Browse Articles

Schleyer hyperconjugative aromaticity as an efficient strategy to induce more delocalization in penguinone and thiopenguinone derivatives: a DFT investigation

Interface‐Engineered Electron‐Deficient Nickel Species for Efficient Depolymerization of Polyethylene Terephthalate

ABSTRACT Polyethylene terephthalate (PET) is the most abundant polyester plastic. Its chemical recycling mainly relies on homogeneous catalysis, often suffering from difficult catalyst separation and substantial waste generation. Previous work using heterogeneous catalysts has primarily focused on increasing Lewis acidity through variation of metal oxide types to improve performance, but catalyst activity remains limited. Here, we adopt an alternative strategy for modulating Lewis acidity with enhanced control by systematically tuning electronic properties of structurally versatile Ni active sites. Nickel can readily form intermetallics and layered double hydroxide (LDH) derivatives, providing substantial flexibility for modulating its electronic structure. We establish an electron‐deficiency–dependent activity framework and discover a Ni 3 Ga/NiAlO x  catalyst that exhibits unexpectedly high activity, surpassing more strongly Lewis‐acidic fully oxidized Ni species and delivering an order‐of‐magnitude activity enhancement compared with conventional Lewis‐acidic oxides. This high activity originates from electron‐deficient interfacial Ni sites where electron withdrawal from O in LDH‐derived NiAlO x  and electron donation from Ga in intermetallic Ni 3 Ga result in appropriate Lewis acidity, enabling near‐quantitative dimethyl terephthalate recovery from post‐consumer PET. Theoretical and experimental validation suggests that such bidirectional electronic modulation balances substrate activation and product desorption, thereby maximizing catalytic efficiency. The catalyst is prepared via an industrially‐established co‐precipitation method and is readily scalable.

A multimodal multi-label deep learning framework with temporal attention for detection of upper-limb motor activities for prosthetic control

Regulating Mechano‐Electrochemical Process for Uniform Lithium‐Ion Extraction in Ni‐Rich Single‐Crystal Cathodes

ABSTRACT Both mechanical and electrochemical processes critically govern the performance of single‐crystal Ni‐rich cathodes of lithium‐ion batteries. Although electrochemically induced lattice defects are widely regarded as detrimental to cycling stability, mechanically introduced defects during electrode fabrication are commonly assumed to be similarly harmful. Contrary to this prevailing assumption, we demonstrate that although mechanical compression does introduce various structural defects, transmission electron microscopy reveals that these pre‐existed defects are self‐passivated during cycling and contribute negligibly to degradation. Instead, densification process unexpectedly enhances both cycling stability and rate capability, primarily due to reduced porosity and improved electronic connectivity. We further identify that capacity degradation is dominated by lattice distortions arising from rapid c ‐axis contraction during the H2‐H3 phase transition, which triggers strain accumulation, planar gliding, and crack propagation — all of which are significantly alleviated in densified electrodes. Molecular dynamics simulations corroborate these findings, showing compact electrode structure promotes more uniform lithium‐ion extraction and mitigates stress concentration, thereby preserving the cathode's layered structure. These findings reveal the mechano‐electrochemical coupling from electrode to lattice level, providing a multiscale perspective to optimize electrode manufacturing for durable high‐energy batteries.

Mapping Mpox vaccine hesitancy using an integrated machine learning and structural equation modeling approach

Stepwise Kinetics Promotion for High‐Rate Aqueous Zn Metal Batteries

ABSTRACT Metallic zinc anodes in aqueous zinc batteries suffer from uncontrolled dendrite growth and parasitic side reactions, leading to poor cycling stability, especially under high‐rate and high‐capacity conditions. Herein, we proposed a stepwise kinetics promotion process to achieve high‐rate and durable Zn metal anodes, in which the desolvation, bulk transfer, and deposition steps of Zn 2+ are systematically considered and synergistically regulated. Experimental and computational analyses reveal that N‐methyl morpholine‐N‐oxide (NMMO) molecular regulator captures—rather than substitutes—coordinated water molecules in the Zn 2+ solvation sheath, thereby suppressing Zn corrosion and hydrogen evolution without increasing desolvation barriers. Furthermore, the strong interaction between NMMO and free water reconstructs the hydrogen‐bond network, creating an unimpeded proton‐transport channel that accelerates Zn 2+ bulk transfer. Additionally, the preferential adsorption of the NMMO molecule on non‐(101) Zn facets promotes the selective exposure of highly active Zn (101) texture, boosting Zn deposition kinetics. Consequently, Zn||Zn symmetrical cell delivers exceptional lifespan— over 6100 h at 5 mA cm −2 and 1300 h at 30 mA cm −2 —with low overpotentials. Notably, the Zn anodes still maintain stable cycling even at a 70% depth of discharge and ensure stable operation of full cells with a low negative/positive capacity ratio of 2.1.

Joint full waveform inversion and source localization of virtual and actual passive source seismic data

Amorphous MoO _x Interfaces Activate Pt Nanoclusters for Ultralow‐Overpotential Chlorine Evolution

ABSTRACT Direct seawater electrolysis offers a pathway to co‐produce hydrogen and industrial chlorine, yet chlorine evolution at low chloride concentrations is limited by sluggish halide activation and rapid Pt dissolution under oxidative conditions. Here we show that in situ amorphization of molybdenum oxide dynamically reconstructs the metal–support electronic interface, generating Pt nanoclusters with cooperatively enhanced electronic metal–support interaction and lattice tensile strain. This electronically reconfigured interface simultaneously strengthens chloride adsorption, stabilizes Pt against chloro‐complex dissolution, and promotes early formation of reactive Pt–Cl intermediates. As a result, the amorphous‐interface catalyst achieves nearly 100% chlorine selectivity, an overpotential of only 65 mV at 10 mA cm −2 in seawater, and a mass activity 26‐fold higher than Pt/C. Operando Raman spectroscopy reveals pre‐equilibrium halide activation preceding chlorine evolution, consistent with a Volmer–Tafel mechanism enabled by adjacent electronically coupled Pt sites. These findings establish amorphization‐induced electronic interface engineering as a powerful strategy to simultaneously activate, stabilize, and synergistically accelerate electrocatalytic halogen evolution.

Optimized N-deque partition dual-deque merge string sorting algorithm

Modulating Intermediate Adsorption and Interfacial Water Structure to Unlock the Potential of Nickel for Ammonia Electrosynthesis and Zn‐NO ₃ ⁻ Battery

ABSTRACT Metallic Ni stands out to be a promising electrocatalyst for nitrate reduction reaction (NO 3 RR) to ammonia (NH 3 ), yet is bottlenecked by limited water dissociation kinetics for active hydrogen (*H) supply particularly at low potentials and insufficient adsorption/activation capability toward NO 3 − . We unveil for the first time that NO 3 RR performance of Ni can be activated by synergistic unconventional phase design and alloying engineering. Specifically, anomalous hcp Ni with Cu alloying (NiCu‐hcp) is readily engineered via a facile metal–organic frameworks mediated route. Impressively, the NiCu‐hcp can deliver prominent NO 3 RR performance with record NH 3 yield rate of 2.24 mmol h − 1 cm − 2 and Faradaic efficiency of 98.3% at −0.4 V versus RHE, favorably rivaling the state‐of‐the‐art ones. Moreover, integrating NiCu‐hcp into Zn‐NO 3 − battery delivers eminently high power density of 23.9 mW cm − 2 . From experimental and theoretical studies, unusual hcp phase together with Cu alloying engineering over Ni can regulate interfacial water structure for facilitated dissociation to generate *H, and meanwhile, manipulate electronic state, thereby promoting NO 3 − affinity/activation and lowering Gibbs free energy barrier of the rate‐determining step (*NO→*NOH). This contribution presents a new paradigm to unlock the potential of Ni for NO 3 RR via elegant unusual phase design synergistic with alloying engineering.

Emotion regulation variability and flexibility in daily life show distinct associations with well-being, age, and executive functions

Abstract Flexible and effective emotion regulation (ER) is crucial for mental health and well-being. Research on individual differences in ER, however, has often relied on global self-reports or controlled laboratory settings, which may not fully capture the dynamic and context-dependent nature of regulation in daily life. To address this, we examined how ER variability and flexibility in real-world contexts relate to executive functions (EF), affective well-being, and age in a general population sample ( N  = 161, aged 14–78). EF performance was assessed using six online cognitive tasks, while ER variability and flexibility were assessed using a 14-day ambulatory assessment of daily emotional experiences. As expected, EF performance declined with increasing age across shifting, inhibition, and updating domains. Beyond these age-related differences in cognitive performance, older age was robustly associated with lower within- and between-strategy ER variability. In contrast, ER flexibility remained relatively stable across adulthood. Individual differences in EF were not associated with everyday ER variability, suggesting that cognitive control capacity does not account for regulatory dispersion in daily life. For affective well-being, ER flexibility showed specific, nonlinear associations: within-strategy flexibility based on situational valence and social context demonstrated U-shaped relations with unpleasant mood, suggesting that both low and high context sensitivity may be linked to elevated negative affect. In contrast, flexibility indices were unrelated to between-strategy variability or depressive symptoms. Overall, these findings indicate that adaptive ER cannot be reduced to greater executive control capacity, greater variability, or greater flexibility per se. Instead, they underscore the importance of distinguishing variability from flexibility and highlight that the adaptiveness of ER may depend more on the appropriateness of strategy–context matches than on general patterns of strategy use.

Pre‐Cluster Controlled Assembly of Oriented Mesopores in MOF Crystals

ABSTRACT Directional alignment of mesoporous channels in anisotropic crystals defines an unexplored paradigm, unlocking host‐guest interactions, mass transport, and catalytic functions. Here, we report an in situ pre‐cluster‐controlled assembly strategy to construct hierarchically mesostructured MIL‐53(Al) (HMMIL‐53(Al)) with oriented mesopores precisely matched to crystallographic anisotropy. Pre‐assembly of Al chain clusters lowers the nucleation barrier and guides the crystal growth around the micelles, yielding mesopore walls oriented along the [100] crystallographic axis of MIL‐53(Al). Such orientation exposes adjacent Al‐OH sites spaced by approximately 3.4 Å apart on the inner walls of the mesoporous channels, forming bimetallic active centers. Furthermore, the oriented mesopores allow for continuous tuning of their pore size, and can be integrated into diverse hierarchical architectures, forming ultrathin 2D mesoporous nanosheets (NSs), dendritic dual‐mesoporous spheres, and mesoporous nanoparticles. The orderly arrangement of Al‐OH active sites displays spatial configurations and chemical environments that closely resemble those of the bimetallic catalytic centers in natural nuclease. Compared with bulk MIL‐53(Al) or ultrathin NSs dominated by the exposure of other crystal facets, HMMIL‐53(Al) exhibits efficient nuclease‐mimetic behavior, competently hydrolyzing DNA phosphodiester bonds and degrading extracellular DNA to achieve long‐lasting inhibition of biofilm formation. Mechanistic studies confirm that DNA cleavage over HMMIL‐53(Al) proceeds via a bimetallic cooperative catalytic pathway, analogous to natural nuclease. Overall, this work not only achieves precise control over mesopore size and unique mesostructure but also introduces a new perspective by coupling mesopore orientation with the crystallographic anisotropy of MOFs, thereby unlocking their capabilities inaccessible to traditional mesoporous architectures.

A hybrid intelligent model that performs product evaluation via semantic mining and optimized decision processing

Surface Oxide Species on Metal Cocatalysts Mediate Pathways in Water‐Oxidation‐Coupled CO ₂ Photoreduction: Insights From Pd

ABSTRACT Photocatalytic overall CO 2 reduction using H 2 O as an electron donor is hindered by sluggish reaction kinetics and poorly defined interfacial pathways. Here, we demonstrate that surface oxide species on metal cocatalysts act as intrinsic mediators of the reaction pathway in water‐oxidation‐coupled CO 2 photoreduction. Taking Pd as a model system, we construct a Pd@PdO x cocatalyst on TiN, in which metal Pd is partially encapsulated by spontaneously formed surface PdO x species. This pre‐formed Pd/PdO x interface establishes a bifunctional reaction landscape that spatially coordinates proton management and CO 2 activation. In situ spectroscopic analyses combined with theoretical calculations reveal that PdO x domains preferentially adsorb and activate CO 2 , while adjacent metal Pd sites function as proton reservoirs derived from water oxidation. Directional proton transfer across the Pd/PdO x interface lowers the barrier for *COOH formation, suppresses the competing H 2 evolution reaction, and promotes selective CO release. Under full‐spectrum irradiation, Pd@PdO x /TiN achieves a CO yield rate of 200 µmol g −1 h −1 with 81% selectivity, substantially outperforming the counterparts dominated by either Pd or PdO x . This study highlights surface oxide species as structural determinants of pathway selection and provides mechanistic insights for engineering metal cocatalysts for efficient and selective CO 2 photoreduction.

Redefining bladder sympathetic Innervation with three-dimensional image reconstruction

Dual‐Cation Batteries via Synergistic Cation‐Sieving Electrodes and Tailored Electrolytes

ABSTRACT This study presents a dual‐cation battery enabled by electrolyte engineering and cation‐sieving electrodes. The design leverages the high capacity, low working potential, and stable cycling performance of Li + intercalation in the graphite anode along with the high discharge voltage, fast kinetics, and low cost of K + storage in the K 2 Mn[Fe(CN) 6 ] cathode. The proposed hybrid electrolyte promotes Li + ‐anion aggregations and preferential decomposition, producing a Li‐dominant solid electrolyte interphase that suppresses K + intercalation at the anode. Simultaneously, it reduces the number of highly coordinated K + , lowers the desolvation barrier, and facilitates charge transfer, thus enhancing the K + insertion kinetics at the cathode. As a result, the designed dual‐cation cell delivers an average discharge voltage of 3.80 V, a specific energy of 336.7 Wh kg −1 (based on total mass of graphite and K 2 Mn[Fe(CN) 6 ]), 72.5% of capacity obtained at 20 C discharge rate, and 80% capacity retention after 1200 cycles at 3 C. This synergistic electrolyte‐electrode strategy not only overcomes key challenges in hybrid‐ion battery design but also establishes a mechanistic framework for designing cost‐effective, high‐performance dual‐cation energy storage systems.

Patient safety practices and associated factors among healthcare providers at South Wollo Zone primary hospitals, Northeast Ethiopia, 2025. A facility-based cross-sectional study

Mechanistic Insights Into Protonation of Imine‐Linked Covalent Organic Frameworks: The Correlations With Photocatalytic Processes and High‐Performance Hydrogen Evolution

ABSTRACT Covalent organic frameworks (COFs), especially imine‐linked ones, are promising due to facile synthesis, stability, and tunable electronics. In these COFs, imine N acts as a Lewis basic site, exhibiting variable protonation behavior depending on its interaction with protons. Ascorbic acid is commonly used as a sacrificial electron donor in imine‐COF photocatalysis, and its protonation behavior affects hydrogen production. A full understanding of protonation factors and their impact on performance is lacking, hindering optimal design. In this work, we investigated the protonation mechanisms of imine‐linked COFs using model photocatalysts with varying electron‐donating abilities and steric hindrances. In photocatalytic sacrificial hydrogen evolution, we established correlations between protonation behavior and critical photocatalytic process, including light absorption, hydrophilicity, charge separation efficiency, reaction kinetics. Contrary to reports of strong D–A interactions, we found that weak D–A interaction and a planar imine COF (COF–BTT–H) with significant protonation and preserved planarity deliver the highest performance (50.08 mmol g −1 h −1 ). Guided by these insights, we redesigned a new imine‐linked Pt‐loaded COF catalyst, COF–Py–H, achieving 488.48 mmol g −1 h −1 H 2 evolution with ascorbic acid as sacrificial donor and proton source. This protonation‐focused study broadens COF molecular diversity and highlights the importance of protonation in designing imine‐linked COF catalysts.

Patient-independent hybrid generative-discriminative modeling for seizure detection in long-term scalp EEG

A Polyurea‐Crosslinked Gel Polymer Electrolyte for Solvation and Interphase Regulation in Lithium Metal Batteries

ABSTRACT Polyurea (PUR) electrolytes offer molecular tunability, robust mechanics, and strong Li‐salt affinity for lithium metal batteries, but their application is hindered by poor solubility, uncontrolled polymerization, and unstable Li/electrolyte interfaces. Herein, we report two polyurea‐based polymerizable monomers with distinct functionalities, DPN and MPN , and construct flame‐retardant polyurea gel polymer electrolytes ( P‐DPN and P‐MPN ) through an in situ polymerization strategy. This design simultaneously addresses solubility, electrolyte leakage, and interfacial instability. Mechanistic investigations reveal that the carbonyl groups in the urea moieties coordinate with lithium ion (Li + ) to homogenize lithium deposition, while the –NH groups interact with anions to induce weakly solvated Li + structures, thereby accelerating ion transport. Meanwhile, the low HOMO energy level of the polyurea framework promotes the formation of a robust LiF/Li 3 N‐rich inorganic solid electrolyte interphase (SEI), effectively suppressing parasitic reactions and dendrite growth. As a result, the Li|| P‐MPN ||Li symmetric cell exhibits stable cycling for over 2300 h, and full cells paired with diverse cathodes (including NCM811, LCO, and LFP) exhibit outstanding cycling stability under high cathode loading and even at −20°C. This work establishes a molecular design strategy for in situ polyurea electrolytes and deepens the understanding of solvation/interphase regulation in high‐performance and safe lithium metal batteries.