk values decrease with increasing of the length of alkyl side chains. A comparable investigation indicates that a cured polymer exhibits the improvement of the glass transition temperature (Tg) and the expansion coefficient (CTE) when a butyl and a cyclohexyl are served as the asymmetric side chains. It is also found that the alkyloxy side chains make the dielectric properties of the cured polymers deterioration, suggesting that total hydrocarbon chemical structure are beneficial for the improvement of the dielectric properties of the polymers. This study provides a valuable insight into the designing of the new high-frequency low dielectric materials.

Water-soluble flexible organic frameworks (FOFs) can be constructed from multi-topic cationic, anionic or neutral, hydrophilic components through the quantitative formation of dynamic hydrazone or disulfide bond. FOFs have been revealed to possess intrinsic porosity, hydrophobic interior, and controllable nano-sizes. They function well as homogeneous nano-sponges for including proteins, DNA, residual drugs, such as neuromuscular blocking agents and heparins, and endotoxin. Their nano-sizes endow the frameworks with good ability for intracellular delivery of the included proteins and DNA and for the design of self-delivering prodrugs, while efficient inclusion of residual drugs can be utilized to develop FOF antidotes for inactivating the residual drugs. This review summarizes the design, preparations, characterizations and biofunctions of this family of dynamic covalent polymers.

Pyroptosis is a lytic, proinflammatory type of programmed cell death crucial for the immune response to pathogen infections and internal danger signals. Gasdermin D (GSDMD) acts as the pore-forming protein in pyroptosis following inflammasome activation. While recent research has improved our understanding of pyroptosis activation and execution, many aspects regarding the molecular mechanisms controlling inflammasome and GSDMD activation remain to be elucidated. A growing body of literature has shown that S-palmitoylation, a reversible post-translational modification (PTM) that attaches palmitate to cysteine residues, contributes to multi-layered regulation of pyroptosis. This review summarizes the emerging roles of S-palmitoylation in pyroptosis research with a focus on mechanisms that regulate NLRP3 inflammasome and GSDMD activation.

We present the development of three distinct highly efficient visible-light-excitable afterglow systems based on thermally activated delayed fluorescence (TADF) mechanisms, employing an intramolecular charge transfer strategy. The resulting TADF-type afterglow materials demonstrate emission lifetimes in the range of hundreds of milliseconds and photoluminescence quantum yields (PLQY) between 65% and 80%, exhibiting remarkable temperature-responsive properties. By incorporating an additional electron-donor functional group (D') into the molecular framework of donor-acceptor D-A-type luminophores, specifically difluoroboron beta-diketonate (BF2bdk), we designed novel D-A-D'-type compounds that exhibit a moderate rate of reverse intersystem crossing which facilitates the emergence of TADF-type afterglow from BF2bdk in a rigid crystalline matrix. Furthermore, this design approach elevates the highest occupied molecular orbital energy level, thereby realizing TADF-type afterglow emission under visible light excitation. Our findings highlight the significance of this research in advancing the design of high-performance organic TADF afterglow materials.

Sulfur-containing compounds are pivotal in cellular processes such as redox balance and signal transduction. Traditionally, these compounds, especially thiols, are detected using fluorescence probes. However, these probes fall short in targeting thioethers due to their lower reactivity. Moreover, the chiral discrimination of thiols and thioethers typically relies on chromatographic methods, where separation-free, in situ strategies are highly desirable. To address this, we have developed a novel F-19-labeled chiral platinum probe capable of distinguishing both thiols and thioethers. This technique generates distinct F-19 NMR signals that correspond to the stereoconfiguration of the analytes, enabling direct determination of their enantiocomposition. This method holds potential for integration into high-throughput workflows, boosting pharmaceutical and biological research by facilitating rapid, efficient chiral analysis of crucial compounds.

An efficient and mild approach was developed for the difluoroamination of diaryl gem-dichlorides. This transformation was achieved using the ferric chloride as a Lewis acid and difluorosulfamate tetramethylammonium salt as the difluoroamination reagent. The method exhibited moderate functional group tolerance, highlighting its versatility for introducing difluoroamino groups. And the retention of the C-Cl bond in the product offers the potential possibilities for subsequent modifications.

A copper-catalyzed decarboxylative cycloaddition of (perfluoro-tert-butyl)propiolic acid (PFtPA) with azides under mild conditions was developed, enabling the facile synthesis of perfluoro-tert-butyl (PFtB) triazoles. The strong electron-withdrawing nature of the PFtB group facilitates efficient decarboxylative cycloaddition at 30 degrees C using catalytic copper acetate, avoiding the requirement of traditional harsh conditions. This method provides high yields of products and is compatible with a wide range of azides (including bioactive molecules). This protocol serves as a robust synthetic tool for late-stage fluorination of bioactive compounds, as well as for the development of highly sensitive 19F NMR probes.

Herein, we report a straightforward approach to the late-stage oxime O-glycosylation, utilizing unprotected glycosyl fluoride donors under basic aqueous conditions. By employing a diverse array of commercially available aryl/alkyl oximes and modified sugar/steroid oximes, we have successfully synthesized the desired N-O-linked glycosides and oligosaccharides in satisfactory yields, while achieving specific 1,2-trans-selectivity. This approach stands out due to its broad substrate compatibility, capability for gram-scale synthesis, and potential for glyco-diversification of bioactive molecules, thus holding promise for applications in biological and pharmaceutical research.

Catalytic dehydrogenative aromatization (CDA) has emerged as a powerful strategy for the synthesis of substituted phenols. However, most of the known CDA methods suffer from limited functional group compatibility due to the use of strong oxidants, reductants, or bases. Herein, we report a (cis-P2Cl)Ir-catalyzed CDA reaction enabled by transfer dehydrogenation (TD). This catalytic system is effective for CDA of both cyclohexanone and cyclohexanol derivatives and demonstrates excellent tolerance toward a variety of functional groups, including readily oxidizable electron-rich heterocycles. DFT studies further reveal that the (cis-P2Cl)Ir catalyst is thermodynamically disfavored for the formation of a potential out-of-cycle catalyst species, iridium phenoxyl hydride complex, via oxidative addition of the phenol O-H bond, thereby preventing catalyst inhibition observed in the previously reported TD system.

Cyclin-dependent kinases 12/13 play pivotal roles in orchestrating transcription elongation, DNA damage response, and maintenance of genomic stability. Biallelic CDK12 loss has been documented in various malignancies. Here, we develop a selective CDK12/13 PROTAC degrader, YJ9069, which effectively inhibits proliferation in subsets of prostate cancer cells preferentially over benign immortalized cells. CDK12/13 degradation rapidly triggers gene-length-dependent transcriptional elongation defects, leading to DNA damage and cell-cycle arrest. In vivo, YJ9069 significantly suppresses prostate tumor growth. Modifications of YJ9069 yielded an orally bioavailable CDK12/13 degrader, YJ1206, which exhibits comparable efficacy with significantly less toxicity. To identify pathways synthetically lethal upon CDK12/13 degradation, phosphorylation pathway arrays were performed using cell lines treated with YJ1206. Interestingly, degradation or genetic knockdown of CDK12/13 led to activation of the AKT pathway. Targeting CDK12/13 for degradation, in conjunction with inhibiting the AKT pathway, resulted in a synthetic lethal effect in preclinical prostate cancer models.

The difluoromethylene (CF2) group, valued for its unique electronic and steric properties, plays a critical role in pharmaceutical and agrochemical design, as exemplified by drugs like lubiprostone, which requires ethyl 2,2-difluorohexanoate as a key intermediate for its synthesis. Consequently, developing efficient methods to incorporate the ethoxycarbonyldifluoromethyl group into alkanes is highly desirable. Herein, we describe a mild, versatile, and efficient radical hydro-ethoxycarbonyldifluoromethylation of alkenes with BrCF2CO2Et. This process is applicable to both unactivated alkyl alkenes and active aryl alkenes. The protocol is characterized by mild reaction conditions, the absence of expensive reagents, and the elimination of transition metals.

The carbonyl group is one of the most important functional groups in organic chemistry. C=O cleavage and full transfer of the resulting fragments into final products would be extremely attractive and open up new avenues in retrosynthetic planning. In this context, as an N-containing carbonyl compound, the transformations of formamides, wherein C=O cleavage occurring with simultaneous incorporation of 'O' and aminomethine moieties to highly functionalized amines, remain a formidable challenge. Here we disclosed a dirhodium/Xantphos or dirhodium-palladium dual catalysed reaction of diazo compounds and allylic substrates in dimethyl formamide, giving various alpha-aminoketones and cyclopentenone derivatives efficiently featured with extensively reorganized structure, wherein a carbenic carbon was formally inserted into C=O bond and alpha-group of the carbene was shifted to the residual aminomethine moiety. Mechanistic studies revealed that three or six domino steps are involved in this catalytic process, including epoxidation, dyotropic type rearrangement, allylic alkylation, Claisen rearrangement, isomerization and Nazarov cyclization.

The growing demand for flexible conductors in wearable electronics and soft robotics drives the need for elastomeric substrates with multiple functions, including robust mechanical properties, strong interfacial adhesion, and autonomous self-healing. Herein, we report a new class of polyolefin-based elastomers that address these multifaceted requirements. These materials are synthesized via a one-pot, scandium-catalyzed copolymerization of ethylene with thiophenyl-substituted propylenes in a sequence-controlled manner. By varying the substituents on the sulfur atom and the commoner feed ratio, the mechanical properties of the resulting copolymers can be finely tuned across a wide range. Remarkably, phenylthio-substituted copolymers exhibit high toughness, excellent elasticity, and intrinsic self-healing capability. Furthermore, these copolymers exhibit strong adhesion to gold nanoparticles due to the unique affinity between sulfur and gold. This interaction significantly enhances the durability of gold-coated copolymer conductors. This work underscores the potential of catalyst-controlled copolymerization of functionalized olefins for creating multifunctional polyolefin materials for flexible electronic applications.