Browse Articles

Decouple H ₂ O ₂ Electrosynthesis From Microenvironmental Decomposition via Atomic Site Density Engineering

ABSTRACT Electrocatalytic H 2 O 2 production through two‐electron oxygen reduction reaction (2e − ‐ORR) offers a promising route to decentralised chemical synthesis and water purification. However, Faradaic efficiency typically falls short of intrinsic selectivity due to competing H 2 O 2 reduction reaction (HPRR) and disproportionation reaction (HDR). Here, we show that active atomic density engineering governs this microenvironmental loss and can secure the net H 2 O 2 output. Using a series of defect‐rich Co‐N 2 O 2 single‐atom catalysts (SACs), closely spaced sites induce inter‐site electronic coupling and broaden the d‐band, which promotes further reaction with the freshly produced H 2 O 2 toward reduction and disproportionation. Isolating the sites at an optimal Co loading of 0.84 wt.% (Co/NOC‐0.8) effectively suppresses side reactions by increasing the thermodynamic barrier to OH*/O* formation, protecting H 2 O 2 from secondary dissociation. The resulting catalyst reduces secondary H 2 O 2 consumption by up to 79% and closes the gap between intrinsic selectivity (86.5%) and practical Faradaic efficiency (78.7%). When integrated into a flow‐through bilayer electrified membrane reactor, the optimised catalyst combines convection‐enhanced mass transport with rapid product release at the isolated sites, achieving over 90% single‐pass removal of aniline for more than 72 h. These results define a site‐density principle for balancing product formation and product preservation in single‐atom electrocatalysis.

Metallomacrocyclic Ligands Stabilized Icosahedral Superatomic Nanoclusters With NIR‐I to NIR‐II Phosphorescence Modulation

ABSTRACT Coinage metal nanoclusters with near‐infrared‐II (NIR‐II, λ PL > 1000 nm) photoluminescence hold great promise for biological applications. Here, we report the first icosahedral M 13 cluster exhibiting NIR‐II phosphorescence, achieved through an unprecedented metallomacrocyclic ligand coordination combined with an alloying strategy, denoted as M 13 @M 6 clusters. The metallomacrocyclic ligands strongly regulate the photophysical properties of the M 13 core, governing its lowest triplet excited state (T 1 ) and enabling a markedly red‐shifted emission. They also provide a distinctive “core surface→metallomacrocycle→inner core” pathway for stepwise silver doping. Combined theoretical calculations and emission spectra reveal that doping‐induced charge transfer between the M 13 core and M 6 metallomacrocycles drives the photoluminescence shift from the NIR‐I to the NIR‐II region. Furthermore, functionalization of the metallomacrocyclic ligands with bulky pyrene groups enhances NIR‐II emission by an order of magnitude. Catalytic studies demonstrate that site‐specific tuning of metal composition within M 13 @M 6 clusters enables nanometer‐scale modulation of catalytic activity, highlighting the versatility of metallomacrocyclic ligands for regulating both luminescence and catalytic properties. This work not only extends coinage metal cluster protection from conventional organic ligands to metallomacrocycles but also provides a systematic framework for NIR‐II emission modulation through inner‐core and metallomacrocycle doping, ligand engineering at the coordination interface, and outer‐sphere functionalization.

Isotopic Engineering of Water Reactivity for Stable Aqueous Iron‐Metal Batteries

ABSTRACT The development of aqueous iron‐metal batteries (AIBs) is critically hindered by the severe parasitic hydrogen evolution reaction (HER) at the anodes and the resulting structural degradation of the cathode. Moving beyond conventional additive‐based approaches, this work presents a kinetically targeted strategy to suppress HER and enhance overall cell stability through an isotope‐engineered deuterated water (D 2 O)‐based electrolyte. Leveraging the intrinsic differences in zero‐point energy between deuterium and hydrogen, D 2 O features a substantially higher activation energy barrier for water dissociation, effectively taming the reactivity of the problematic Fe anode. Concurrently, control experiments in Fe metal‐free configurations reveal that this isotope effect extends a vital secondary stabilization to the cathode host, establishing a cooperative, dual‐side protection mechanism. Consequently, the D 2 O‐based electrolyte enables a highly reversible iron anode with an average Coulombic efficiency of 99.6% and grants Fe||MoS 2 full cells a stable lifespan of 2000 cycles with an 87.6% capacity retention at 0.5 A g −1 . This work highlights the potential of isotopic modulation as a targeted, high‐efficacy strategy for stabilizing high‐performance aqueous batteries.

Silver‐Catalyzed Vinylogous C(sp ³ )–C(sp ³ ) Coupling of Bicyclo[1.1.0]Butanes With Vinylcarbenes

ABSTRACT Owing to the intrinsically high reactivity of the carbenoid center, the vinylogous reactivity of metallovinylcarbenes—specifically the selective construction of quaternary alkyl–allyl bonds—remains largely underexplored in organic synthesis. We herein describe the first silver‐catalyzed vinylogous C(sp 3 )–C(sp 3 ) cross‐coupling of bicyclo[1.1.0]butanes (BCBs) with in situ‐generated vinylcarbenes from vinyl triftosylhydrazones. This reaction proceeds under mild conditions, furnishing diverse allyl‐substituted cyclobutenes containing a quaternary carbon center with high yields, excellent regioselectivity, and diastereoselectivity. Further derivatization of the cyclobutene derivatives verifies their role as versatile synthetic linchpins for various downstream synthetic operations. Mechanistic studies combined with DFT calculations clarify an unprecedented γ‑addition of BCBs to silver vinylcarbene, followed by a 1,5‐proton transfer pathway, revealing the fundamental basis for the exclusive regio‐ and diastereoselectivity of this transformation.

Electronic‐Geometric Pre‐Compensation Enables Intermetallic RhSb Bimetallenes for Efficient Nitrite Electroreduction

ABSTRACT Sustainable electrochemical synthesis aims to produce high‐value chemicals under mild conditions, but its advancement is hindered by electrocatalyst deactivation caused by the strong adsorption of poisoning intermediates. Strategies that mitigate deactivation by weakening the adsorption of poisoning intermediates are constrained by the linear scaling relationships of adsorption energies, which simultaneously reduce the binding of other key reactive species, leading to insufficient catalytic performance or demanding reaction conditions. In this study, we propose and validate a pre‐compensation strategy between electronic structure and geometric structure specifically toward Rh active sites to mitigate *NO poisoning in the nitrite electroreduction reaction (NO 2 ERR). In the fabricated intermetallic RhSb bimetallenes (RhSb IMMs), Sb boosts the adsorption capacity of Rh toward reactants by modulating the electronic structure, compensating for the geometrically constrained weak adsorption configuration imposed by the ordered alloy structure. Consequently, RhSb IMMs operate stably for over 880 h with an outstanding Faradaic efficiency of over 90% at −0.3 V (vs. RHE) and achieve an average ammonia (NH 3 ) yield rate of 107.5 g h −1 g cat −1 for NO 2 ERR at a current density exceeding 0.45 A cm −2 . This compensation strategy provides a rational design principle for reconciling fundamental trade‐offs in catalysis and beyond.

Dynamic Bifunctional Sites on a COF Enable Efficient Immobilization and Conversion of Iodine Species Toward Li‐Iodine Batteries

ABSTRACT The thermodynamic instability of iodine cation (I + ) and shuttle effect of polyiodide in the two‐electron Li‐iodine (Li‐I 2 ) batteries remain an unresolved bottleneck. The design and preparation of an advanced cathode capable of effectively anchoring and activating iodine species is a desirable but highly challenging target to overcome these issues. In this study, we strategically synthesized a pyridine‐functionalized COF (BPY‐COF‐HI) cathode that enables highly reversible multivalent transition of iodine (I − /I 0 /I + ) within Li‐I 2 batteries. The pyridine sites reversibly switch between protonated state (NH + ) and neutral state (N), allowing them to anchor I 3 − via electrostatic interactions and activate I + via halogen bonding, respectively. Benefiting from this dynamic bifunctional regulation driven by the single pyridine site, a carbon‐nanotube‐integrated composite cathode (BPY‐COF@CNT‐HI) delivers a high‐voltage discharge plateau at 3.58 V corresponding to the reversible I + /I 0 redox and achieves a gravimetric energy density of 642 Wh kg I −1 at 0.3 A g −1 . Remarkably, the cathode maintains ultralong cycling stability over 8000 cycles at 2.0 A g −1 with an exceptionally low capacity fade of 0.0055% per cycle. This result widens perspectives for designing high‐performance cathodes for Li‐I 2 batteries with two‐electron redox chemistry.

Correction: Dietary cauliflower (Brassica oleracea var. botrytis) mitigates benzo[a]pyrene-induced oxidative stress, immune dysfunction, and tissue damage in Nile tilapia

Local Antiaromaticity‐Mediated Chiral Donor–Acceptor Strategy for Efficient Circularly Polarized Luminescence

ABSTRACT Achieving highly efficient circularly polarized luminescence in organic light‐emitting diodes remains a fundamental challenge, because conventional chiral‐perturbation strategies are intrinsically limited by weak electronic coupling between chiral units and the emissive center. To address this limitation, a local antiaromaticity‐mediated chiral donor‐acceptor strategy is introduced. By integrating a locally antiaromatic chiral donor with one or two electron‐accepting triazine units, donor–acceptor and acceptor–donor–acceptor architectures are constructed that exhibit hybridized local and charge‐transfer excited states and enable hot‐exciton channels. Unlike conventional designs, the antiaromatic chiral donor directly contributes to the frontier molecular orbitals and excited‐state spin density distribution, inducing pronounced helical charge redistribution at the emissive center during charge‐transfer excitation. The localized antiaromatic character further strengthens the magnetic transition dipole moment, providing a synergistic amplification of circularly polarized emission. As a result, the optimized emitter ABH‐2TRZ affords deep‐blue circularly polarized electroluminescence with a dissymmetry factor of +7.4 × 10 −3 , a maximum external quantum efficiency of 6.38%, and color coordinates of (0.154, 0.089), close to the deep‐blue display standard. This work establishes antiaromatic chiral donors as an effective platform for high‐performance circularly polarized optoelectronic materials.

Focused ultrasound stimulation of the centromedial amygdala disrupts facial emotion recognition via reduced amygdala–insula connectivity

Light‐Induced Electron‐Rich Gold Directs Nitrate Reduction to Dinitrogen

ABSTRACT Electrocatalytic nitrate reduction reaction (NO 3 RR) provides a controllable route for nitrate conversion, while nitrate purification requires directing the reaction endpoint toward inert N 2 instead of soluble reactive nitrogen species. Here, we establish operating‐state electron enrichment as a design principle for directing NO 3 RR toward N 2 and construct a Cu‐induced electronically reconfigured Au (ER‐Au) interface that enters an electron‐rich state under illumination. Electrochemical in situ interfacial characterization and theoretical calculations show that this electron‐rich environment transforms *NO‐related intermediates from isolated adsorption states into N‐N coupling reactive configurations, selectively enabling the NO 3 − to N 2 branch. Consistent with this branch regulation mechanism, ER‐Au selectively converts NO 3 − to N 2 with 90.84% Faradaic efficiency at pH = 1, as confirmed by product analysis and isotope‐labeling experiments, and further maintains stable operation for 100 h under illuminated acidic NO 3 RR conditions. The high N 2 Faradaic efficiency shows competitive performance among representative NO 3 RR electrocatalysts reported in the literature, especially considering the challenge of directing nitrate reduction toward the inert N 2 endpoint. More broadly, these findings identify operating‐state electron enrichment as a key mechanism and design principle for endpoint‐selective NO 3 RR.

High-frequency induction heat sintering of 316L stainless steel: a systematic investigation of ultra-low-pressure processing, microstructure, and corrosion performance

Abstract The present work provides a systematic evaluation of direct pressure-assisted High-Frequency Induction Heat Sintering (HFIHS) of gas-atomized 316 L stainless steel powder at 40 MPa, approximately 50 kHz, 1000–1150 °C, a 5 min hold, and approximately 1 × 10⁻³ Torr. Relative density, Vickers hardness, maximum compressive stress, microstructure, and corrosion behavior in 3.5 wt% NaCl were evaluated. Relative density increased from 88.87% at 1000 °C to 98.61% at 1150 °C. Hardness measurements increased from 156.5 ± 5.2 HV10 to 263.0 ± 14.4 HV10, while the measured maximum compressive stress increased from 284 to 379 MPa. Fiji-based image analysis showed decreasing pore-area fraction, pore size, and pore connectivity, together with increasing pore circularity and grain size. The lowest polarization-derived corrosion rate was obtained at 1100 °C, whereas the 1150 °C specimen had the highest density and a comparatively clean post-corrosion surface. Within the investigated conditions, the results indicate that direct HFIHS can consolidate 316 L stainless steel to near-full density within a short processing cycle and at substantially lower applied pressure than the conventional press-and-sinter baseline used for comparison.

Induced‐Fit for Oxygen Adsorption: Flexible Conjugated Microporous Polymers With Self‐Adaptive Active Sites for H ₂ O ₂ Photosynthesis

ABSTRACT Photocatalytic hydrogen peroxide (H 2 O 2 ) synthesis via oxygen reduction reaction (ORR) offers a sustainable alternative to energy‐intensive anthraquinone processes. However, its efficiency is hindered by poor selectivity and instability stemming from reactive superoxide intermediates through the two‐step two‐electron (2e − ) route. Herein, inspired by the “induced‐fit” mechanism of enzymes, a strategy of self‐adaptive active sites modulation using flexible conjugated polymers engineered with nonplanar linking units was proposed. The flexible conjugated microporous polymers facilitated a transition of O 2 adsorption from Pauling‐type to Yeager‐type. Among the designed polymers, CMP‐B4, which was constructed from 4,4′‐position‐coupled bipyridine units, exhibited optimal geometric matching capability for O 2 activation. Specifically, upon the approach of O 2 , the interaction between the lone‐pair electrons of nitrogen atoms in flexible bipyridine unit and π* orbitals of O 2 induced a dihedral rotation (e.g., approximately 10° in CMP‐B4), playing a key role in promoting the one‐step 2e − ORR pathway, thus overcoming the limitations of poor adaptability to diverse O 2 adsorption modes and restricted versatility of dual‐nitrogen units in the rigid nitrogen‐rich polymers. Such configuration of CMP‐B4 suppressed the formation of *OOH intermediates and achieved an excellent photocatalytic H 2 O 2 production rate of 6.21 mmol g −1 h −1 under continuous‐flow photocatalytic conditions over 24 h.

Pediatric intestinal enteroids derived from very early onset inflammatory bowel disease reveal differences in growth, morphology, and barrier function

Enhancing the Versatility of Polyethylene Terephthalate (PET) Through Strategic Biomolecular Functionalization

ABSTRACT As biocatalytic strategies for PET recycling reach maturation, insights gained from PET hydrolase research can be leveraged to inform the design of proteins and surface‐functionalization strategies that promote stable association of functional proteins with PET surfaces, enabling the development of functional protein‐plastic hybrid materials. Herein, we examine recent developments in biofunctionalization strategies of PET and related materials, with a focus on chemical biology approaches that offer more precise control of the orientation of proteins on PET and related materials. Biophysical insights from protein‐polymer interface chemistry studies can inform protein selection, design, and engineering approaches to minimize denaturation and maximize function of proteins upon attachment to surfaces. Finally, we highlight applications of protein‐functionalized PET and related synthetic polymers, including for biomedical applications and scalable biocatalysis, showcasing the potential of integrating biological activity into durable synthetic polymers.

Effectiveness of nicotine gum for intervention and role of behavior counselling for smokeless tobacco cessation in adults in a dental setting: A randomized control trial

Tandem Catalysis for pH‐Universal Hydrogen Oxidation in Fuel Cells

ABSTRACT Minimizing platinum‐group metal (PGM) usage in anion‐exchange membrane fuel cells (AEMFCs) and proton‐exchange membrane fuel cells (PEMFCs) is essential for cost reduction. However, achieving power densities exceeding 1 W cm −2 requires high PGM loadings at the anode, particularly in AEMFCs (>0.1 mg cm −2 ), to sustain hydrogen oxidation reaction (HOR) kinetics. Nickel‐based catalysts offer a low‐cost alternative but are typically limited by poor activity and oxidative instability. Here, we address these limitations by developing a core–shell nanoreactor comprising Ni nanoparticles (NPs) encapsulated by N‐doped graphitic carbon (NC) that is embedded with atomic Ru and Ni species. With an ultralow Ru loading of 1 µg cm −2 , anodes using this catalyst deliver peak power densities of 2.36 and 3.26 W cm −2 in AEMFC and PEMFC, respectively, with negligible structure change after 200 h of continuous operation at 1 A cm −2 in both devices. Mechanistic studies in alkaline media reveal a tandem catalytic pathway in which NPs shielded from the electrolyte dissociate H 2 to H*, and adjacent atomic metal species enable H* spillover across the NC shell to react with surface‐anchored OH*. This work provides a general strategy for designing tandem electrocatalysts for multi‐step catalytic processes.

Pupil size as an early and accessible biomarker of memory performance: a comparative intracranial EEG study

Abstract Noninvasive and real-time methods for tracking the neural dynamics of memory processing remain limited. Here, we tested whether fluctuations in pupil size were associated with trial-to-trial variations in memory performance and how their temporal and discriminative properties compared with intracranial EEG (iEEG) signals. Seven epilepsy patients implanted with electrodes for seizure monitoring performed a free-recall verbal memory task while pupillometry and iEEG signals were recorded simultaneously. Trials were categorized as good or poor based on immediate recall performance, revealing pupil responses that differentiated the trial type  600 ms before word presentation and  200 ms before recall vocalization. These effects showed broadly comparable timing, discriminative strength, and classification performance to simplified iEEG power-in-band features obtained from multiple cortical regions and frequency bands. Our results suggest using pupil dynamics as an accessible biomarker of immediate memory performance in research, clinical and other applications.

Outside Front Cover: Chelation Drives Surface Substitution in Hybrid‐MXenes

Bayesian-optimized explainable boosting models for compressive strength of non-circular LRS-FRP-confined concrete

Abstract Large rupture strain fiber-reinforced polymer (LRS-FRP)-confined concretes are increasingly used in safety–critical infrastructure due to their high ductility and load-carrying capacity; however, accurate prediction of compressive strength (CS) in non-circular sections remains challenging due to non-uniform confinement induced by geometric irregularities, which limits the reliability of existing empirical models and design codes developed mainly for circular sections. To address this limitation, this study develops a reliability-oriented, data-driven framework that combines Bayesian-optimized ensemble machine learning, model interpretability, and uncertainty quantification. Six algorithms including random forest (RF), extremely randomized trees (ERT), extreme gradient boosting (XGBoost), histogram based gradient boosting (HistGBM), light gradient boosting machine (LightGBM) and categorical boosting (CatBoost) were trained using an experimental database of 174 non-circular LRS-FRP-confined concrete specimens. Model interpretability was achieved using Shapley additive explanations (SHAP), while predictive reliability was systematically evaluated through uncertainty-aware performance assessment. All models demonstrated strong generalization, with testing coefficients of determination (R 2 ) ranging from approximately 0.96–0.99, and boosting-based methods consistently outperforming bagging approaches. CatBoost (testing R 2  ≈ 0.985) exhibited the best overall performance, the lowest prediction errors, and the most reliable uncertainty estimates. Accordingly, the overall performance ranking was identified as CatBoost > HistGBM > XGBoost > ERT > LightGBM > RF. The results clearly indicate that high predictive accuracy alone is insufficient for reliable modeling of non-circular LRS-FRP-confined concrete and that uncertainty-aware evaluation is essential. SHAP-based analysis yielded physically consistent insights, identifying LRS-FRP thickness, unconfined concrete strength, and section corner radius as the dominant contributors to CS, while highlighting the critical role of post-transition LRS-FRP stiffness in sustaining effective confinement. Overall, the proposed framework offers an interpretable and reliability-aware alternative to conventional models and provides a robust predictive tool for engineering design and assessment of non-circular LRS-FRP-confined concrete.

Synergy Between Photon‐to‐Phonon Pathway and Active Lattice Oxygen Enables Efficient and Stable Syngas Synthesis

ABSTRACT Light‐driven dry reforming of methane (DRM) offers a promising route for syngas synthesis while simultaneously mitigating greenhouse gas emissions of CO 2 and CH 4 . However, the attractive mild‐temperature operating window imposes kinetic constraints on C─H/C═O activation and promotes thermodynamic tendencies for coke formation, resulting in limited efficiency and stability. Herein, manganese oxide (MnO x ) is employed as a multifunctional support to integrate the classic Rh catalytic center, establishing a new benchmark photothermo catalyst for DRM. The system achieves record‐high syngas production rates (H 2 : 948 mmol g −1 h −1 ; CO: 992 mmol g −1 h −1 ) without external heating, alongside exceptional long‐term stability (∼500 h). These production rates and stability also surpass conventional thermocatalysts in similar temperature ranges, with stability exceeding most thermocatalysts by an order of magnitude. Under a separate low‐conversion, high‐gas hourly space velocity (GHSV) protocol, a light‐to‐chemical efficiency (29.5%) can also be reached. MnO x functions as a broadband light harvester, generating a localized thermal field at the micrometre‐scale via an efficient photon‐to‐phonon pathway to facilitate C─H bond activation on Rh. Concurrently, its active lattice oxygen enables a dynamic O L ‐O V cycle for timely removal of C* intermediates and C═O activation. This work underscores the critical role of support engineering in advancing light‐driven DRM.