Browse Articles

Synergistic Pore Microenvironment Engineering in Zinc Metal–Organic Frameworks for High SF ₆ /N ₂ Selectivity and Humidity‐Resistant Trace SF ₆ Capture

ABSTRACT Sulfur hexafluoride (SF 6 ) is a potent greenhouse gas widely used in electrical insulation. Although the size difference between SF 6 and N 2 enables separation in principle, achieving high SF 6 selectivity at trace concentrations, large adsorption capacity, and long‐term stability remains a formidable challenge. Herein, we report a family of new zinc‐based metal‐organic frameworks ( Zn‐tcpb , Zn‐tcpb‐bim , Zn‐tppb‐bim ) with systematically tunable pore sizes and electrostatic microenvironments. By integrating a mixed‐ligand strategy (tetracarboxylic acids plus 2,2'‐biimidazole) with pore functionalization, we achieve synergistic control over adsorption and separation properties. Among them, Zn‐tppb‐bim— featuring electron‐withdrawing pyrazine rings—exhibits a remarkable low‐pressure SF 6 uptake of 3.06 mmol/g at 0.1 bar, and an excellent SF 6 /N 2 IAST selectivity of 606 (1:9, 1 bar), achieving a balance between uptake and selectivity. Theoretical calculations reveal that the N‐heterocyclic units in Zn‐tppb‐bim generate a stronger positive framework charge, enhancing C─H···F interactions with SF 6 . Dynamic breakthrough experiments confirm complete separation of SF 6 /N 2 mixtures. Remarkably, the materials retain full separation performance even at 80% relative humidity. This work demonstrates a viable and generalizable design strategy that synergistically optimizes adsorption capacity, selectivity, and humidity resistance, providing a rare example of metal–organic framework that are both highly efficient and stable under practical conditions.

Blood‐Brain‐Barrier‐Crossing Fluorinated Luciferase Prosubstrates Enable Sensitive Monitoring of D‐Cysteine Levels in Brain Diseases

ABSTRACT D‐Cysteine (D‐Cys) is critically involved in regulating redox homeostasis within the brain, and its dysregulation has been closely related to the pathogenesis of various neurological disorders. However, the precise mapping of cerebral D‐Cys levels in situ remains a formidable challenge due to the lack of specific detection tools. Herein, we report a new class of fluorinated firefly luciferase prosubstrates for sensitive and noninvasive detection of D‐Cys in the brain via nitrile‐aminothiol bioorthogonal reaction. The lipophilic 7'F‐CBT exhibits enhanced blood‐brain barrier (BBB) permeability and reacts with endogenous D‐Cys to form a luciferin analog in situ, generating prolonged and intense bioluminescence. It sensitively detected D‐Cys in vitro, achieving a detection limit of 1.37 nM, and successfully imaged endogenous D‐Cys in the mouse brain with a high signal‐to‐noise ratio (60:1) after intravenous administration. Furthermore, 7'F‐CBT enabled unprecedented video‐rate visualization of D‐Cys in freely moving glioblastoma‐bearing mice. More importantly, by leveraging BBB‐permeable 7'F‐CBT , we revealed a precipitous reduction of brain D‐Cys levels in a drug‐induced Parkinson's disease (PD) mouse model for the first time. This study paves the way for diagnosing D‐Cys‐related brain diseases and provides a novel diagnostic tool.

Feasibility and safety of transcranial direct current stimulation in the treatment of adolescent depression in a naturalistic inpatient setting: a double-blind randomized controlled trial

Abstract Transcranial direct current stimulation (tDCS) has potential as a treatment for adult depression, but its effectiveness in adolescents remains unexplored. This study evaluated the feasibility, safety, and efficacy of tDCS in young in-patients with depression. In a randomized, double-blind, sham-controlled trial, 34 adolescent in-patients (mean age 15.48 years) received ten sessions of either tDCS or sham stimulation over two weeks, alongside standard treatment. Depression severity, quality of life, emotional and behavioral issues, and executive functions were assessed before, immediately after, and two weeks post-treatment. The results indicated that tDCS was feasible and well-tolerated, with 28 patients completing at least eight sessions. Side effects were reported in nearly half of the sessions (45% sham, 48% tDCS), primarily mild to moderate, and no sessions were interrupted due to discomfort. Both groups experienced significant improvements in depressive symptoms and high treatment satisfaction, but no significant differences were found between the tDCS and sham groups. In conclusion, while tDCS appears to be a safe treatment option for adolescents with depression, this study could not show it to be superior to sham treatment. Further research with greater statistical power is needed to control for covariates.

Correction: Italy’s progress towards the objectives of the national action plan to combat antimicrobial resistance

Non‐Superacid‐Catalyzed Preparation of Anion Exchange Membranes for High‐Performance Water Electrolyzers

ABSTRACT Recent advances in anion exchange membrane water electrolyzers (AEMWEs) have been primarily driven by anion exchange membranes (AEMs) prepared via superacid‐catalyzed polymerization. However, the reliance on highly corrosive trifluoromethanesulfonic acid (TFSA; pKa = −14.7) employed both as catalyst and solvent poses significant safety, handling, and scalability challenges for industrial AEM manufacturing. Herein, we report a nonsuperacid polymerization strategy for AEMs, utilizing methanesulfonic acid (MSA; pKa = −1.9) to catalyze the Friedel–Crafts alkylation between electrophilic aminobenzaldehyde and electron‐rich dibenzo‐18‐crown‐6. Crown ether incorporation expands interchain spacing, thereby facilitating the formation of continuous hydrophilic ion‐conducting channels. Furthermore, complexation of potassium ions with crown ether moieties weakens the electrostatic interaction between K + and OH − , thereby lowering the dissociation energy of the KOH electrolyte. As a result, the optimized QPCA‐70 membrane exhibits a high alkaline conductivity of 628.93 mS cm −1 at 80 °C and delivers a current density of 8.8 A cm −2 at 2.0 V using a NiFeCo anode. Critically, MSA serves as a safer, more practical, and cost‐effective alternative to TFSA: it eliminates the extreme hazards associated with superacid handling, thereby enabling scalable, industrially viable, and low‐risk AEM production.

Engineering Na–Au ^δ ⁻ Interfaces for Enhancing Selective Methane Hydroxylation With O ₂ via Controlled In Situ H ₂ O ₂ Generation

ABSTRACT The selective oxidation of methane (CH 4 ) to value‐added oxygenates (e.g., methanol, acetic acid) under mild conditions remains a pivotal yet formidable challenge in catalysis. Herein, we design Na‐decorated Au nanoparticles supported on mordenite (MOR) nanosheets, which leverage electronic metal‐support interactions to dynamically tune the electronic state and local microenvironment of the active sites for directional C─H activation under CH 4 /CO/O 2 /H 2 O at 150° C. This catalyst affords near‐100% selectivity toward hydroxylated oxygenates derived from CH 4 with a remarkable productivity of 2.02 mmol·g cat −1 ·h −1 , outperforming most reported catalysts under comparable conditions. In situ spectroscopic studies and density functional theory (DFT) calculations reveal that Na‐induced electronic modulation creates a unique Na‐Au δ − interfacial structure, driving the Au species into an electron‐deficient state that boosts the oxygenate formation rate by more than an order of magnitude compared to the pristine Au δ− sites. The Na‐Au δ− interface enhances catalysis by enabling accelerated in ‐situ H 2 O 2 generation and concurrent C─H bond activation, while avoiding methanol overoxidation, thereby boosting overall catalytic performance. This work deciphers the dynamic role of in situ generated H 2 O 2 in methane activation under mild conditions, and establishes electronic microenvironment engineering as a powerful strategy for the selective and controllable oxidation valorization of methane.

Theoretical study of drug delivery behavior of graphitic carbon nitride nanosheets for mesalazine in the gas and solvent phases

Experimental study on mechanical response of soft soil freezing in underground excavation using artificial ground freezing method

To ensure the stability of the artificial frozen wall during the underground excavation of a proposed subway station using the artificial ground freezing method in soft soil strata, and to guarantee the construction safety of the proposed station under-crossing beneath an existing operating station. Based on the project of a proposed subway station under-crossing an existing station via underground excavation with artificial ground freezing method, four typical soft soils, namely silty clay, mucky soil, residual cohesive soil, and fully weathered ignimbrite, were selected to conduct systematic physical and mechanical tests of frozen soil under the temperature range of −20°C to −5°C. The influence mechanism of temperature and confining pressure on the thermodynamic behavior of frozen soil was revealed through the transient hot wire method, unidirectional frost heave and thaw settlement test, and triaxial shear test. The results show that the thermal conductivity of soil samples increases significantly at low temperatures, with the largest increase observed in fully weathered ignimbrite and the smallest in mucky soil. The freezing temperature of soil samples under natural moisture content ranges from −2.25°C to −0.8°C, with the lowest value recorded for residual cohesive soil. The creep of frozen soil exhibits obvious stress dependence: it presents typical three-stage creep characteristics at the stress level of 0.5σs, and its long-term strength is approximately 0.5–0.7 times the instantaneous strength. In engineering practice, lower freezing temperature or strict control of loading duration should be adopted for soil layers with high creep potential. The triaxial shear strength of frozen soil increases with the decrease of temperature, and the most significant increase occurs in the temperature range of −5°C to −10°C. The strength of the tested soils ranks as follows: fully weathered ignimbrite > residual cohesive soil > silty clay > mucky soil. The influence of confining pressure on strength varies with soil types. During construction, differentiated freezing and support control measures shall be implemented according to the characteristics of soil layers, and monitoring shall be strengthened for sections with abnormal confining pressure response. The research results can provide an important basis for design optimization and construction risk control of subway underground excavation projects using artificial ground freezing method in soft soil areas.

Hydrogen‐Tolerant CuO/TiO ₂ Catalysts Enabled by Oxygen Anchoring for Nitrile Hydrogenation

ABSTRACT Designing reducible metal oxide catalysts that remain stable under hydrogenation conditions represents a longstanding challenge in heterogeneous catalysis, as most oxides are readily reduced and structurally degraded in H 2 ‐rich environments. Here, we report an oxygen‐anchoring strategy that enables hydrogen‐tolerant metal oxide catalysts. Using this approach, a CuO/TiO 2 catalyst stabilized by an oxygen‐rich C─O framework (HT‐CuO/TiO 2 ) was constructed for the selective hydrogenation‐coupling of nitriles to secondary amines. The oxygen functionalities within the C─O framework act as anchoring sites that stabilize CuO nanoclusters and suppress their reduction under hydrogen. The stabilized CuO nanoclusters function both as hydrogen activation centers and Lewis acid sites for nitrile adsorption. Meanwhile, the introduction of TiO 2 leads to the formation of intimate CuO─TiO 2 interfacial structures, accompanied by the presence of Ti 3+ species and enhanced hydrogen activation behavior. Notably, this hydrogen‐tolerant behavior extends to a range of reducible metal oxides, including CuO, Cu 2 O, CoO, and NiO, demonstrating the generality of the oxygen‐anchoring stabilization principle. This work establishes a general strategy for stabilizing reducible metal oxides under hydrogen and unlocks their catalytic potential for hydrogenation chemistry.

RATEX: A Scalable RNA‐Based Platform for Logical and Multi‐Layered Cellular Programming

ABSTRACT Scalable genetic circuits are essential for implementing complex functions in living cells. Toward this goal, RNA regulators can provide a much‐needed parts library with added benefits of low metabolic load, design flexibility, and logic capacity. However, despite the great potential of synthetic RNA circuits, constructing such circuits with wide dynamic ranges and multiplexed regulatory cascades remains a challenge. To address this, we introduce RATEX (Ribosome‐Assisted Transcriptional EXpression controller) by integrating a translation‐to‐transcription converter with synthetic RNA regulators, enabling a compact and scalable RNA‐programmed circuit architecture. The RATEX platform repurposes a large library of well‐characterized translation regulators with up to 1,492‐fold gene regulation, while leveraging natural ribosome‐mediated sensing of diverse environmental inputs, such as metabolites. We demonstrated multi‐input logic processing with up to a 6‐input OR logic gate for RNA inputs and hybrid 3‐input logic gates to sense diverse metabolite and small‐molecule inputs alongside RNA signals. Signal amplification with multiplexed combinatorial control of RNA outputs was achieved through multiplexed signaling cascades. Finally, the RNA‐ and metabolite‐sensing 3‐input AND gates were used to control cellular morphology and intracellular spatial organization. Together, the RATEX platform, with its scalable and modular architecture, offers a broad potential design space for synthetic biology and biotechnology.

A qualitative study of young people’s experiences of counselling in headspace Denmark as a civic approach to youth mental health

Airborne spread of severe acute respiratory syndrome coronavirus 2 between rooms in a sealed, mechanically ventilated ward: Evidence from a hospital outbreak investigation

Airborne transmission of severe acute respiratory syndrome coronavirus 2 in enclosed, mechanically ventilated hospital wards remains poorly characterized. In February 2025, a coronavirus disease cluster involving 17 individuals occurred across multiple rooms in a sealed Japanese hospital ward. Several infected individuals had no documented close contact with the index patient, raising concerns about ventilation-related airflow-induced inter-room aerosol transmission. A multimodal environmental investigation was conducted via (1) CO 2 decay experiments to quantify air change rates (ACHs), (2) particulate matter (PM) 2.5 aerosol dispersion measurements using fog as a surrogate tracer, and (3) computational fluid dynamics (CFD) simulations to visualize airflow and scalar transport. Measurements were taken in the index room (Room A), corridor, and adjacent Rooms B–D under closed- and open-door conditions. Opening the patient room door significantly increased indoor ACHs (3.29/h → 4.01/h, p = 0.030) and allowed CO 2 tracer gas to escape into the corridor. In the PM 2.5 dispersion experiment, aerosols released in Room A were detected within the room, corridor, and neighboring rooms, with the highest out-of-room aerosol burden observed at the corridor sensor (area under the curve = 2.6 × 10 5 μg·s/m 3 ). PM 2.5 and PM 10 concentrations were strongly correlated (r = 0.9997), revealing intermediate-sized particles capable of longer-range transport. CFD simulations reproduced key qualitative features of the experiments, including tracer accumulation within curtain-enclosed compartments, delayed leakage through the doorway, and downstream transport toward the corridor. Inter-room aerosol transport can occur in sealed, mechanically ventilated wards without natural ventilation or structural openings between rooms. Opening doors improves in-room ventilation and promotes aerosol leakage, revealing a trade-off between the dilution and contamination of shared spaces. Architectural elements such as privacy curtains contribute to airflow stagnation and uneven aerosol removal. Effective infection control strategies must incorporate airflow pathway management and localized filtration to prevent unintended aerosol migration in mechanically ventilated healthcare settings.

Visualizing Senescent–Normal Cell Boundaries Through Environment‐Dependent Bidirectional Luminescent Contrast

ABSTRACT Unlike tumors, senescent tissues lack well‐defined boundaries at the cellular level because senescence develops gradually, leading to spatial intermixing of the senescent and normal cells. This ambiguity poses a major conceptual challenge for surgical decision‐making, where insufficient resection risks recurrence while excessive removal compromises tissue integrity. Existing probes fail to resolve this ambiguity because signal‐silent regions may represent either normal cells or unlabeled senescent populations. Therefore, designing new signal logic for luminescent probes (e.g., environment‐dependent bidirectional signal modulation, depending on the cellular environment of the normal and senescent cells, respectively), is crucial for precise delineation of senescent–normal cell boundaries. In this work, luminescent probes enabling bidirectional photomodulation were constructed by modifying hydrophilic β‐galactose groups onto hydrophobic hydroxyl‐hexathiobenzene, which can exhibit the following performance: (1) Direction 1: In normal cells, the probes remain non‐emissive, but become emissive upon photoexcitation‐induced aggregation (signal up‐regulated); (2) Direction 2: In senescent cells, β‐galactosidase (β‐Gal)‐triggered deglycosylation immediately generates hydrophobic products with an aggregation‐induced emission characteristic, whose strong emission can be down‐regulated upon a following photoexcitation‐induced molecular reorganization. This environment‐dependent bidirectional photomodulation using the same probe enables dynamic contrast between senescent and normal cells, thereby providing a new paradigm of resolving biological ambiguity at the cellular scale.

A compositional framework for automated discovery of adversarial attacks

Tumor-associated M2 macrophages promote prostate cancer invasion through the M-CSF-PCLAF pathway

Background Prostate cancer (PCa), particularly in its advanced and castration-resistant forms, remains a major threat to men’s health, with the tumor microenvironment (TME) playing a crucial role in its progression. Tumor-associated macrophages (TAMs), especially the M2 phenotype, are key components of the TME. Our previous work identified that M2 TAMs in PCa upregulate M-CSF secretion via the MS4A6A-MYC pathway. This study aims to identify the critical downstream effector within PCa cells that mediates the tumor-promoting effects of M-CSF. Methods The impact of M-CSF on PCa cell (PC3 line) viability, invasion, and migration was assessed using CCK-8, Transwell, and wound healing assays. To identify M-CSF-regulated downstream proteins, a comprehensive proteomic analysis (DIA-PASEF) was performed on PC3 cells treated with or without M-CSF. Bioinformatic analyses screened for differentially expressed proteins. Key candidate PCLAF was further validated using Western blot, analysis of TCGA-PRAD data, and immunohistochemistry on a prostate tissue microarray (79 patients). The functional role of PCLAF was confirmed through in vitro experiments and an in vivo xenograft model in nude mice, comparing tumors from PC3 control cells, PC3 cells overexpressing KIAA0101/PCLAF (PC3-KIAA0101+), and PC3 cells with local M-CSF injections. Results M-CSF stimulation significantly enhanced PC3 cell viability, invasion, and migration in a concentration-dependent manner. Proteomic analysis revealed 95 differentially expressed proteins following M-CSF treatment. Among the top candidates, PCLAF/KIAA0101 was the only protein consistently and significantly upregulated by M-CSF in validation experiments. Analysis of TCGA data confirmed PCLAF’s significant overexpression in PCa tumors and its association with poorer disease-free survival. Tissue microarray analysis demonstrated that PCLAF expression was significantly higher in PCa tissues compared to benign tissues and positively correlated with higher Gleason Grade Groups and ISUP risk groups. In the xenograft model, both PC3-KIAA0101+ and PC3 + M-CSF groups exhibited significantly increased tumor growth, volume, and weight compared to the control group. IHC, Western blot, and PCR analyses of the xenograft tumors confirmed that PCLAF expression levels followed the pattern: PC3-KIAA0101+ > PC3 + M-CSF > control, and were positively correlated with tumor growth. Conclusions This study indicates that M-CSF, secreted by M2 TAMs, promotes prostate cancer progression by upregulating the expression of PCLAF/KIAA0101 in cancer cells. PCLAF is overexpressed in PCa, correlates with tumor malignancy and poor prognosis, and its upregulation is sufficient to enhance tumor growth in vivo. These findings indicate the M-CSF-PCLAF axis as a key mechanism through which TAMs drive PCa invasion and progression, identifying PCLAF as a potential therapeutic target.

An Enantioselective Alkene Aminoarylation to Form Chiral Indolines via Electrostatically‐Directed Palladium Catalysis

ABSTRACT Most design strategies in asymmetric transition metal catalysis invoke repulsive interactions between ligand and substrate. Yet those that incorporate attractive interactions can offer advantages, such as rate acceleration and greater generality, due to the fundamentally different mode of operation. Here we deploy electrostatically‐directed Pd catalysis using the chiral sulfonated ligand sSPhos to realize an asymmetric aminoarylation of ortho ‐allyl anilines under mild conditions. A wide variety of substituted aryl bromides and anilines provide access to 2‐benzylindolines with high enantioselectivity. Our study uncovers trends relating the electronics of both coupling partners to ee . These trends allowed tuning of the sulfonamide protecting group to enable good results across a broader range of substrates.

Multi‐Objective Catalyst Discovery in High‐Entropy Alloy Composition Space: The Role of Noble Metals on the Pareto Front for Oxygen Reduction Reaction

ABSTRACT Discovering new materials for electrocatalytic energy conversion reactions is a key step toward energy sustainability. However, for catalysts to be viable in practice, they must perform in multiple, potentially conflicting objectives. We demonstrate this challenge for the acidic oxygen reduction reaction (ORR), where activity, stability, and material cost must be balanced. Using the continuous composition space of high‐entropy alloys (HEAs) together with our established models for activity and dissolution, we identify a Pareto‐optimal set of ORR catalysts within the Ag─Au─Cu─Ir─Pd─Pt─Rh─Ru system via multiobjective Bayesian optimization. Additionally, we introduce a fine‐tuned machine learning model that predicts adsorption energies for alloys spanning 12 elements and 9 adsorbates. Our results show that alloying expands the hypervolume spanned by the Pareto front, consisting of low‐ to medium‐entropy alloys composed primarily of Ag, Au, Cu, Pd, and Pt. We further propose an approach for analyzing the Pareto front by quantifying the loss in hypervolume when critical elements (Au, Pd, and Pt) are removed, clarifying their relative contributions to optimal performance. This work highlights the need to consider all relevant objectives in catalyst optimization and the advantage of HEAs as a powerful platform for multiobjective catalyst discovery.

A multi-programmed cell death-related LncRNA signature for prognosis and immune microenvironment evaluation in kidney renal clear cell carcinoma

Vulnerability assessment to tropical cyclones in the North Caribbean Coast of Nicaragua (1988–2022)

The North Caribbean Coast Autonomous Region of Nicaragua (RACCN) is one of the most vulnerable areas to tropical cyclones (TCs), a condition exacerbated by climate change and internal structural disparities. Despite its historical exposure to TCs, significant gaps remain in the systematic analysis of its vulnerability. This research assesses the vulnerability levels of RACCN municipalities to TCs by constructing a Tropical Cyclone Vulnerability Index (VItc), and a municipal typology based on exposure, susceptibility, and adaptive capacity factors. Twelve indicators were selected, normalized, and analyzed using factor analysis with varimax rotation. The resulting sub-indices were integrated through weighted aggregation, and a municipal typology was developed using the Natural Breaks (Jenks) classification method. Findings reveal marked territorial disparities among municipalities. Bonanza exhibits high exposure and susceptibility combined with low adaptive capacity while Waslala demonstrates greater structural resilience. The VItc enabled the identification of three municipality clusters, with differentiated vulnerability profiles, facilitating the design of targeted interventions. The results underscore the role of social, demographic, and infrastructure factors in shaping local vulnerability. Despite limitations in data availability, the VItc provides a diagnostic tool that may help identify priority areas and the development of strategies for disaster risk reduction and resilience in the RACCN. The study highlights the need to improve data availability and strengthen institutional capacities. It also points to important directions for future research, including the integration of territorial, socioeconomic, and gender-sensitive approaches, as well as dynamic variables such as climate projections, land-use change, and migration, together with participatory methods that integrate local knowledge.

Microdroplets Boosted Photocatalytic H ₂ O ₂ Production Over Covalent Organic Frameworks via Tri‐Phase Interface Catalysis

ABSTRACT Photocatalytic H 2 O 2 production from H 2 O/O 2 is a green solar energy conversion strategy, but the conventional bulk liquid systems suffer from poor mass transfer and limited active site accessibility. Here, by introducing sessile water microdroplets into the system using a covalent organic framework (DS‐OH‐COF) as a photocatalyst, the H 2 O 2 production rate was significantly enhanced. The yield strongly depends on droplet size. At 1 µL under air atmosphere, H 2 O 2 yield reached 11.11 mmol g −1 h −1 , representing a 12.3‐fold increase over bulk water systems. Under O 2 , the yield increases to 14.79 mmol g −1 h −1 , outperforming most reported photocatalysts. The large specific surface area of microdroplets enhances O 2 mass transfer into the liquid phase, promoting interaction with catalyst active sites. Most importantly, the gas‐liquid‐solid tri‐phase interface plays a vital role in the catalytic process. Density functional theory calculations confirm that the O 2 adsorption behavior is modulated by the substrate, which regulates O 2 reduction at the tri‐phase interface. The microdroplet system also enabled efficient methyl orange degradation, demonstrating its practical potential. This microdroplet‐based catalytic path effectively overcomes the inherent limitations of insufficient oxygen mass transfer and low efficiency in bulk reactions, providing new insights for catalytic H 2 O 2 generation.