Browse Articles

Semiclassical Theory of Stepped Electrodes and Step Bunching

Abstract Atomic-scale steps markedly influence electrochemical activity and stability and exhibit structural instability under electrochemical conditions. Yet the microscopic mechanisms that cause these behaviors remain largely unclear. Herein, we study the microstructure and thermodynamics of the electrical double layer at stepped electrodes, using the semiclassical density-potential functional theory. The theory captures trends observed in experiments regarding the differential capacitance and the potential of zero free charge (PZFC) with step density for stepped Au and Ag . Departing from the case of flat electrodes, the PZFC deviates from the potential of minimum capacitance at stepped electrodes, necessitating local PZFCs to describe heterogeneous surface charging conditions. Furthermore, linking step-induced PZFC shifts to changes of the surface tension, the theory predicts that step bunching is thermodynamically driven at more positive electrode potentials and sensitive to the electrolyte composition.

Streptococcus mutans colonization around orthodontic brackets bonded with flash-free versus conventional adhesives: an in-vitro study

Unlocking Anion Reduction of Lithium Perchlorate via Electrochemically Coupled Oxygen Atom Transfer

Abstract The growing demand for high energy density electrochemical energy storage necessitates energy vectors that maximize the number of electrons transferred per formula unit of active material. Herein, we introduce electrochemically coupled oxygen atom transfer (OAT) as a new paradigm to harness the energy of p-block oxoanions in a Li–metal solid-state battery. Using carbon-supported Fe nanoparticles in a dual role of OAT catalyst and conversion-type cathode active material, we demonstrate the eight-electron anion reduction of ClO4– at >50% conversion, delivering a capacity of 1150 mA h g–1 and an energy density of 1950 W h kg–1. We further demonstrate strategies to enhance the energy density at the electrode level, establishing a foundation for oxoanion-based anion redox in battery systems.

Early biomarker trajectories after stage-linked surgery for p16-negative oral squamous cell carcinoma

Coulombic Metal–Organic Frameworks Assembled from π-Stacked Organic Nodes and Polyoxometalate Inorganic Linkers

Abstract Metal–organic frameworks (MOFs) are typically constructed by forming coordination bonds between inorganic nodes and organic linkers. Here we present an alternative framework chemistry that does not rely on coordination bonding but instead exploits proton-transfer-facilitated Coulombic and hydrogen-bonding interactions. Protonation of basic amine molecules by acidic Keggin-type polyoxometalates (POMs) generates complementary organic cations and inorganic anions that rapidly self-assemble into crystalline frameworks at room temperature upon simple solution mixing. Solvent acidity modulates proton transfer and charge balance, thereby controlling amine–POM stoichiometry and packing modes and driving a structural evolution from π-stacked organic arrays (CouMOF-1) to a MOF-like node–linker network (CouMOF-2) and ultimately to a continuous POM-stacked phase (CouMOF-3). The intermediate phase, CouMOF-2, comprises a primitive cubic (pcu) net in which π-stacked organic molecules serve as 6-connected supramolecular organic nodes bridged by 2-connected POM clusters, producing a MOF-like topology without coordination bonding and representing a rare inversion of the conventional inorganic-node/organic-linker architecture of MOFs. These materials exhibit different sulfide oxidation activities and selectivities, highlighting solvent-controlled assembly as a route to tuning structure–function relationships. This assembly strategy extends to diverse amine monomers and polyoxometalates, and the synthetic simplicity together with the large chemical space of amine–POM combinations highlights organic–inorganic acid–base assembly as a versatile route to crystalline ionic frameworks that use nondirectional Coulombic interactions to generate ordered framework architectures, without resorting to coordination chemistry.

Bridge three-dimensional reconstruction model based on improved YOLOv9 and unmanned aerial vehicle photography

Photoactive Heteropore Covalent Metal–Organic Frameworks for CO2 Photoreduction

Abstract Metal–organic frameworks (MOFs) as a class of promising photocatalysts have been used for photocatalytic CO2 reduction reaction (CO2RR). Although many strategies have been developed for enhancing the photocatalytic activities, constructing photoactive heteropore MOFs for CO2RR remains largely unexplored. Herein, we report the synthesis of two two-dimensional (2D) copper cyclic trinuclear unit (Cu-CTU)-based heteropore covalent MOFs (CMOFs) and two homopore analogues. Interestingly, the heteropore CMOFs showed two times higher CO2 uptake than their homopore analogues. Moreover, the introduction of photosensitive units into heteropore CMOFs promoted light harvesting as well as charge separation, achieving a CO generation rate of 3548 μmol g–1 h–1 with 94.7% selectivity and an apparent quantum yield (AQY) of 6.78% at 420 nm in the presence of [Ru(bpy)3]Cl2. Notably, the photoactive heteropore CMOFs delivered high photocatalytic activity under diluted CO2 and natural sunlight conditions. Our work demonstrated that incorporation of heteropore structures and photosensitive units into MOFs can synergistically enhance photocatalytic CO2RR performance.

Sliding-dependent anharmonic phonon transport in Janus MoSiGeN4 bilayers

The Effect of Nanoparticle Structure on the Thermodynamics and Kinetics of Proton-Coupled Electron Transfer Reactions to V2O5

Abstract Proton-coupled electron transfers (PCETs) to metal oxides are key reactions for sustainable catalytic and energy storage processes. The factors that control PCET reactions on metal oxides are, however, not well understood, with the effect of particle morphology/surface faceting on the thermodynamics and kinetics of PCET being essentially untested. We measured the thermodynamics and kinetics of PCET from CpCr(CO)3H to five V2O5 samples of varying morphologies/surface faceting. Their nanostructures were assessed by Rietveld refinement accounting for preferred crystallite orientation, giving a semiquantitative measurement of surface faceting. PCET to V2O5 occurs via proton insertion-coupled electron transfer (PICET), where H· diffuses into the bulk of the particle. The thermodynamics of PICET are controlled by particle structure, with nonequilibrium morphologies requiring structural rearrangement during PICET. The kinetics of PICET are controlled by the rate of H· diffusion into the bulk, with diffusion along the interconnected V2O5 layers being 10x faster than between the layers. Samples with hindered H· diffusion also show low activity in the oxidation of methanol, demonstrating that diffusion of H· into the bulk occurs during catalysis. This work demonstrates that particle morphology is critical for PCET reactions to anisotropic metal oxides and must be considered when examining their reactivity.

Prevalence and determinants of gastroscopy in Northern Italy

Abstract Gastric cancer remains a major global health concern due to its late-stage diagnosis and high mortality rate. Early detection through gastroscopy can significantly improve outcomes. Screening programs have shown success in Eastern Asia, but their implementation and effectiveness in Western countries require further investigation. The present study was designed to investigate real-world gastroscopy utilization and factors associated with referral to upper gastrointestinal endoscopy in primary care, rather than to evaluate participation in an established gastric cancer screening program. This study, part of the GastroScreening project, aimed to assess the prevalence and determinants of gastroscopy among individuals aged 40–79 in Brescia, Northern Italy. The study involved 4426 participants who completed an online questionnaire covering sociodemographic factors, lifestyle habits, family history, and symptoms. Results Of the participants, 33.3% had ever undergone gastroscopy, 9.0% reported undergoing periodic gastroscopy, and 4.5% had received a gastroscopy in the past year. Alarm symptoms, such as nocturnal epigastric pain and fatigue, were present in 16.3% of the sample, while non-specific symptoms were reported by 60% of participants. Factors such as family history of gastric cancer, contact with people infected by Helicobacter pylori, and the presence of alarm symptoms were associated with increased likelihood of undergoing gastroscopy. The observed age- and sex-distribution of gastroscopy utilization did not mirror the corresponding age- and sex-distribution of gastric cancer incidence. Additionally, 1.8% of participants reported previous gastric surgery, primarily for bariatric reasons. The study highlights that only a small fraction of the general population undergo gastroscopy, moreover the sex-age distribution of gastroscopy utilization did not parallel the sex-age distribution of gastric cancer incidence. Alarm symptoms, together with family history of gastric cancer and contact with people infected by Helicobacter pylori seem to promote utilization of gastroscopy.

Photocatalytic Conversion of Aminocyclopropanes to γ-Lactams by Sequential Ring-Expansion and Peripheral Diversification

Abstract Rings underpin pharmaceuticals, agrochemicals, and materials, driving renewed interest in skeletal ring expansion. Current skeletal ring expansion strategies mainly focus on single-atom insertion or rearrangement; reliable methods for multiple single-atom insertion and peripheral diversification of saturated small rings are lacking. Herein, we report a general and efficient photocatalytic system directly converting aminocyclopropanes to γ-lactams via sequential C-/N-single-atom [n + 2] ring-expansion and peripheral diversification. The system accomplishes both γ-lactam formation and subsequent diversification at the γ-position via six distinct bond-forming reactions across hundreds of synthetic examples under predictable reaction conditions. Experimental and computational studies converge on photoredox-mediated radical pathways.

Phthalate induced testicular degeneration in mice: biochemical, histopathological and immunohistochemical evidence for the interplay of oxidative stress, caspase-3, and NF-κB signaling

Abstract Phthalates, including dibutyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP), are widely used plasticizers associated with male reproductive toxicity. This study evaluated the dose- and temporal-dependent effects of DBP and DEHP (100, 200, and 400 mg/kg for 15 days) on testicular structure and function in immature Swiss albino mice at 36, 45, 50, and 70 days of age. Biochemical analyses revealed significant glutathione depletion accompanied by increased nitric oxide and lipid peroxidation levels, suggesting oxidative imbalance. Histological evaluation demonstrated severe dose-dependent testicular injury, particularly at 36–45 days, with the 400 mg/kg groups showing 100% damaged seminiferous tubules and marked reductions in Johnsen’s scores (3.5 ± 0.17 vs. 9.9 ± 0.10 in controls). Increased Caspase-3 and NF-κB expression suggested possible involvement of apoptotic and inflammatory responses. Longitudinal assessment from 50 to 70 days revealed a dose-dependent recovery pattern, with substantial restoration in lower-dose groups, whereas higher doses remained associated with persistent tubular damage at 70 days (47.0% in DBP and 58.8% in DEHP groups). These findings suggest that the severity of testicular injury and the extent of recovery are influenced by phthalate exposure dose. Therefore, further studies are required to fully understand the underlying molecular mechanisms.

Enzyme-Activatable Fluorogenic Probes: Design Strategies, Biomedical Applications, and Future Perspectives

Abstract Enzymes are pivotal regulators of cellular metabolism and organismal homeostasis, and their dysregulation is often associated with the onset and progression of disease. Therefore, accurate monitoring of the real activities of target enzymes is essential for deciphering biological mechanisms and gaining pathological insight. Through decades of iterative refinement, a diverse repertoire of enzyme-activatable fluorogenic probes (EAFPs) have been developed, enabling the capture of aberrant enzyme dynamics with high spatiotemporal resolution and multifunctional biosensing capabilities. In this context, we highlight the current state-of-the-art EAFPs, spanning fundamental design principles to proof-of-concept applications. First, the molecular engineering, sensing mechanisms, and design strategies of EAFPs are introduced. Next, a wide range of cutting-edge probes for imaging and sensing target enzyme(s) are presented, with emphasis on structural features, recognition mechanisms, and biomedical applications. Representative examples in biomarker imaging, disease diagnosis, drug screening, and therapeutic testing are highlighted to illustrate both the design principles and practical utility. Finally, the existing challenges and future trajectories for EAFPs in specific application scenarios are discussed. The insights presented here will inspire and accelerate the development of high-performance multifunctional EAFPs for both fundamental and translational research.

Cohort, gender and spatial patterns of delayed school enrolment in third-grade children from 2009 to 2025

Abstract Delayed school enrolment can be an important marker for developmental delays and be associated with adverse health events. Analysing enrolment delays on an epidemiological level provides valuable insights in social, rural, socioeconomic or temporal variations. Using data from the EMOTIKON study, the influence of gender, rural and temporal variation was assessed on the frequency of children older than the key age (OTK) in a sample of 292,181 third-grade children in the Federal State of Brandenburg in Germany from 2009 to 2025. Temporal variation was analysed considering interference from significant events, specifically a change in regulation incorporating parental preferences and the onset of the SARS-CoV-2 pandemic. A generalised linear mixed model (GLMM) approach with a regression discontinuity design (RDD) revealed a substantial increase in the frequency of OTK children initiated by the change in regulation which persisted through the onset of the pandemic. The analysis further identified high regional socioeconomic deprivation, living far from metropolitan areas, living in midsize centres and being a boy as correlates of delayed school enrolment. These patterns suggests delays in school enrolment as a proxy for developmental delays to be heavily influenced by regulatory and social contexts, and at the same time highlights the importance of regional and gendered factors for school readiness assessments.

Controlling the Double Layer of Platinum by Selective Passivation of Step Sites Using Adatom Modification

Abstract The structure of the electric double layer at platinum electrodes remains incompletely understood, even for the model Pt(111)/HClO4 interface, which deviates significantly from Gouy–Chapman–Stern theory. While Pt(111) exhibits a true double-layer window (0.40–0.60 VRHE) that enables direct measurement of the double-layer capacitance, stepped Pt surfaces do not because hydrogen and/or hydroxyl species adsorb at low-coordinated step sites across the entire potential range. We previously showed that hydroxyl adsorption on (110)-steps is potential-independent within this nominal double-layer window, leading to decreasing capacitance with increasing (110)-step density due to suppression of the step Helmholtz capacitance. In contrast, (100)-steps exhibit potential-dependent hydroxyl adsorption that introduces a substantial pseudocapacitive contribution and increases capacitance with step density. Here, we selectively passivate Pt step sites by depositing Au* and Ag* adatoms. We find that Au*step-modification suppresses step-specific adsorption, restoring predominantly electrostatic behavior for (100)-type stepped Pt surfaces and reversing the capacitance trends observed for the bare stepped surfaces. In contrast, Ag*step-modification introduced an additional chemical contribution, manifested as substantially increased capacitance and enhanced CO oxidation activity due to adsorption of oxophilic species on Ag*. These results demonstrate that Pt step-site chemistry, and consequently the electrical double-layer structure and electrocatalytic activities, can be tuned and probed to a remarkable degree of controllability through selective adatom modification.

Interpretable Machine Learning Unveils Hydroxyl/Amino Synergy and Guides Discovery of Optimal MOF Photocatalysts for Hydrogen Evolution

Abstract Metal–organic frameworks (MOFs) are premier platforms for photocatalytic hydrogen evolution (PHER), yet navigating their multidimensional parameter space typically relies on inefficient trial-and-error approach. While machine learning (ML) can accelerate discovery, it is often hindered by ″black-box″ predictions that lack mechanistic transparency and experimental validation. Herein, we establish an interpretable ML-to-experimental framework for rational MOF engineering. By training a CatBoost model on a curated database and employing SHapley Additive Explanations (SHAP), we deconstructed the hierarchical influence of ligand motifs on catalytic activity. This revealed the cooperative effect of hydroxyl and amino dual functionalization, which optimizes the electronic landscape through balanced bandgap dynamics and hard–soft acid–base (HSAB) matching. Guided by these insights, we synthesized benzophenanthrene-based mixed-ligand MOFs. The champion catalyst achieved a peak HER rate of 73.7 mmol g–1 h–1─without external photosensitizers or cocatalysts─exhibiting a 4.18% deviation from algorithmic predictions and a 15.8% enhancement over the top of the data set. This work develops a high-performance photocatalytic system and provides a generalizable, interpretable paradigm for data-driven discovery of advanced energy materials.

A simple clinical model using waist circumference and cholesterol predicts liver fibrosis in MAFLD

Abstract Metabolic dysfunction-associated fatty liver disease (MAFLD) involves chronic low-grade inflammation; however, the utility of inflammatory markers for fibrosis risk stratification remains unclear. We aimed to investigate the relationships between inflammatory cytokines, steatosis, and fibrosis and to develop a simple predictive model for liver stiffness. We enrolled 49 patients with MAFLD who underwent anthropometric measurements, laboratory testing (including Interleukin-6 (IL-6) and High-sensitivity of C-reactive protein (hs-CRP), and vibration-controlled transient elastography (FibroScan) for steatosis ( controlled attenuation parameter, CAP) and fibrosis (liver stiffness measurement, LSM). Correlations between inflammatory markers, metabolic parameters, and liver outcomes were analyzed. Logistic regression identified fibrosis predictors (LSM ≥ 6.0 kPa, indicating any degree of fibrosis), and predictive performance was compared with that of traditional indices. Internal validation was performed using bootstrap resampling with 5000 iterations (bias-corrected accelerated method). A sensitivity analysis further adjusted for age, sex, diabetes, and use of glucose-lowering and lipid-lowering medications.(exploratory, not bootstrapped). IL-6 levels were positively correlated with CAP ( R  = 0.390, P  = 0.007), triglycerides, and uric acid levels, and negatively correlated with high density lipoprotein (HDL) levels. hs-CRP showed strong correlations with LSM ( R  = 0.639, P  < 0.001), body mass index (BMI), and liver enzymes. Waist circumference (odds ratio [OR] = 1.21, P  = 0.004) and cholesterol levels (OR = 4.80, P  = 0.011) independently predicted early fibrosis in the parsimonious model. After adjusting for age, sex, diabetes, and medication use, waist circumference (OR = 1.226, 95% CI: 1.055–1.425, P  = 0.008) and cholesterol (OR = 4.677, 95% CI: 1.249–17.509, P  = 0.022) remained significant, with AUC 0.897, sensitivity 73.7%, specificity 86.2%, and accuracy 81.3%. Bootstrap internal validation confirmed model stability, with bootstrap-corrected ORs of 1.230 (95% CI: 1.070–1.499) for waist circumference and 5.366 (95% CI: 1.376–32.187) for cholesterol, with AUC 0.866, sensitivity 73.7%, specificity 89.7%, and accuracy 83.3%. The combined model yielded an area under the curve (AUC) of 0.862 (95% CI: 0.744–0.980), which compared favorably with APRI (0.722), FIB-4 (0.537), and AST/ALT ratio (0.340). Central obesity and lipid dysfunction are key determinants of MAFLD-related fibrosis. A simple model using waist circumference and cholesterol provides robust, internally validated risk stratification for early fibrosis, independent of common metabolic confounders. External validation in larger cohorts is required before clinical implementation.

Synthesis of Chiral Triarylmethanes via Catalytic Asymmetric Skeletal Editing

Abstract Catalytic asymmetric skeletal editing (CASE) has emerged as a powerful strategy for accessing chiral organic molecules through enantioselective modification of parent molecular skeletons. Herein, we report an enantioselective Rh-catalyzed single-carbon insertion into indole rings with diazoesters via either desymmetrization or kinetic resolution, thereby enabling arene-to-arene transmutation and, for the first time, the construction of exocyclic carbon-centered stereocenters. Starting from indole-containing triarylmethanes, a broad range of optically active triarylmethanes bearing diverse arene/heteroarene combinations with distinct aromatic electronic properties were obtained in moderate to good yields and high enantioselectivities (up to 96% ee). The method was further extended to desymmetrizing skeletal editing of alkyl- and alkenyl-substituted bis(indolyl)methanes, indole-containing simple natural products and pharmaceutical motifs. Its potential for structural transmutation was further demonstrated by a 3-fold programmable skeletal editing sequence of an indene-substituted bis(indolyl)methane.

Explainable feature selection in high-dimensional time series using the sequential squeeze algorithm improves predictive accuracy and interpretability

3D Electron Microscopy Reveals Evidence for Strong Electric Fields at Nanoconfined Air–Water Interfaces

Abstract Strong electric fields at air–water interfaces are widely invoked to explain accelerated interfacial chemistry, yet direct, probe-free evidence under evaporation-free conditions has remained challenging. Here, we confine aqueous solutions and air within ∼50 nm-diameter multiwalled carbon nanotubes to stabilize nanoscale air–water interfaces for three-dimensional transmission electron microscopy. Reconstructed multiphase structures reveal ∼10 nm gas domains separated from the nanotube walls by ultrathin water films spanning molecular to nanometer thicknesses. Curvature analysis yields Laplace and disjoining pressure distributions indicating a repulsive pressure of ∼10 MPa that prevents film collapse. This repulsion is consistent with an interfacial electric field on the order of several volts per nanometer, primarily associated with oriented water dipoles and potentially enhanced by the electric double layer. Consistent with this inferred field strength, the reduction of chloroauric acid (HAuCl4) to gold nanoparticles occurs exclusively within ∼2 nm of the interface. These results provide evidence for intense, spatially confined electric fields at air–water interfaces through the combined observations of strong non-Derjaguin–Landau–Verwey–Overbeek repulsive pressures and localized interfacial Au reduction and establish their fundamental role in nanoscale interfacial chemistry across chemical, environmental, and energy-relevant systems.