To efficiently capture low-concentration chemical warfare agents (CWAs), which pose severe threats to human health and the environment, this study employed an AI big-data-driven high-throughput computational screening strategy to systematically analyze and evaluate the capture and separation performance of tens of thousands of metal-organic framework (MOF) adsorbents for trace CWAs in air. Grand Canonical Monte Carlo simulations were employed to evaluate the CWAs uptake of 15333 Computation-ready experimental MOFs under a gas mixture containing N₂, O₂, and toxic gas at 298 K and 101.325 kPa. A trade-off score (TSN) combining selectivity and adsorption capacity was introduced as a comprehensive performance metric. Predictive models were constructed using six algorithms (Decision Tree, Random Forest, Gradient Boosting Regression Tree, Extreme Gradient Boosting (XGB), Backpropagation Neural Network, and Light Gradient Boosting Machine) based on seven key descriptors of MOFs—namely, Largest Cavity Diameter (LCD), density of MOF (ρ_MOF), Pore-Limiting Diameter (PLD), porosity (φ), Volumetric Surface Area (VSA), Henry Coefficient (K), and heat of adsorption (Q⁰_st). And the XGB algorithm yielded the best predictive performance, with the R² up to 0.923. ​​SHapley Additive exPlanations analysis revealed that K was the most critical descriptor for CWAs adsoprtion, with optimal φ and VSA ranges for maximal sarin and soman adsorption​​ being 0.7~0.8 and 2000~2500 m²•cm^-3, respectively​​. Then, the structural commonalities of the top 1% high-performance MOFs were analyzed by integrating the XGB algorithm with the MOFid standardized identifier. The results reveal that the synergistic effect between open transition metal sites (​​particularly Cr, Nb, Al, In, Li​​) and rigid organic linkers of MOFs enhances the adsorption affinity towards CWAs. Meanwhile, the high occurrence probability of specific topological structures (​​such as sql and kgm​​) indicates that they are conducive to forming favorable pore structures, thus enhancing the adsorption effect. ​​Guided by these insights, 26 novel MOFs were rational designed for enhanced CWAs capture. This study, employing AI big-data mining driven by MOFid method, provides critical guidance for optimizing MOF adsorption performance and screening highly efficient materials, thereby facilitating the efficient capture of trace chemical warfare agents in air ​​and advancing the development of protective equipment​​.

Mesoporous alumina (MA) material with a well-developed mesoporous structure was synthesized by a facile solvent confined hydrolysis-condensation route without introducing organic template. In the proposed route, under vigorous stirring at 60 ℃, the hydrolytic agent (a mixture of deionized water and anhydrous ethanol with a volume ratio of 1:9) was added dropwise into a homogeneous aluminum isopropoxide solution with anhydrous ethanol as solvent to induce an incomplete hydrolysis of aluminum isopropoxide molecules, due to the water molecules dissolved in the anhydrous ethanol solvent exhibiting a significantly reduced accessibility with aluminum isopropoxide molecules; meanwhile, the presence of -OR groups in the intermediate aluminum species and the dispersion role from anhydrous ethanol resulted in an observably moderated condensation reaction of aluminum hydroxyl groups. Consequently, the local crosslinking of oligomerized aluminum hydroxyl species could lead to the formation of nanocluster-like Al-OH species surrounding the organic solvent molecules. During the subsequent solvent evaporation process at 60 ℃, the removal of organic solvent molecules filled in the spaces derived from the further cross-linking of nanocluster-like Al-OH species could drive the formation of mesostructure with uniform porous size. The crystal phase and textural and surface properties of the resulted MA material were further optimized by regulating the calcination conditions. Afterwards, the obtained MA-T samples calcined at different temperature were used as supports of Pt-based catalysts with a low Pt loading amount (w=0.5%) for methylcyclohexane (MCH) dehydrogenation. The characterization and catalytic results demonstrated that at an optimal calcination temperature of 450 ℃, the obtained MA-450 support possesses a γ-Al₂O₃ crystal phase and exhibits the highest specific surface area and pore volume. More importantly, the presence of abundant surface Ib type Al-OH species can effectively promote the homogenous dispersion of Pt precursor (chloroplatinic acid) molecules onto the surface of support MA-450 by an electrostatic interaction between Ib type Al-OH species and chloroplatinic acid molecules. As a result, the resultant catalyst Pt/MA-450 calcined at 500 ℃ for 3 h to thermally decompose the chloroplatinic acid molecules loaded on its surface displayed a notable catalytic activity with a maximum hydrogen evolution rate of 2112 mmol•g_Pt^–1•min^–1, which is inspiringly superior to the state-of-the-art supported Pt-based catalysts. Interestingly, even after a long-time reaction up to 100 h or regeneration, catalyst Pt/MA-450 still maintained more than 80% of original activity. The obviously boosted catalytic reactivity of catalyst Pt/MA-450 can be attributed to the highly homogenous dispersion of Pt active sites in a form of ultra-small nanoclusters and the excellent structural and textural properties of support MA-450, which play important roles in remarkably increasing Pt utilization efficiency and effectively improving the mass/heat transfer efficiency.

This study investigates the reaction mechanisms and anti-poisoning performance associated with Sr/Fe doping in LaMnO₃ perovskite catalysts for CO selective catalytic reduction using density functional theory. The results demonstrate that both Fe single doping and Sr-Fe co-doping significantly enhance the adsorption capacity of CO and NO molecules on the catalyst surface, while Sr single doping inhibits NO adsorption. Fe doping transforms the surface Fe sites into centers of CO oxidative activity, whereas the Mn sites predominantly facilitate NO adsorption. On the surface of LaSrMnFeO₃, CO preferentially reacts with lattice oxygen to produce CO₂, generating oxygen vacancies. Subsequently, NO adsorption leads to the formation of an N₂O₂* intermediate that fills these vacancies, with an activation energy barrier of 0.69 eV, resulting in the formation of an N₂O* intermediate. This gas-phase N₂O* then adsorbs at the Lewis acid sites on the catalyst surface, where its dissociation produces N₂* and surface-adsorbed oxygen. Ultimately, CO and the surface-adsorbed oxygen overcome an activation energy barrier of 0.21 eV, facilitating an oxidation reaction that drives the equilibrium of the N₂O*→N₂*+O* reaction to the right, thereby significantly reducing the accumulation of N₂O* by-products. These findings indicate that the core reaction mechanism for CO-selective catalytic reduction (CO-SCR) on the surface of the LaSrMnFeO₃ catalyst follows the Mars-van Krevelen mechanism, transitioning from a bimodal mechanism to the Mars-van Krevelen mechanism. Notably, the reaction energy barrier for the key rate-controlling step (N₂O*→N₂*+O*) is significantly reduced to 1.64 eV, compared to 1.14 eV for the undoped bimodal reaction mechanism of LaMnO₃. Additionally, the adsorption performance of H₂O and SO₂ on the surface of the LaMnO₃ doping system was investigated. Our findings reveal that Fe single doping effectively enhances the catalyst’s sulfur resistance but exacerbates the irreversible adsorption of H₂O molecules, leading to catalyst poisoning and inactivation. In contrast, the synergistic effect of Sr-Fe co-doping provides excellent resistance to both water and sulfur, thereby offering a theoretical foundation for the design of efficient anti-poisoning perovskite catalysts.

This study achieves highly selective photoelectrocatalytic CO₂ reduction to ethanol through plasmon-enhanced Cu₂O/Ag photocathodes, overcoming inherent limitations of Cu₂O including narrow light absorption and rapid charge recombination. The fabrication involved sequential electrodeposition on fluorine-doped tin oxide transparent conducting glass (FTO): CuSCN at –0.3 V vs. Ag/AgCl (0.1 mol/L CuSO₄•5H₂O, 0.1 mol/L ethylenediaminetetraacetic acid (EDTA), 0.1 mol/L KSCN) followed by Cu₂O at –0.1 mA•cm^–2 (0.4 mol/L CuSO₄, 3 mol/L lactic acid, pH 12.5). Triangular Ag nanoparticles (AgNPs) synthesized via light-assisted reduction were deposited via drop-casting at 70 ℃, with 100 μL•cm^–2 identified as optimal loading. Comprehensive characterization validated the structure and mechanism: field emission transmission electron microscope (FE-TEM) confirmed epitaxial Ag(111)/Cu₂O(110) growth; XPS revealed interfacial electron transfer via Cu⁺2p_3/2 (931.04→931.66 eV) and Ag 3d_5/2(369.08→368.52 eV) shifts; UV-Vis DRS demonstrated localized surface plasmon resonance (LSPR)-mediated absorption extension to 700 nm; and 40% PL quenching indicated suppressed recombination. Under AM 1.5G illumination in 0.1 mol/L KHCO₃, the optimized photocathode achieved a photocurrent density of –2.02 mA•cm^–2 at 0 V vs. RHE, a 30% enhancement versus bare Cu₂O (–1.56 mA•cm^–2). Electrochemical analyses revealed increased carrier concentration (5.56×10¹⁶ cm^–3) and reduced Tafel slope, signifying accelerated kinetics. Crucially, CO₂ reduction at –0.2 V vs. RHE yielded ethanol with 81.3% Faradaic efficiency (0.358 μmol•h^–1•cm^–2) while suppressing hydrogen evolution (<1% FE). Total carbon product FE exceeding 100% suggests participation of non-Faradaic catalytic cycles. Performance degradation at excessive loading (300 μL•cm^–2; 32% photocurrent reduction) confirmed aggregation effects. Finite-Difference Time-Domain (FDTD) simulations corroborated the mechanism, showing 15-fold electromagnetic field enhancement at AgNPs tips under 600 nm illumination, aligning with peak Incident Photon-to-Current Efficiency (IPCE). The record ethanol selectivity stems from synergistic LSPR effects: near-field enhancement facilitates *CO intermediate formation and adsorption, hot electron injection promotes multi-electron transfers crucial for C—C coupling, and the Ag/Cu₂O Schottky barrier effectively suppresses parasitic hydrogen evolution reaction (HER). This work establishes a material design paradigm for efficient solar-to-fuel conversion targeting value-added multi-carbon products.

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurring at bifunctional oxygen electrodes are fundamental to numerous electrochemical energy storage and conversion technologies, including fuel cells and water electrolysis. However, both ORR and OER involve multi-step proton-coupled electron transfers, resulting in sluggish reaction kinetics and requiring high activation overpotentials. Consequently, developing efficient electrocatalysts to lower the reaction energy barriers and accelerate electron transfer is critical for enhancing energy conversion efficiency. This work presents a synergistic strategy integrating bimetallic catalysis with interface engineering. Specifically, a cobalt/nickel bimetallic metal-organic framework (MOF) precursor undergoes polyvinylpyrrolidone (PVP)-assisted pyrolysis, transforming into a hierarchically porous nitrogen-doped carbon matrix embedded with cobalt-nickel alloy nanoparticles (P-CoNi-N-C). Electrochemical characterization reveals that P-CoNi-N-C exhibits ORR performance rivaling commercial Pt/C (onset potential of 1.053 V, half-wave potential of 0.825 V, and electron transfer number of 3.96) and exceptional OER activity (E_j=10 of 1.609 V, low overpotential of 0.379 V, and mass activity of P-CoNi-N-C at 1.60 V is five times that of Co-N-C). Similarly, P-CoNi-N-C has remarkable long-term stability with a current attenuation rate of only 0.84%•h^-1. Comprehensive material characterization confirms that the superior bifunctional performance of P-CoNi-N-C stems from the synergistic interplay of its hierarchically porous architecture, optimized adsorption energy for oxygen intermediates, and unique heterointerface structure. Furthermore, the P-CoNi-N-C catalyst exhibits excellent electrochemical performance (charge current density of 127 mA•cm^-2 and power density of 127.3 mW•cm^-2) and cycling stability (capacity retention rate of 92% after 80 h) in rechargeable zinc-air batteries.

The P2-type manganese-rich layered oxides have emerged as highly promising cathode materials for sodium-ion batteries owing to their exceptional advantages including high specific capacity and low cost. However, huge challenges remain for their practical applications, particularly the capacity degradation under deep desodiation conditions and the structural sensitivity to calcination temperatures during material synthesis. In this study, we successfully fabricated a P2/P3 biphasic Na_0.67Mn_0.9Ni_0.1O₂ (designated as NMNO-800) cathode material through a carefully controlled self-propagating combustion synthesis method with precise temperature regulation. Comprehensive X-ray diffraction characterization revealed that the calcination temperature plays a critical role in phase formation. NMNO-700 (calcined at 700 ℃) exhibited a pure P3-phase structure with R3m space group, while NMNO-900 (calcined at 900 ℃) showed a pure P2-phase structure with P63/mmc space group. Remarkably, the NMNO-800 sample calcined at the optimal temperature of 800 ℃ demonstrated a well-defined and stable P2/P3 biphasic structure, with the phase ratio quantitatively determined to be 42.4% P2-phase and 57.6% P3-phase through Rietveld refinement analysis. Scanning electron microscope (SEM) observations further confirmed that the NMNO-800 possesses a unique hierarchical nano-micro composite architecture, consisting of well-dispersed micron-sized particles ranging from 1.94 to 2.57 μm in diameter, with numerous nanoparticles distributed on the surface of these micron-scale sheet-like particles. This ingenious designed biphasic Na_0.67Mn_0.9Ni_0.1O₂ successfully combines the advantageous features of both P2 and P3 phases, maintaining the excellent structural stability characteristic of P2-phase while preserving the high initial capacity inherent to P3-phase, thereby achieving superior electrochemical performance. Specifically, the NMNO-800 delivers an outstanding reversible capacity of 165.44 mAh/g at 0.2 C rate, maintains a respectable capacity of 89.18 mAh/g even at an extremely high rate of 10 C, and shows excellent cycling stability with 84.2% capacity retention after 100 cycles at 0.5 C rate, significantly outperforming all single-phase counterparts. All the results indicate that the P2/P3 biphasic structure enhances the rate performance of manganese-rich layered oxide cathode materials, improves sodium ion diffusion efficiency, and maintains good cycling stability.

As an important chemical, urea has a wide range of applications. However, the conventional Bosch-Meiser process suffers from high energy consumption and substantial carbon emissions. This study proposes a novel mechanochemical strategy for urea synthesis under ambient temperature and pressure using N₂, CO₂, and H₂O as feedstocks. Five transition metal oxide catalysts (TiO₂, ZnO, Cu₂O, Nb₂O₅, Fe₂O₃) were investigated for their mechanocatalytic effects in a ZrO₂ jar equipped with ZrO₂ balls, with TiO₂ exhibiting the highest performance. Urea production rate was up to 133.59 μg•L^-1•h^-1 with the presence of TiO₂, which is 2.2 times larger than that the catalyst-free conditions. TiO₂ was characterized using transmission electron microscope (TEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and Raman spectroscopy, revealing an increase in oxygen vacancies after the mechanochemical reaction. Fourier transform infrared spectroscopy (FT-IR) analysis was used to detect the adsorbed species on the TiO₂ surface, providing mechanistic insights. Density functional theory (DFT) calculations identified H₂O dissociation and N₂ activation as critical steps. The oxygen vacancies (Vo) in TiO₂ not only enhanced the adsorption of N₂ and H₂O but also facilitated H₂O dissociation to release free H atoms and weakened the N≡N bond. Both the H₂O dissociation and the C—N coupling between *N₂ and *CO were determined to be the rate-limiting step in urea formation. This study presents a green and energy-efficient mechanochemical approach for urea synthesis and elucidates the catalytic role of titanium dioxides in the process.

Chromone derivatives are widely found in natural products and biologically active molecules, and serve as important building blocks in organic synthesis. Although significant progress has been made in the synthesis of chromone-based molecular frameworks, exploring new synthetic methods for chromone derivatives using a building-block chemistry strategy remains of great importance. The ortho-hydroxyaryl enaminones cyclization cascade has become the preferred method for constructing chromones (especially C3 substituted chromones), offering efficient and selective access to these valuable scaffolds. Hexafluoroisopropanol (HFIP) has emerged as a versatile solvent and promoter in organic synthesis, owing to its unique combination of high ionization ability, low nucleophilicity, and strong hydrogen bond donor capacity. The strategic incorporation of morpholine and other cyclic amine motifs into heterocyclic frameworks significantly enhances bioactive compounds' drug-like properties, accelerating the discovery of novel therapeutic candidates. In light of this, we developed a streamlined three-component tandem cyclization of ortho-hydroxyaryl enaminones, morpholine, and aryl glyoxals in HFIP, enabling efficient synthesis of C3-functionalized chromones. This metal-free protocol leverages HFIP's dual role as solvent/promoter at room temperature, offering operational simplicity, broad substrate scope, and excellent functional group tolerance with commercially available starting materials. The results demonstrated that the target C3-functionalized chromone derivatives containing cyclic amine were obtained with moderate to excellent yields. The optimized reaction conditions of one pot synthesis of chromone derivatives are as follows: into a dry 10 mL reaction flask were sequentially added a magnetic stir bar, morpholine 2 (0.9 mmol), phenylglyoxal monohydrate 3 (0.45 mmol), and 1.5 mL of HFIP. The mixture was stirred at room temperature for 30 min. Subsequently, enaminone 1 (0.45 mmol) was evenly added portion wise in five equal portions (with 20-min intervals between additions). The reaction was stirred at room temperature for 12 h. The reaction progress was monitored by thin layer chromatography (TLC). After completion, the reaction mixture was concentrated under reduced pressure. The crude product was purified by column chromatography to afford the desired product 4.

Thioamides, an important functional molecular skeleton, have wide application in the fields of pesticides and pharmaceuticals. They also serving as key intermediates for synthesizing sulfur-containing fine chemicals. This study has developed an efficient method for synthesizing novel thioamide derivatives using cyclic amidines (CA), benzaldehyde, and H₂S as starting materials. Notably, H₂S was utilized as the sulfur source instead of traditional sulfur reagents, enabling the successful synthesis of a variety of novel thioamide derivatives. In addition, the reaction mechanism was elucidated through in situ infrared spectroscopy, which revealed a multi-step reaction process. Initially, the cyclic amidine reacts with H₂S to form a CAH⁺HS⁻ intermediate. Subsequently, the HS⁻ anion nucleophilically attack the carbonyl group of benzaldehyde to form an active intermediate containing an oxygen anion. This intermediate then nucleophilically attacks CAH⁺, generating a C—O—C key intermediate, which undergoes intramolecular rearrangement to produce lactam and thiobenzaldehyde. Ultimately, a series of novel thioamide derivatives were efficiently constructed through this tandem three-component reaction. This study demonstrates for the first time that the oxygen atom in benzaldehyde exhibits a dual function. It serves as a nucleophile to attack CAH⁺ and initiate ring-opening reaction of cyclic amidines, while simultaneously promoting oxygen atom migration to the lactam through intramolecular rearrangement. This discovery provides a novel approach for the design and synthesis of sulfur-containing fine chemicals. A typical general procedure for the synthesis of thioamides is described as follows: As an example, the procedure for the synthesis of thioamides from the starting matiarials H₂S, 1,8-diazabicyclo[5.4.0]- 7-undecene (DBU, 1a) and benzaldehyde (2a) is described, and similar methods are applied to other substrates. 1a (0.1520 g, 1.0 mmol), 2a (0.2120 g, 3.0 mmol), and tetrahydrofuran (THF, 2 mL) were loaded into a 15 mL stainless-steel autoclave equipped with a magnetic stirrer. Subsequently, the reactor was charged with H₂S (89.6 mL, 4.0 mmol). The reactor was placed in a constant-temperature sand bath, and the reaction mixture solution was stirred for 24 h. After the reaction was completed, a saturated NaCl aqueous solution was added to the reaction mixture solution, followed by extraction with EtOAc three times. The combined organic layer was washed with brine and dried over anhydrous MgSO₄, filtered, and concentrated under reduced pressure. The crude product was then purified by silica gel column chromatography (V(petroleum ether)/V(ethyl acetate)=1/1) to give the desired product N-(3-(2-oxoazepan-1-yl)propyl)benzothioamide (3a).

In this study, a novel narrow-band long-wave ultraviolet (UVA) phosphor, Ba[B₈O₁₁(OH)₄]: Eu²⁺ (BBH:Eu²⁺), was synthesized via a low-temperature self-reduction method. The structural and luminescent properties of the phosphor were systematically characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), diffuse reflectance spectroscopy (DR), density functional theory (DFT) calculations, photoluminescence spectra (PL), thermoluminescence spectra (TL), and decay time curves (DT). The SEM results revealed that the phosphor exhibits a well-defined hexagonal plate-like morphology with dimensions of approximately 1.39±0.31 μm in length and 0.68±0.17 μm in width. The DR experimental results demonstrate that BBH exhibits high reflectivity in the ultraviolet region. DFT calculations indicate that this material is a direct-bandgap semiconductor with a bandgap energy of 5.55 eV. TGA results indicate that the thermal decomposition of BBH occurs at 420 ℃. The excitation spectrum of BBH:Eu²⁺ features a broad peak between 200 to 360 nm, peaking at 277 nm, while the emission spectrum spans from 300 to 420 nm, peaking at 385 nm with a full width at half maximum (FWHM) of 35 nm, exhibiting typical narrow-band UVA emission features. The quantum yield of BBH:2%Eu²⁺ was determined to be 34.6%, and the corresponding decay time was measured as 727 ns. When the temperature increased to 100 ℃, the luminescence intensity of BBH:2%Eu²⁺ decreased to 48.9% of its initial value at room temperature, indicating relatively poor thermal stability. The underlying cause can be attributed to the material's large Stokes shift, which reaches 10127 cm^-1 (108 nm). This large Stokes shift significantly enhances the electron-phonon coupling effect, thereby negatively impacting thermal stability. The observed thermal quenching behavior is primarily governed by the thermally activated cross-relaxation mechanism. Based on the XPS and TL data, the self-reduction mechanism of Eu³⁺ within the BBH matrix was elucidated. This research not only introduces a new approach for synthesizing Eu²⁺-activated phosphors but also successfully develops a high-performance UVA narrow-band phosphor with significant potential for applications in anti-counterfeiting, medical diagnostics, and other fields.

To overcome the problems of high toxicity and poor selectivity of cisplatin-based drugs, a novel 8-hydroxyquinoline-modified platinum(II) polypyridine complex, [Pt(IQ-O)(Py)]Cl (PyPt), was synthesized using 5,7-diiodo-8-hydroxyquinoline platinum(II) complex [Pt(IQ-O)(DMSO)Cl] (PtIQ) as an intermediate and 2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)quinolin-8-ol (Py) as an auxiliary ligand. The structures of PyPt and PtIQ were characterized by nuclear magnetic resonance (NMR), ultraviolet-visible spectrophotometry (UV-vis), infrared spectroscopy (IR) and elemental analysis. Density functional theory calculations showed that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of PyPt and PtIQ were 2.3 eV and 3.2 eV, respectively, indicating that there were differences in the anticancer activities of PyPt and PtIQ. Comparing with human lung cancer cells (A549) and human lung cancer cisplatin-resistant cells (A549/DDP), PyPt exhibited better inhibitory effects on human breast cancer cells (MDA-MB-231), with an IC₅₀ value of (0.05±0.04) μmol/L, which was superior to cis-[PtCl₂(DMSO)₂] (>50.0 μmol/L), PtIQ [(9.0±0.1) μmol/L], IQ-OH (>50.0 μmol/L), Py (>50.0 μmol/L) and the clinical drug cisplatin [(11.1±0.3) μmol/L]. Additionally, PyPt had little toxicity to normal liver cells (HL-7702), indicating that PyPt had better selectivity for MDA-MB-231 cancer cells. Flow cytometry and microscopic imaging showed that PyPt could significantly induce apoptosis [ca. (48.0±0.9)%] and senescence [IOD value=(1.9±0.1)×10⁶] in cells, which was superior to PtIQ [apoptosis rate=(44.2±0.6)%, senescence IOD value=(1.8±0.1)×10⁶] and the blank control group (apoptosis rate=(6.1±0.6)%, senescence IOD value=(2.1±0.1)×10⁵). Molecular docking results indicated that the binding energy of PyPt with the DNA strand in telomerase reverse transcriptase (hTERT) was –53.0 kJ/mol, which was significantly stronger than that of PtIQ (–30.2 kJ/mol). Comet assay, immunofluorescence assay, real time-PCR detection (RT-qPCR) and western blotting experiments showed that PyPt induced apoptosis and senescence in MDA-MB-231 cancer cells by inhibiting hTERT expression, activating caspase3/7 proteins and inducing DNA damage, and its induction ability was stronger than that of PtIQ. In vivo experiments showed that PyPt had a good inhibitory effect on MDA-MB-231 solid tumors with an inhibition rate of 44.4%, and did not affect the survival rate (n=6) and body weight of mice. In conclusion, a novel 8-hydroxyquinoline-modified platinum(II) polypyridine anticancer metal drug targeting DNA and hTERT was developed.

Nitrogen heterocycles serve as key structural components in modern pharmaceutical, materials, and agrochemical applications. Addressing the intrinsic limitations of conventional C—N coupling catalysts—particularly their poor catalytic efficiency and narrow substrate range—this investigation engineered an advanced catalytic architecture based on an Al(BPY) metal-organic framework (MOF). The synthetic route involved: (1) hydrothermal assembly of microporous Al(BPY) MOF employing 2,2'-bipyridine (BPY, rigid bidentate N-ligand) and AlCl₃, followed by (2) controlled liquid-phase loading of Cu(BF₄)₂ as a bifunctional reagent (dual etchant and metal source). This innovative approach successfully accomplished two critical objectives concurrently: (i) in situ formation of hierarchically porous networks (pore size distribution: 1~50 nm) and (ii) atomic-level precision immobilization of mono-disperse copper active centers. Structural analysis showed $\text{BF}_{4}^{-}$ etches Al—O—C bonds forming mesopores, while Cu²⁺ coordinates with pyridinic N ensuring atomic dispersion. Rigorous evaluation of Al(BPY)-Cu(BF₄)₂'s catalytic behavior in Ullmann C—N coupling reactions established distinct structure-activity correlations, with the Cu(BF₄)₂-modified catalyst exhibiting substantially superior activity relative to Cu(NO₃)₂-, CuCl₂-, and Cu(acac)₂-modified analogs. The Al(BPY)-Cu(BF₄)₂-0.5 demonstrated optimal catalytic performance, achieving 93% product yield under optimized reaction parameters (Cs₂CO₃ base, dimethylsulfoxide solvent, 120 ℃, 16 h). Notably, the catalyst displayed exceptional functional group compatibility (55%~95% yields across 42 diverse substrates including fused-ring systems, non-aromatic N-heterocycles, and P—H compounds) while maintaining remarkable tolerance toward both electronic and steric perturbations. The system successfully transcended conventional catalytic constraints by accomplishing: (i) efficient coupling of sterically demanding non-aromatic amines and (ii) pioneering MOF-mediated C—P bond formation—the first documented instance of such transformation in MOF-based catalytic systems. Furthermore, the material exhibited outstanding cycling stability, retaining >94% initial activity through 8 successive reaction cycles with negligible copper leach-ing (<0.2 mg/L). The exceptional catalytic efficiency originates from synergistic interplay between hierarchically porous channels (facilitating enhanced mass transport and active site accessibility) and atomic Cu centers (activating aryl iodides and X—H bonds).

Over 90% of global hydrogen (H₂) production is derived from natural gas reforming, making efficient carbon removal and H₂ purification crucial for high-purity hydrogen applications. Metal-organic framework (MOF) nanosheet membranes, with highly ordered porous structures, show great potential for H₂ purification. Gas transport in conventional MOF nanosheet membranes is constrained by horizontal stacking, which severely limits gas mass transfer efficiency. Here we propose a fast current-driven synthesis strategy for in situ fabrication of vertically aligned MOF nanosheet membranes within a short duration of 10 min. The electric field assistance effectively induces linker deprotonation, thereby accelerating the nucleation and preferential growth of MOF nanosheets on the substrate. As the reaction progresses, the increasing spatial constraints hinder crystal lateral growth, compelling the crystal growth to preferentially proceed along the direction of minimal resistance. In other words, the growth orientation gradually transitions from an initially parallel arrangement to a vertically aligned structure. Compared with conventional horizontally stacked structure, the vertically aligned structure significantly shortens the gas diffusion pathways, effectively eliminating mass transfer limitations caused by horizontal stacking. The resulting vertically aligned copper 1,4-benzenedicarboxylate (CuBDC) nanosheet membrane exhibits outstanding H₂ permeance of 1.5×10^-6 mol•m^-2•s^-1•Pa^-1, approximately 5 times higher than that of conventional nanosheet membranes with horizontally stacked structure. Meanwhile, the vertically aligned CuBDC nanosheet membrane maintains excellent selectivity in H₂/CO₂ separation, with a selectivity of ca. 20, driven by both adsorption and diffusion. Due to both the higher diffusion resistance of larger gas molecules and the strong interactions between metal sites and CO₂ molecules, CO₂ transport within the membrane is significantly hindered, while H₂ molecules permeate more readily, ultimately resulting in enhanced H₂/CO₂ separation performance. This work not only confirms the critical role of vertically aligned structures in improving molecular transport efficiency but also provides new theoretical insight and a practical strategy for fabricating vertically aligned 2D MOF membranes for efficient gas separation.

Nitrogen-containing heterocycles are the most common structural units in numerous natural products, drugs, and bioactive compounds. Among them, functionalized tetrahydropyridine derivatives are widely present in many alkaloids, biologically active molecules and drug molecules. Consequently, the synthesis of this class of nitrogen heterocyclic compounds has attracted widespread attention from chemists. Despite many known powerful methods, some of the existing protocols still require use of expensive transition metal catalysts or harsh reaction conditions, thus limiting their extensive application. Herein, we report an efficient and practical method for synthesis of functionalized 1,2,3,6-tetrahydropyridine derivatives by visible-light-induced nitrogen radical-mediated addition/cyclization of vinylcyclopropanes. This process involves controlled generation of sulfonamidyl radicals from N-aminopyridinium salts to trigger the addition/cyclization reaction with vinylcyclopropanes. This work not only enriches the reaction scope of photogenerated nitrogen radicals, but also provides a new approach for the construction of 1,2,3,6-tetrahydropyridines. Notably, the N-aminopyridine salts in this reaction act as a bifunctional reagent, both as a nitrogen radical precursors and a nitrogen nucleophilic reagents. Vinylcyclopropanes serve as versatile four-atom coupling partners, undergoing radical addition followed by ring-opening and cyclization. This work significantly expands synthetic approaches for heterocyclic construction by demonstrating a novel reaction mechanism for visible-light-catalyzed nitrogen radical generation, providing a direct and modular synthetic pathway for tetrahydropyridine core structures. After extensive condition screening, the optimal conditions for this reaction were determined as follows: 10-phenylphenothiazine (Ph-PTZ) as the photocatalyst and 1,2-dichloroethane (DCE) as the solvent under irradiation of 390 nm purple LEDs. Subsequently, the substrate scope of N-aminopyridine salts and vinylcyclopropanes was examined, leading to the synthesis of 42 examples of 1,2,3,6-tetrahydropyridine analogs in up to 77% isolated yield. In addition, this method can be scaled up to the gram scale while the product undergoes various transformations of functional groups. Finally, a possible reaction mechanism was proposed for the reaction based on free radical trapping experiments and fluorescence quenching experiments.

Polyethylene wax has the physical properties of ethylene oligomer, and can be used as lubricant, stabilizer and adhesive. It is widely used in plastics, rubber, ink, cosmetics and other fields. Its preparation technology has been upgraded from the traditional thermal cracking process to catalytic ethylene polymerization technology. In this work, we synthesized three iminopyridyl nickel catalysts Ni1~Ni3 with different steric effects and bulky 2,4,6-tris(4-fluorophenyl)methyl substituents, and investigated their catalytic performance in ethylene chain-walking polymerization processes. Results demonstrated that catalyst structure and polymerization conditions directly influence ethylene catalytic activity, as well as the molecular weight and branching degree of the resulting polyethylene wax. All catalysts successfully produced branched polyethylene waxes with methyl groups and long side chains, exhibiting narrow dispersion. By adjusting polymerization temperature (0~75 ℃), the branching structure of polyethylene wax could be effectively controlled (15~61/1000C). A solid powder of polyethylene was obtained at lower temperatures, primarily composed of methyl branches. These catalysts exhibited nearly identical superior performance to toluene in industrial solvent n-heptane. The Ph-substituted Ni2 showed high catalytic activity of 4.55×10⁶ g•mol^－1•h^－1 in n-heptane versus 4.72×10⁶ g•mol^－1•h^－1 in toluene. This technology enables direct synthesis of branched polyethylene wax materials through chain-walk polymerization, featuring simple preparation, cost-effectiveness, high catalytic efficiency, and excellent solvent tolerance. It paves new pathways for high-value production of polyethylene waxes in industrial applications.

As an important type of polymer material, polyester is widely used due to its diverse properties and plays a significant role in the plastic economy, accounting for about 10% of the global plastic market. Facing the environmental problems caused by discarded plastics, the development of new types of polyesters with closed-loop chemical recycling properties has become the focus of attention in both academic and industrial research. In this work, benzo-fused caprolactone 4,5-dihydrobenzo[b]oxepin-2(3H)-one (DHBO) was synthesized from α-tetrahydronaphthone via Baeyer-Villiger oxidation reaction, and structurally characterized via NMR spectroscopy and single crystal X-ray diffraction. The ring-opening polymerization of DHBO under varied conditions was investigated using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst, and the molecular weights of the resultant poly(DHBO) obtained via gel permeation chromatography are lower than theoretical values due to transesterification. The polymerization kinetics of DHBO in toluene with TBD/4-MeBnOH shows a first-order dependence on DHBO concentration. The poly(DHBO) is amorphous with a glass transition temperature T_g of 4.8 ℃, and a thermal decomposition temperature T_d (5% weight loss) of 194 ℃, which can be enhanced to 252 ℃ by capped the chain-end OH group with acetyl. In addition, the polyester can be rapidly thermally degraded into the initial monomer DHBO without any catalyst at 110 ℃ under reduced pressure, with a recovery rate of 97% and a monomer purity of 99%. Moreover, using bis(triphenylphosphine) iminium chloride (PPNCl) as the catalyst, DHBO can undergo ring-opening copolymerization with commercial epoxides, such as phenyl glycidyl ether (PGE), allyl glycidyl ether (AGE), 1,2-butylene oxide (BO), (R)-(BO), (S)-(BO), 1,2-hexene oxide (HO) and cyclohexene oxide (CHO) in bulk, producing poly(ether-ester) with highly alternating sequences. Representative copolymers were characterized with NMR spectroscopy (¹H, ¹³C, DOSY) and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS). These poly(ether-ester)s showed good thermal stability with T_d over 290 ℃, where the poly((S)-BO-alt-DHBO) exhibited the highest T_d of 353 ℃. The structure of epoxides effected the T_gs of corresponding poly(ether-ester), and wide range of T_g from －19 ℃ to 43 ℃ can be regulated. Finally, the mechanism of the alternating poly(ether-ester) formation was investigated.

Noble metal Pt is widely applied in propane dehydrogenation reaction due to its excellent ability to activate C—H bonds and its relatively low tendency to break C—C bonds. However, in the course of propane dehydrogenation catalyzed by traditional Pt-based catalysts, the rapid deposition of coke can cover the active sites, which in turn leads to the deactivation of the catalyst. Furthermore, frequent regeneration will trigger irreversible changes in the structure of the active sites, resulting in permanent deactivation. Therefore, the development of Pt-based catalysts with high activity and high stability is of crucial significance. In this work, PtFe/Silicalite-1 (PtFe/S-1) catalysts with different Fe loadings (mass fraction from 0.1% to 2.0%) were prepared by co-impregnation method, and their performance in propane dehydrogenation was investigated. The results indicate that the introduction of Fe can effectively strengthen the interaction between Pt and the support, enhance the dispersion of Pt species, and thus form small-sized Pt species with high stability. At the same time, Fe regulates the electronic structure of Pt through electron transfer, thereby improving the selectivity towards propylene. The loading amount of Fe has a significant impact on the catalytic performance: when the loading is low, the catalyst exhibits low activity and poor stability; when the loading is high, the initial propylene selectivity decreases due to side reactions. Among them, the Pt1.0Fe/S-1 catalyst shows the highest propane dehydrogenation performance, with the initial propane conversion of 59.8%, which still remains at 52.9% after 6 h, and the propylene selectivity increases from 89.1% to 96.4%. This finding demonstrates that an appropriate amount of Fe (mass fraction 1.0%) can achieve a balance between catalytic activity and stability by improving Pt dispersion, regulating the electronic properties of Pt, thus providing an important reference for the design of efficient propane dehydrogenation catalysts.

Electrochemical nitrate reduction reaction (NO₃RR) has gained significant attention as a dual-purpose strategy for sustainable wastewater treatment and value-added ammonia synthesis. However, the practical implementation of NO₃RR is fundamentally constrained by the lack of efficient electrocatalysts capable of achieving high activity, superior ammonia selectivity, and satisfactory Faradaic efficiency simultaneously. To address these challenges, we herein report a molecular-level coordination engineering approach to optimize the NO₃RR performance by incorporating precisely controlled copper active sites into a robust three-dimensional covalent organic framework (3D COF). The designed catalyst, denoted as Cu-8mgATZ-COF, was synthesized through a post-modification strategy that ensures uniform copper coordination while maintaining structural integrity. Extensive characterization confirms its highly porous architecture, exceptional stability, and well-dispersed metal sites. When evaluated as an electrocatalyst for nitrate reduction, Cu-8mgATZ-COF delivers outstanding performance under high nitrate concentration (mass fraction 0.3%), markedly surpassing the unmodified COF-300 benchmark. It achieves a notable ammonia Faradaic efficiency of 34% and a high ammonia yield rate of 2284.5 μg•mg_cat⁻¹•h⁻¹, making it among the best-performing noble-metal-free COF catalysts reported for nitrate-to-ammonia conversion. Furthermore, the catalyst exhibits remarkable operational durability across multiple cycling tests. This study not only presents the first successful example of a copper-integrated 3D COF for high-concentration nitrate electroreduction but also offers new insights into the rational design of molecularly defined porous catalysts for sustainable electrochemical applications such as environmental remediation and energy-efficient ammonia production.

Owing to their unique enrichment and phase-separation properties, coacervates not only enable the efficient capture and removal of pollutants but also differ fundamentally from conventional oil-water separation systems by operating in an aqueous environment, thereby offering significant advantages in pollutant remediation. Surfactant-based coacervates, in particular, exhibit superior solubilization capacity for pollutants while maintaining simple molecular structures and high degradability. Consequently, the development of surfactant-based coacervates holds considerable promise as an emerging technology for wastewater treatment. This study investigated the intermolecular interactions and aggregation behaviors of the mixed system comprising anionic cyclodextrin derivative sulfobutyl-β-cyclodextrin sodium salt (SBE-β-CD) and cationic gemini surfactant alkanediyl-α,ω-bis(dimethyldodecylammonium) bromide (12-s-12) through turbidity titration, cryo-transmission electron microscopy (Cryo-TEM), proton nuclear magnetic resonance (¹H NMR), and zeta potential analysis. The results reveal that upon gradually adding 12-s-12 to a fixed concentration of SBE-β-CD, the two components form complexes through electrostatic attraction and host-guest interactions, which further assemble into small-sized spherical aggregates. As the concentration of 12-s-12 increases, these spherical aggregates associate into larger chain-like aggregates via hydrophobic bridging between the tails of the complexes. With the gradual reduction of net charge in the system, the chain-like aggregates become increasingly entangled, ultimately leading to the formation of coacervates. When 12-s-12 is excessive in the system, the electrostatic repulsion between aggregates increase, causing the coacervates to revert to chain-like aggregates and eventually to small spherical aggregates. Comparison of coacervate formation regions for different 12-s-12 structures shows that as the methylene units in the spacer group of the gemini surfactants increase from 3 to 6, their ability to form coacervates with SBE-β-CD strengthens, resulting in a broader formation range. Besides, the coacervates formed by SBE-β-CD/12-6-12 can achieve complete enrichment and extraction of congo red and methyl orange from aqueous solutions, demonstrating excellent dye enrichment performance. In contrast, the system exhibits relatively low extraction efficiency for acid blue and methylene blue. This selective enrichment behavior suggests its application in the separation of dyes and wastewater treatment.

Due to the electron-deficient characteristics of boron, boron clusters exhibit a variety of structures with size changes, and the doping of different metal atoms can further enrich the structures and properties of boron clusters. We investigated a series of actinide metal-doped boron clusters AnB₈ (An=Ac, Th, Am, Cm) by using the global minimum structural searches and density functional theory (DFT) methods. For each isomer, different spin states were considered at the PBE0/6-311＋G*/RECP and TPSSH/6-311＋G*/RECP theoretical levels. It is found that each AnB₈ cluster possesses two configurations, half-sandwich and chair-like structures. Except for ThB₈, the half-sandwich structures of AcB₈, AmB₈ and CmB₈ are more stable, while the energy difference between the two structures of ThB₈ is small, indicating that both may coexist in experiments. The half-sandwich structures of AcB₈, ThB₈, AmB₈, and CmB₈ correspond to doublet, singlet, octet, and nonet states, respectively. ThB₈ is a closed-shell singlet system, in which the electronic configuration of the Th element may be [Rn]6d². Voronoi deformation density (VDD) and Hirshfeld charges suggest that charge flows from the actinide elements to the boron ligands. The half-sandwich structures of these boron clusters are stable M^II[${B}_{8}^{2-}$]-type divalent actinide complexes. Molecular orbital (MO) analysis shows that the An—B bonding orbitals of AcB₈ and ThB₈ mainly originate from An 6d orbitals, while those of AmB₈ and CmB₈ are primarily contributed by An 5f orbitals. Other analyses of bonding properties also indicate that there exist covalent interactions between An and B atoms in all complexes, and ThB₈ has stronger covalent interactions. For these AnB₈ complexes, the ${B}_{8}^{2-}$ ligands show double aromaticity features, which have six delocalized σ electrons and six delocalized π electrons. According to dissociation energy analysis, all the AnB₈ complexes are highly stable, especially ThB₈. These results indicate that the ${B}_{8}^{2-}$ ligands are capable of stabilizing the divalent actinides.

This study focuses on the treatment of cisplatin-induced acute kidney injury (AKI). Extensive research has demonstrated that oxidative stress and inflammatory responses caused by excessive production of reactive oxygen species (ROS) play a critical role in the progression of AKI. Therefore, exploring effective and safe antioxidants and an ti-inflammatory agents to scavenge overexpressed ROS and regulate excessive inflammation has become a promising therapeutic strategy. Glutathione and iron selenide both possess anti-inflammatory and antioxidant properties. Based on this, we successfully developed glutathione-modified iron selenide nanoparticles (GSH-Fe_3－XSe₃ NPs) with a particle size of approximately 200 nm, which exhibit excellent biosafety. This study comprehensively investigated the antioxidant and anti-inflammatory capabilities of GSH-Fe_3－XSe₃ NPs. Firstly, the anti-inflammatory and antioxidant properties of GSH-Fe_3－XSe₃ NPs were assessed at the cellular level. Additionally, the effects of GSH-Fe_3－XSe₃ NPs on ROS and malondialdehyde (MDA) levels and the expression of inflammation-related cytokines (TNF-α, IL-6) in lipopolysaccharide (LPS)-induced inflammatory cells were investigated. The antagonistic effect of GSH-Fe_3－XSe₃ NPs on LPS-induced inflammation in RAW264.7 cells was confirmed. Secondly, the anti-inflammatory mechanism of GSH-Fe_3－XSe₃ NPs was explored using western blot (WB). Finally, in this study, an AKI mouse model was established by intraperitoneal injection of cisplatin. The safe dosage of GSH-Fe_3－XSe₃ NPs in healthy mice was determined, and the biosafety of GSH-Fe_3－XSe₃ NPs was analyzed. The therapeutic effect of GSH-Fe_3－XSe₃ NPs on mice with acute kidney injury was evaluated by measuring serum levels of AKI-related inflammatory factors. Experimental results demonstrated that GSH-Fe_3－XSe₃ NPs can simultaneously scavenge ROS, MDA, and nitric oxide (NO), showing excellent cytoprotective effects against oxidative stress-mediated damage. Furthermore, in a cisplatin-induced AKI mouse model, GSH-Fe_3－XSe₃ NPs significantly reduced the expression levels of blood urea nitrogen (BUN), serum creatinine (SCR), MDA, tumor necrosis factor-α (TNF-α), and interleukin-6 (IL-6) under AKI conditions, markedly improving the symptoms of AKI mice. In conclusion, the GSH-Fe_3－XSe₃ NPs prepared in this study, through their dual mechanisms of antioxidant and anti-inflammatory actions, achieved therapy for cisplatin-induced AKI, providing a novel therapeutic approach for AKI treatment.

Solid-liquid hybrid hypergolic propellants have potential application in space power systems, in order to explore novel hypergolic fuels, four metal complex hypergolic fuels MCCHFs 1~4 were designed and synthesized by using Co(II) and Ni(II) as the central metal ions, 1-methylimidazole and 1-methyltetrazolium as ligands, and cyano-borohydride as the anion. The crystal structures of these complexes were accurately determined, and their thermal behavior, mechanical sensitivities, hypergolic and energetic performances were studied in detail. The results show that the peak temperatures of the thermal decomposition of the four complexes were in the range of 152.4~176.3 ℃, MCCHF-1 and MCCHF-4 exhibit mechanical stimulation sensitivity (IS: 8 J, 17 J; FS: 288 N, 216 N), MCCHF-2 and MCCHF-3 are insensitive to mechanical stimulation (IS>40 J, FS>360 N). The four compounds are all able to react with white fuming nitric acid by spontaneous ignition, and the ignition delay time are in the range of 2~57 ms, with MCCHF-1 performing the best of 2 ms. The heat of combustion of MCCHF-2 is the highest, with a mass energy density of 25.41 kJ•g⁻¹ and a volumetric energy density of 32.17 kJ•cm⁻³. MCCHF-1, MCCHF-4 with HNO₃, N₂O₄, and H₂O₂ three liquid oxidizers, show good specific impulse performance, in which the propellant combined with H₂O₂ has the best performance, with a vacuum specific impulse as high as 268.37 s, which was higher than that of the traditional spontaneous combustion fuels, such as meta-dimethylhydrazine (258 s). As a new type of hypergolic solid fuel, the active metal complexes based on cyanoborohydride anion are expected to promote the development of solid-liquid propellant technology.

In recent years, optical thermometry based on inorganic nanomaterials has demonstrated significant application potential in biomedical temperature sensing due to its high sensitivity, non-contact measurement capability, and excellent biocompatibility. Compared with a single temperature sensing mode, the development of a multi-mode optical temperature sensing strategy is expected to significantly improve the accuracy and reliability of temperature detection, which has become an important research direction in this field. In this work, a series of CaF₂:Mn²⁺ nanoparticles with particle size of about 10~20 nm have been successfully prepared through a solvothermal approach. In order to further reveal the structure-activity relationship of CaF₂:Mn²⁺, its structural composition and microscopic morphology were systematically characterized by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. The luminescence properties and temperature-dependent response behavior of CaF₂:Mn²⁺ were explored in detail by spectroscopic analysis. On this basis, the potential application prospects of the material in the field of optical temperature sensing are further discussed. The experimental results demonstrate that the nanoparticles exhibit significant temperature-dependent characteristics in luminescence intensity, emission peak position, and fluorescence lifetime. Further investigation revealed that the CaF₂:Mn²⁺ nanoparticles exhibited characteristic emission from Mn²⁺-Mn²⁺ dimers (680~950 nm) within the first near-infrared biological window (650~950 nm), and showed stronger thermal quenching effects compared to Mn²⁺ ions. Based on these experimental results, we have established a multimodal optical temperature sensing strategy utilizing CaF₂:Mn²⁺ nanoparticles. Among these, the temperature sensing models based on luminescence intensity of the Mn²⁺-Mn²⁺ dimer, the luminescence intensity ratio (Mn²⁺ ions / Mn²⁺-Mn²⁺ dimer), and the lifetime of the Mn²⁺-Mn²⁺ dimer demonstrate optimal temperature sensing performance within the physiological temperature range (300~330 K). Corresponding relative sensitivities are 2.82%•K⁻¹ (330 K), 0.79%•K⁻¹ (305 K), and 0.65%•K⁻¹ (330 K), respectively, providing a reliable multi-mode measurement scheme for biological thermometry. This study not only confirms the application potential of CaF₂:Mn²⁺ nanoparticles in the field of biological temperature sensing, but also provides important theoretical references and experimental basis for the development of novel high-sensitivity biothermometry probes.

The mechanical properties of the extracellular matrix (ECM), including stiffness and stress relaxation, play an instructive role in regulating cellular behaviors. Given the inherent heterogeneity of tissue viscoelasticity in vivo, the precise influence of viscoelastic variations on cellular behaviors remains incompletely understood. To study these mechanobiological responses in vitro, gradient hydrogels have been developed to mimic the mechanical heterogeneity of native ECM. However, current fabrication strategies, including photomask polymerization and diffusion-based methods, face several limitations, such as complex operation, narrow material applicability, and compromised biocompatibility due to harsh reaction conditions. To address this challenge, we developed a programmable syringe pump system (PSPS) comprising three syringe units to fabricate a gradient viscoelastic hydrogel (GoHG) at a 600 μm scale. The hydrogel was synthesized through dynamic imine crosslinking between oxidized hyaluronic acid (oxi-HA) and gelatin, with precise spatial control over viscoelastic properties achieved by independently modulating the flow rates of individual injection units. This strategy enabled precise control over hydrogel composition, resulting in continuous stiffness gradients (19~47 kPa) and stress relaxation gradients (6~62 s) while maintaining excellent cytocompatibility (>95%). The results on the effect of viscoelastic gradient on cell spreading behavior indicate that different cell types exhibited distinct responses to the viscoelastic gradient. Fibroblasts (NIH-3T3) displayed enhanced spreading behavior in regions with higher stiffness (28.5 kPa) and slower stress relaxation (34.7 s), whereas myoblasts (C2C12) showed larger spreading area in areas with lower stiffness (23.6 kPa) and faster stress relaxation (30.0 s), highlighting cellular specificity to mechanical cues. These findings underscore the importance of viscoelasticity as a critical regulator of cell behavior. In conclusion, the PSPS-based fabrication method offers significant advantages, including simplicity, scalability, and broad material compatibility, making it a versatile platform for mechanobiology research. Furthermore, this approach advancing our understanding of cell-ECM mechanical interactions and shows great potential for tissue engineering applications, where mimicking native ECM mechanics is essential for guiding cell function and tissue regeneration.

Organic light-emitting diode (OLED) technology has been widely applied in the fields of full-color flexible displays and solid-state lighting. As one of the three primary colors, blue light plays a crucial role in OLED technology, making blue-emitting materials a focal point of research in this domain. To achieve blue light emission with high color purity, blue-emitting materials need to emit light within a narrow wavelength range. However, this narrow-band emission often comes at the cost of reduced luminescence efficiency, as precise regulation of molecular energy levels to realize narrow-band emission is highly challenging in practical material design. Considering this, this work proposes an innovative molecular design strategy. Through the Suzuki-Miyaura coupling reaction of pyridine units with corresponding boronate esters, three bipyridine derivatives with different substitution sites were successfully synthesized. Subsequently, 3,6-di-tert-butylcarbazole groups were introduced to the ortho, meta, and para positions of the pyridine nitrogen atoms in the bipyridine core via C—N coupling reactions, yielding three target compounds with distinct twisted structures. In these materials, the 3,6-di-tert-butyl- carbazole unit acts as the donor and the pyridine unit as the acceptor. A significant dihedral angle exists between the carbazole substituents and the bipyridine core. This steric-induced twisted structure effectively restricts the extension of the molecular conjugated system and suppresses the energy loss due to intramolecular vibrations, thereby ensuring high color purity of blue light. Thermogravimetric analysis indicates that all three materials exhibit excellent thermal stability, with decomposition temperatures exceeding 310 ℃. Photophysical tests reveal that 2,2'-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,3'-bipyridine (2TCzOBPy) and 4,4'-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,3'-bipyridine (2TCzPBPy) show deep blue light emission at 440 nm and 422 nm, respectively, in doped films. OLED devices fabricated with these two compounds as the emissive layers have CIE coordinates of (0.152, 0.063) and (0.172, 0.098), respectively, with y values of the color coordinates both less than 0.1, indicating deep blue light emission with high color purity. Additionally, devices based on 3,3'-bis(3,6-di-tert-butyl- 9H-carbazol-9-yl)-4,4'-bipyridine (2TCzMBPy) exhibit blue-green light emission, achieving a maximum external quantum efficiency (EQE) of 3.6% and a maximum brightness of 5423 cd•m⁻².

In this paper, a multifunctional nanotheranostic agent DPP-PEG/BSA-MnO₂ was constructed for photoacoustic (PA)/near-infrared fluorescence (NIR Ⅱ FL) dual-mode imaging and photodynamic (PDT)/photothermal (PTT)/chemodynamic (CDT) synergistic therapy effects. A diketopyrrolopyrrole (DPP)-based amphiphilic conjugated polymer, DPP-PEG, was synthesized by direct (hetero) arylation polymerization (DHAP) of a DPP derivative monomer modified with polyethylene glycol (PEG) hydrophilic side chains and another DPP derivative monomer substituted with 2-ethylhexyl side chains. DPP-PEG nanoparticles (NPs) exhibited strong fluorescence emission in the NIR II region of 1000~1400 nm with a fluorescence quantum yield of 0.374%, which can quickly light up the mouse's systemic vascular network within 2 min, achieving clear fluorescence imaging of brain and leg blood vessels. DPP-PEG was complexed with bovine serum albumin (BSA)-manganese dioxide (MnO₂) to construct a water-soluble composite nanomaterial DPP-PEG/BSA-MnO₂ (abbreviated as DPP-PEG/B-M). Comparative studies with DPP-PEG/B and B-M showed that DPP-PEG/B-M exhibited evident PDT/PTT/CDT synergistic effect in the tumor microenvironment (TME). Both DPP-PEG/B and DPP-PEG/B-M can effect-tively inhibit the proliferation effect in the tumor microenvironment (TME). Both DPP-PEG/B and DPP-PEG/B-M can effectively inhibit the proliferation of 4T1 tumor cells under 808 nm laser irradiation, as DPP-PEG produced excellent PDT/PTT synergistic effects. Compared with DPP-PEG/B, DPP-PEG/B-M showed a significant increase in cytotoxicity under the same conditions. The overexpressed glutathione (GSH) and H₂O₂ in TME can effectively convert MnO₂ into Mn^2＋, which further underwent a Fenton-like reaction with H₂O₂ to generate •OH, thereby producing additional CDT therapeutic effects. Furthermore, MnO₂ reacted with H₂O₂ to produce O₂, promoting the generation of ¹O₂ and enhancing the PDT effect. The consumption of MnO₂ weakened the scavenging effect of GSH on •OH and ¹O₂, further synergistically enhancing the PDT/CDT effect. Moreover, DPP-PEG/B-M was injected into 4T1 tumor-bearing mice via the tail vein. 24 h post-injection, the photoacoustic and NIR-II fluorescence signals at the tumor site reached their highest intensity, indicating that DPP-PEG/B-M can be enriched to the tumor site through the enhanced permeation and retention (EPR) effect. Therefore, DPP-PEG/B-M exhibited excellent tumor-targeting photoacoustic imaging and NIR-II fluorescence imaging performance in 4T1 tumor-bearing mice, and was expected to be applied in PDT/PTT/CDT synergistic therapy guided by photoacoustic/NIR-II fluorescence dual-mode imaging, playing a role in precise and efficient tumor therapy.

Sulfur-fluoride exchange (SuFEx) click chemistry, introduced in 2014, has rapidly evolved into a powerful synthetic platform. Centered on sulfonyl fluoride reactivity, it enables the swift and efficient construction of sulfonylated scaffolds. Owing to their unique electrophilic character, sulfonyl fluorides have found broad utility in organic synthesis, chemical biology, drug discovery and advanced materials. Recent years have witnessed SuFEx not only driving the preparation of hypervalent sulfur-fluorine compounds but also delivering promising antitumor, antibacterial and antioxidant agents with markedly improved bioactivity. Drawing upon the design of small-molecule S-F building blocks, the authors provide a comprehensive overview of recent advances in sulfonyl fluoride synthesis. As pivotal intermediates, these compounds are poised to catalyze progress across chemistry, materials science and biomedicine. Sulfuryl fluoride (SO₂F₂), a widely recognized SuFEx synthon, mediates diverse functional-group interconversions. Here, we employ SO₂F₂ to transform aryl ethanols into aryl ethylenes practicably and efficiently under basic conditions that dispense with expensive metals, ligands or additives. Broad functional-group tolerance is observed and yields range from 72% to 90%. After screening organic and inorganic bases in both identity and stoichiometry, together with temperature, we settled on the following protocol. To a 25 mL sealed tube are charged phenethyl alcohol (1.0 mmol), t-BuOK (5.0 equiv.) and anhydrous dimethyl sulfoxide (DMSO) (5 mL). The vessel is then purged and maintained under a slight positive pressure of SO₂F₂ delivered from a balloon via syringe needle. The mixture is stirred at 60 ℃ for 12 h. Work-up consists of dilution with water (10 mL), extraction with CH₂Cl₂ (10 mL×3), washing the combined organic layers with brine, drying over Na₂SO₄, concentration, and purification by flash column chromatography (EtOAc/petroleum ether, V∶V=1∶20) to afford the desired styrene. The method accommodates twelve electronically and sterically varied styrenes and has been scaled to gram quantities for 4-phenylphenethyl alcohol and 2-naphthylethanol. The proposed mechanism proceeds via tandem nucleophilic substitution-elimination: deprotonation of the alcohol generates an alkoxide that attacks the electrophilic sulfur of SO₂F₂, furnishing a transient fluorosulfate. Rapid base-promoted elimination of fluorosulfinate then delivers the alkene product.

The advancement of non-noble metal catalysts holds immense importance for the broad industrial use of organic liquid hydrogen storage. In this study, Ni_aAl_b-layered double hydroxides (LDHs) were synthesized via co-precipitation method. Typically, a mixed solution of 100 mL Ni(NO₃)₂•6H₂O and Al(NO₃)₃•9H₂O was dropped into 100 mL Na₂CO₃ solution under vigorous stirring. The precipitation was carried out at room temperature, to achieve the desired pH value, a 3 mol/L NaOH solution was added to maintain the solution pH between 10±0.5. The resultant green precipitate underwent centrifugation and washing until nearly neutral, followed by drying for an extended period at 110 ℃. Thereafter, the sample was subjected to reduction at different temperatures for a duration of 2 h, with a meticulously controlled heating rate of 2.5 ℃/min. Finally, the influence of the Ni/Al ratio and reduction temperature on the catalytic activity was examined. The catalyst obtained by reducing NiAl-LDH at 450 ℃ (Ni₂Al_1-re450) exhibited the highest activity among the catalyst samples examined. Structural and compositional analyses of the catalyst were carried out using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectrometry (ICP-OES), and N₂ physisorption analysis (BET). The results indicated that the high hydrogenation activity of Ni₂Al_1-re450 was attributed to its larger specific surface area and smaller nickel particle size. Under the optimized reaction conditions (150 ℃, 6 MPa H₂, 2 h), the catalyst achieved a 100% conversion rate of NMID and a yield of 8H-NMID of 96.06% in a batch reactor, surpassing the commercial 0.5%Ru/Al₂O₃ hydrogenation catalyst. The hydrogenation reaction rate of NMID was positively correlated with temperature, with an apparent activation energy of 61.25 kJ/mol and a turnover frequency (TOF) of 52.62 h^－1. Moreover, Ni₂Al_1-re450 was continuously operated for 100 h in a micro packed-bed reactor under reaction conditions of 180 ℃ and 6 MPa. The results showed that the NMID conversion rate remained stable between 97%~100%, the selectivity for 8H-NMID was 97%~100%, and the hydrogen storage capacity was 5.55% (w)~5.76% (w).