Browse Articles

Optimization of speech emotion recognition using hybrid dataset integration and deep learning-based feature fusion with a novel balanced focal entropy loss

Temporal predictions shape somatosensory perception

Abstract Although intensity expectations have been thoroughly studied in relation to pain, there has been a notable lack of investigation into temporal expectations. One important temporal pain effect, the so-called dread effect, suggests that future pain becomes more aversive with increasing delay. Here we investigated temporal expectations including the dread effect by presenting probabilistically cued painful heat and non-painful cold stimuli after different delay periods. Actual stimulus latency had no effect on perceived intensity in both non-painful cold and painful heat conditions. However, our data clearly show that the expectation of longer delays amplified somatosensory perception, indicating that the dread effect is related to expected and not to experienced delay. Electroencephalography data show that temporal expectations modulate alpha/beta activity during cue presentation, but not during stimulation. Actual stimulus timing is represented in alpha-to-beta frequencies during heat and cold stimulation.

Single-cell insights: Mosquito Toll activation enhances granulocyte differentiation and immune surveillance via Notch suppression

Activation of the Toll, Immunodeficiency (IMD), Jun-kinase (JNK), and Signal Transducer and Activator of Transcription (STAT) innate immune signaling pathways limits Plasmodium infection in Anopheles gambiae . Hemocytes (mosquito immune cells) restrict malaria transmission by eliminating Plasmodium parasites through complement-mediated lysis and phagocytosis. However, the mechanisms underlying mosquito hemocyte lineage determination and maturation remain poorly understood. Here, we used single-cell transcriptomics to investigate how these immune signaling pathways regulate hemocyte differentiation and function. Analysis of 37,529 hemocytes revealed oenocytoid and granulocyte subpopulations not previously described that express specific molecular markers, as well as the expansion of selective subpopulations by different signaling pathways. Toll and JNK activation trigger terminal differentiation of granulocytes (phagocytic cells) with a dramatic increase in megacytes and reduce oenocytoids by transcriptionally suppressing Notch signaling. Toll activation strongly affects gene expression in most hemocyte clusters, whereas STAT and IMD activation impact only specific clusters. Moreover, Toll activation induces the expression of extracellular matrix-interacting genes in megacytes, enhancing midgut immune surveillance. Collectively, these findings uncover how immune signaling modulates hemocyte differentiation and function in a medically relevant mosquito species, providing insights into the mechanism by which hemocytes hinder Plasmodium infection.

Nonlinear dynamics and control of a 3-echelon chaotic supply chain system having two stable equilibrium points

Abstract This research work introduces a novel 3-echelon chaotic supply chain model incorporating a sinusoidal nonlinearity to represent modeling uncertainty, extending the Anne supply chain model. Through analytical calculations, we show that the new model exhibits chaotic behavior, verified by Lyapunov exponents and Kaplan–Yorke dimension. The largest Lyapunov value of the new model is 1.8336, which is higher than the existing Anne supply chain model. Interestingly, the proposed model has one unstable and two stable equilibrium points, which is rare in the literature. The dynamical analysis is carried out using classical nonlinear tools such as bifurcation plots and Lyapunov exponent spectra. Additionally, the multistability phenomenon is observed in the new model through bifurcation analysis and attractor plots. Finally, 1D and 2D offset boosting control schemes are applied to regulate the position of the attractor without affecting the chaotic dynamics of the system. In future research, these control strategies can be leveraged to optimize resource allocation and waste reduction, thereby enhancing the long-term sustainability of complex supply chain networks.

SpiR is a gut microbial enzyme that drives cholesterol conversion

Abstract The gut microbiota contributes to cholesterol homeostasis by converting cholesterol into coprostanol, a non-absorbable sterol excreted in the feces. However, the enzymes mediating this process remain poorly defined. Here, we identify spiR , a steroid Δ 5-4 isomerase/3-keto reductase from Eubacterium coprostanoligenes that catalyzes the initial oxidation of cholesterol to cholestenone, a requisite step in coprostanol production. We confirm that SpiR oxidizes both cholesterol and pregnenolone, and stereospecifically reduces 3-keto-steroids to 3β-hydroxylated forms. We show that SpiR preferentially binds to cholesterol over related steroids and functions as an NAD(H)-dependent homodimer. Through phylogenetic analysis, we show that spiR clusters with known Δ 5-4 isomerases and is restricted to an uncultured clade within Acutalibacteraceae, where it frequently co-occurs with species encoding ismA , a gene previously implicated in cholesterol conversion. We analyze a multi-omic dataset from three human cohorts and find that spiR homologs were strongly enriched in individuals exhibiting cholesterol conversion. We also show that spiR homologs have a greater predictive power for cholesterol conversion than ismA homologs, establishing them as superior markers of microbial cholesterol metabolism. Our findings refine the enzymatic model of cholesterol metabolism in the gut and establish spiR as a critical biomarker and mechanistic driver for microbiome-mediated cholesterol reduction.

Toward the simultaneous detection of multiple diseases with a highly cost-effective cell-free DNA methylome test

Plasma cell-free DNA (cfDNA), originating from multiple organs, holds significant potential for noninvasive diagnostics and prognostics. Current cfDNA methylation assays primarily focus on single clinical indications by targeting specific genomic loci. In contrast, comprehensive profiling of cfDNA methylome can enable simultaneous detection of multiple diseases by capturing organ-specific methylation signatures, thereby offering a holistic view of health, when disease etiology is unclear or when conventional biochemical diagnostics are unavailable. However, deep sequencing required for sensitive detection of methylation abnormalities remains prohibitively expensive, limiting widespread clinical use. To overcome this barrier, we developed MethylScan , a highly cost-effective approach for cfDNA methylome sequencing. We demonstrated its broad clinical utility in a cohort of 1,061 individuals across diverse applications, including multicancer detection in general population, liver cancer surveillance in high-risk individuals, liver disease classification, identification of organ abnormalities, and race prediction from cfDNA. In multicancer detection (liver, lung, ovarian, and stomach cancers), MethylScan achieved an area under the receiver operating characteristic curve (AUROC) of 0.938 (95% CI: 0.920 to 0.954), with a sensitivity of 63.3% (95% CI: 58.9 to 67.9%) at 98.0% specificity for all cancer stages. For early-stage cancers, the AUROC was 0.916 (95% CI: 0.890 to 0.940), with 55.3% sensitivity (95% CI: 49.1 to 62.1%) at the same specificity. In liver cancer surveillance, MethylScan achieved an AUROC of 0.927 (95% CI: 0.889 to 0.959), with 79.6% sensitivity (95% CI: 70.6 to 87.8%) at 90.4% specificity. The assay also demonstrated strong performance in additional diagnostic tasks, supporting its potential as a versatile platform for comprehensive cfDNA-based health monitoring.

Circulating pro-angiogenic cells are preserved despite myocardial angiogenic signal deficits in HFpEF model

Abstract Heart failure with preserved ejection fraction (HFpEF) has no cure, and microvascular dysfunction is a major contributing factor to its pathophysiology. Circulating endothelial progenitor cells (EPCs) and Angiogenic T (i.e., Tang) cells which support vascular repair are deficient in clinical HFpEF. The lack of data on circulating EPC and Tang cell counts in HFpEF models is an unmet critical gap in knowledge for potential therapeutic and biomarker development for HFpEF. In the clinically relevant HFpEF model (i.e., ZSF-1 obese rats), we hypothesized that circulating EPCs and Tang cell counts are significantly decreased compared to healthy control (WKY) rats. Thirty-eight-week-old male ZSF-1 obese and WKY rats were subjected to comprehensive phenotyping protocol, including echocardiography, exercise tolerance, aortic pressure measurement, and left ventricular diastolic function assessment. Blood was analyzed by flow cytometry for early (CD146⁺/CD34⁺/CD133⁺) and late (CD34⁺/CD146⁺) EPCs, as well as Tang cells (CD3⁺/CXCR4⁺/CD31⁺). Left ventricular expression of angiogenic genes (SDF1α, VEGFα) and pro-inflammatory IL-1β gene was quantified. ZSF-1 obese rats exhibited severe HFpEF phenotype with impaired diastolic function, elevated filling pressures, and significant exercise intolerance. Contrary to our expectations, circulating EPC and Tang cell counts in ZSF-1 obese rats are comparable to those of WKY rats whereas myocardial expression of SDF-1α and VEGF-α were markedly reduced and IL-1β gene increased. These findings suggest a novel dissociation between circulating and tissue angiogenic profiles in HFpEF. Preserved circulating pro-angiogenic cells despite myocardial angiogenic deficits suggests angiogenic dissociation as a potential mechanism underlying microvascular dysfunction in HFpEF. While ZSF-1 lean rats would have been the ideal control instead of WKY, targeting myocardial angiogenic pathways in HFpEF may represent a promising therapeutic strategy.

Unexpected detection of Mycobacterium tuberculosis DNA in US-born patients in putative association with clinical syndromes

Spider venom phospholipase D toxin structure: Interfacial binding site, mechanism, activation, and head group preference

Envenomation by sicariid spiders such as the brown recluse can cause loxoscelism, a syndrome involving localized dermonecrosis and/or systemic effects like hemolysis. The causative venom toxins are unusual interfacial phospholipase D enzymes that cyclize sphingolipid and lysophospholipid substrates when bound to membrane surfaces. Crystal structures of several of these toxins have been reported, but none of them directly illuminates how lipids bind in the active site and at the interfacial binding site (IBS); indeed, as a general rule the lipid interfaces of peripheral membrane proteins resist crystallographic determination. Here, however, we report X-ray crystal structures at 1.85 to 2.6 Å resolution of a venom toxin from the Chilean six-eyed sand spider Sicarius levii (terrosus) bound to a micelle-like agglomeration of product and substrate sphingolipids. Each enzyme subunit binds three sphingolipid molecules, one in the active site and two at adjacent noncatalytic sites, generating an interface that approximates the IBS predicted by molecular dynamics. The conformations of substrate and cyclic product in the active site definitively confirm our previously proposed catalytic mechanism. Comparisons with lipid-free structures show conformational changes in two loops that suggest a mechanism for allosteric/surface activation. Docking studies suggest that the variable preference of these toxins for phosphocholine and phosphoethanolamine head groups involves subtle changes in size and shape of the active-site pocket. The structures reveal key facets of the molecular basis of loxoscelism and show that in favorable cases crystallography can illuminate the IBS of peripheral membrane proteins.

Boosting Dehydration via Coupling With the Water‐Gas Shift Reaction

ABSTRACT To address the challenge of removing water from dehydration reactions when reaction components share similar physical properties with water, we developed a reaction coupling strategy that integrates dehydration with the water‐gas shift (WGS) which was enabled by the Pt/hydrophobically modified Al‐SBA catalyst (Pt/Al‐SBA‐C 12 ). Through quasi in situ characterizations and molecular dynamics simulations, the dynamic evolution process of water generation, transport, and activation has been elucidated. At the Lewis acid sites on the hydrophobic SBA surface, lactic acid, and alcohol molecules react to form esters and water. Subsequently, driven by the wettability gradient, water molecules undergo directional transport from the SBA surface to the Pt sites within 7.5 ns, accompanied by the induction of contact electrification. The dissociated * OH over Pt sites further reacts with adsorbed CO to form an * COOH intermediate, ultimately producing CO 2 and H 2 . Leveraging this system, the Pt/Al‐SBA‐C 12 catalyst achieves a lactic acid conversion of 96.1% in the coupled reaction, substantially higher than the 52.3% attained by unmodified Pt/Al‐SBA under standalone esterification conditions. Moreover, the Pt/Al‐SBA‐C 12 catalyst maintains stable performance over at least 10 cycles. With broad substrate applicability, our approach enables water removal without relying on differences in physical properties, showing great potential for practical applications.

Ion‐Exchange and Energy‐Stress Strategies Amplified Dual‐Site Nanozyme‐Mediated Ferroptosis/Pyroptosis Inhibition for Neuroprotection

ABSTRACT Early neuroprotection is crucial for improving the prognosis of secondary injury after intracerebral hemorrhage (ICH). Herein, this work developed an intelligent blood–brain barrier (BBB)‐permeable dual‐site nanozyme (TCZM@EcN) prepared by tannic acid (TA) etching to block microglial ferroptosis and pyroptosis for neuroprotection. TCZM@EcN specifically chelated Fe 2+ in the ICH region through an ion‐exchange strategy and obtained higher anti‐oxidant property in situ, as well as released Zn 2+ to upregulate glutathione peroxidase 4 (GPx4) expression for reinforced ferroptosis inhibition. Metformin (Met) hindered fatty acids biosynthesis via an energy‐stress strategy, protecting cells from ferroptosis at the source of lipid metabolic pathway. Moreover, ATP inhibition of Met and the chelating nature of TA synergically reduced cell free DNA (cfDNA) content to suppress pyroptosis. Finally, the coating of Escherichia coli Nissle 1917 (EcN)‐derived double‐layered membrane vesicles (DMVs) with inflammatory inhibitory effect assisted TCZM@EcN hitchhiking neutrophils to cross the BBB and enrich in the ICH region rapidly for more locally efficient oxidative stress reduction and neuroinflammation alleviation. This study confirmed the feasibility and prominent synergistic effects of dual‐site nanozyme‐induced ion‐exchange and energy‐stress strategies, which enabled dual inhibition of microglial ferroptosis/pyroptosis for neuroprotection against ICH‐induced secondary injury.

Mechanochemical H‐Bonding Organocatalysis Enabled Controlled Synthesis and Recycling of High‐Molecular‐Weight Poly(ɛ‐Caprolactone)

ABSTRACT The use of organocatalysts for the ring‐opening polymerization (ROP) to achieve high‐molecular‐weight poly(ε‐caprolactone) (PCL) remains challenging. In this study, we present a mechanochemical hydrogen‐bond‐catalyzed ROP (mechano‐HROP) strategy. This approach combines a tris‐urea/base co‐catalysis together with ball milling to achieve rapid and controlled solid‐state polymerization of ɛ‐caprolactone (ɛ‐CL) at room temperature. The mechano‐HROP demonstrated exceptional polymerization activity ( k obs = 0.053 min −1 ) while suppressing transesterification reactions compared to conventional bulk ROP. This method enabled the complete conversion of monomers into high‐molecular‐weight PCLs with M n up to 185.0 kDa and narrow distribution ( Ð < 1.28). The PCL synthesized via mechano‐HROP exhibited high chain‐end fidelity, as evidenced by MALDI‐TOF analysis and successful chain extension from its active chain ends. Density functional theory calculations confirmed the presence of an intramolecular hydrogen‐bonding self‐activated imidate species under solvent‐free condition. Furthermore, we introduced a mechanochemical methanolysis method for PCL recycling under solvent‐free and room temperature conditions. Kinetic comparisons with stirred methanolysis highlight the efficiency of mechanochemistry in PCL depolymerization. In summary, this work establishes a highly efficient mechanochemical route for the synthesis and recycling of high‐molecular‐weight PCLs.

Overcoming the Bandgap‐Birefringence Trade‐Off: Proton‐Transfer Engineering of High‐Performance Ultraviolet‐Transparent Organic Crystal

ABSTRACT Birefringent crystals are key materials for controlling the polarization state of light, and breakthroughs in their performance are crucial for advanced optical devices. In this study, π‐conjugated groups [C 7 N 2 H 11 ] + and [C 5 N 4 H] − with high polarizability anisotropy (Δα), are constructed via a proton transfer strategy. The Δα of these groups is significantly higher than that of the corresponding neutral molecules. Based on this design, two centimeter‐sized crystals are successfully prepared: [(C 7 N 2 H 11 ) + (C 5 N 4 H) − ]·C 7 N 2 H 10 ·H 2 O (birefringence Δ n = 0.233 @ 546 nm, band gap 3.66 eV) and [(C 7 N 2 H 11 ) + (C 5 N 4 H) − ]·H 2 O (birefringence Δ n = 0.629 @ 546 nm, band gap 3.79 eV). [(C 7 N 2 H 11 ) + (C 5 N 4 H) − ]·H 2 O exhibits the highest birefringence among organic crystals with a wide band gap (> 3.0 eV). Structural analysis and theoretical calculations indicate that the inherently high Δα of [C 7 N 2 H 11 ] + and [C 5 N 4 H] − , combined with relatively small intermolecular dihedral angles between adjacent functional groups in the crystal, contribute synergistically to the excellent birefringence properties. Additionally, [C 5 N 4 H] − stabilizes water molecules through hydrogen‐bond networks, enhancing the material's air stability. This work provides a new strategy for designing high‐performance birefringent crystals based on proton transfer and π‐conjugated groups with high polarizability anisotropy.

Sulfur‐Modulated Fully‐Conjugated Self‐Assembled Monolayers for Synergistic Dual‐Interface Optimization in Inverted Perovskite Solar Cells

ABSTRACT To achieve high efficiency and stability in inverted perovskite solar cells (PSCs), it is essential to ensure uniform self‐assembled monolayers (SAM) coverage on the substrate and to passivate defects effectively at the buried interface of perovskite. Herein, two sulfur‐modulated fully‐conjugated SAMs, 4‐(bis(4‐methylthiophenyl)amino)phenylphosphonic acid (SMe‐TPA‐PA) and 5‐(4‐bis(4‐methylthiophenyl)amino)phenyl) thiophenylphosphonic acid (SMe‐TPA‐ThPA) are developed for inverted PSCs by employing substituent regulation and linker adjustment. The incorporation of methylthio substituents in both SAMs enhances their defect‐passivation capability at the interface. Moreover, the thiophene linker in SMe‐TPA‐ThPA strengthens intermolecular interactions, improves energy level alignment with the perovskite, enables stable and uniform molecular coverage on ITO, and facilitates efficient hole extraction. As a result of synergistic dual‐interface modification of the ITO/perovskite system, inverted PSCs based on SMe‐TPA‐ThPA and SMe‐TPA‐PA achieve significantly improved power conversion efficiencies (PCEs) of 26.52% and 25.40%, respectively, surpassing the control device based on methoxyl‐substituted SAM (OMe‐TPA‐PA, 24.31%). Remarkably, devices incorporating SMe‐TPA‐ThPA also exhibit exceptional operational stability, retaining 91.8% of their initial PCE after 1700 h of continuous light soaking and 91.2% after 1700 h of continuous thermal aging at 65 °C.

Directed Amorphous‐to‐Amorphous Reconstruction Toward Efficient Oxygen Evolution

ABSTRACT To fully unlock catalytic potential in the oxygen evolution reaction (OER), it is essential to guide the reconstruction process, orienting the evolution from the initial amorphous state into a more potent amorphous structure. We develop an amorphous cobalt coordination polymer (aCo) pre‐catalyst via monodentate end‐capping. In‐situ synchrotron radiation X‐ray diffraction reveals that CH 3 CN coordination disrupts the long‐range topological order while preserving local motifs. The obtained metastable amorphous structure redirect spontaneous surface reconstruction into an amorphous cobalt oxyhydroxide (a‐CoOOH) active layer due to strong d–π* interactions with the lower energetic barrier (−8.175 eV) compared to the crystalline phase on its counterpart (−7.441 eV). The unique amorphous‐to‐amorphous transformation effectively activates lattice oxygen within the metastable framework, switching the OER pathways from the adsorbate evolution mechanism to a lattice oxygen‐mediated mechanism and consequently enhancing OER efficiency and stability. The optimized amorphous aCo can achieve an overpotential of 186 mV at 10 mA cm −2 , much lower than those of RuO 2 (233 mV) and crystalline cCo (308 mV), and it demonstrates stability of over 100 h at 2 A cm −2 . This strategy offers a directed surface‐induced approach for designing next‐generation OER electrocatalysts, providing fundamental insights into the correlation between lattice oxygen activity and structural long‐range disorder.

Dynamic Covalent Chemistry in Systematic Construction of Hydrogen‐Bonded Organic Frameworks

ABSTRACT Dynamic covalent chemistry (DCC), which enables error correction during the reversible covalent reaction process, presents an efficient approach for the design of crystalline porous materials with different topologies and pore structures. However, the application of DCC in the systematic construction of hydrogen‐bonded organic frameworks (HOFs) remains largely underexplored. Herein, we introduce a DCC approach for the direct and efficient synthesis of single‐crystal HOFs (termed as DCC‐HOFs) with gram‐scale products. Specifically, through a one‐pot Schiff base reaction of pyrazole amine and aromatic aldehyde precursors affords two types of DCC‐HOFs, including four [3+3] two‐dimensional (2D) DCC‐HOFs and two robust highly porous isoreticular [4+4] three‐dimensional (3D) DCC‐HOFs via pyrazole N─H···N hydrogen‐bonding trimers and tetramers, respectively. Furthermore, we demonstrate that the robust, high porous 3D DCC‐HOF‐Si with a pore size of up to ∼0.8 nm, can serve as an efficient drug carrier. This work provides a simple solution for the scalable fabrication of functional HOFs for a wide range of applications.

Oxyphilic Ru‐O‐Mn ²⁺ Interfaces on Ru/MnO Catalysts: Unprecedented Activity for Low‐Temperature CO ₂ Methanation

ABSTRACT Catalytic CO 2 methanation using renewable H 2 presents a promising strategy for carbon neutrality and renewable energy storage, yet achieving high efficiency at low temperatures remains a formidable challenge. Herein, we report a Ru/MnO catalyst featuring in situ constructed highly oxyphilic Ru–O–Mn 2+ interfaces that demonstrate remarkable CO 2 methanation performance. At 180°C and a space velocity of 36,000 mL g −1 h −1 , the catalyst achieves 94.9% CO 2 conversion with a CH 4 production rate of 84.7 µmol g cat −1 s −1 , surpassing state‐of‐the‐art catalysts, while maintaining robust stability. Combined experimental and theoretical investigations identify the Ru–O–Mn 2+ interface as the pivotal active center, revealing a direct positive correlation between the amount of interfacial oxyphilic species, the quantity of weakly adsorbed CO 2 , and the turnover frequency. This oxyphilic interfacial site establishes an extensive network for weak CO 2 adsorption, thereby promoting CO 2 activation at low temperatures. The successful extension of this strategy to Ni‐based systems underscores the universality of MnO‐mediated interfacial engineering. These findings establish a new design paradigm for low‐temperature catalysis and deepen the fundamental understanding of interfacial oxyphilicity in heterogeneous catalysis.

Triple Matrix Confinement‐Induced Ultrabright Afterglow From Carbon Dots With Multivariate Responsive Afterglow Colors for Advanced Dynamic Information Encryption

ABSTRACT Dynamic afterglow carbon dots (CDs) materials, capable of long‐duration emission and dynamic color changes after excitation, hold promise for widespread applications in high‐level encryption and visual sensing. However, the single‐variable response afterglow color changing limits the potential of CDs for multidimensional information encoding and dynamic encryption in complex environments. Here, we report metal‐free CDs with triple‐variable responses (time, temperature, and excitation wavelength) for multiple dynamic afterglow colors and an ultra‐high afterglow brightness (406 cd m −2 ) far exceeding those of other afterglow materials. Based on the synergistic effect of triple matrix confinement and interface effects, room‑temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) are integrated into a single CD system. Owing to the different lifetimes of the dual‐mode afterglow (phosphorescence and TADF) and their varying sensitivities to temperature and excitation wavelength, time‐dependent afterglow colors (TDAC), excitation‐dependent afterglow colors (EDAC), and thermochromic afterglow (TCAG) are simultaneously achieved. Finally, we also designed a three‐dimensional variable‐response color code that varies with time, temperature, and excitation wavelength, spanning the entire visible spectrum. This platform enables high‐capacity, programmable, full‐gamut, and visually intuitive information encryption and display, providing a promising pathway for advanced, multidimensional anti‐counterfeiting and secure communication technologies.

Engineering Multivalent Copper Catalysts From Cu‐MOF Towards High‐Performance C ₂ Electrosynthesis

ABSTRACT Electrocatalytic CO 2 reduction reaction (ECO 2 RR) stands as a crucial process for converting CO 2 into valuable chemicals, particularly C 2+ products. Yet, achieving high selectivity towards C 2+ chemicals remains challenging. Among the catalysts explored to date, Cu‐based catalysts with multivalent Cu are widely used for this process. However, the precise tuning of Cu‐based catalysts, especially stabilization of multivalent Cu species, remains a difficult issue for enhancing selectivity toward C 2+ products. In this work, we report an efficient Cu‐based catalyst (designated as Cu‐MOF/Cu x O/CF‐40), containing Cu‐terephthalic acid (PTA) (Cu‐MOF) generated on a Cu foil (CF) and Cu x O (Cu 2+1 O and CuO) mainly stemming from Cu‐MOF, in achieving ECO 2 RR to C 2 chemicals. The catalyst delivers a total C 2 Faradaic efficiency (FE C2 ) of up to 91.8% and a total current density of 34.6 mA·cm −2 at ‐1.1 V (vs. RHE) in 0.1 M KCl (H‐cell). The Cu 2+1 O and CuO species, with multivalent Cu properties, adsorb and activate CO 2 , and improve the electrical conductivity of the catalyst. Cu‐MOF stabilizes the multivalent feature and long‐term performance of the catalyst. In situ ATR‐FTIR and DFT calculations identify *OCCOH as the key C–C coupling intermediate. This work provides a rational design strategy for efficient, stable Cu‐based catalysts and demonstrates a single‐source route to engineer multivalent Cu sites for selective CO 2 ‐to‐C 2 conversion.

Selective Conversion NOx Into Isoxazoles via Co–Zn Electrocatalyst Steering the Reaction Pathway

ABSTRACT The electrocatalytic upcycling of NOx species into valuable N ‐heterocycles presents an attractive route, but it is challenged by complex paths and low catalytic activity. This work reports a highly selective strategy for the electrochemical reduction of NOx to isoxazoles via coupling with 1,3‐dicarbonyls, enabled by a Co–Zn dual‐atom catalyst (Co–Zn–NC). Interestingly, the system achieves a remarkable Faraday efficiency of 92% for isoxazole and significantly inhibits hydrogen and ammonia production. The unique electronic structure significantly regulates the energy barrier of nitrate reduction reaction and the hydrogen adsorption energy revealed by density functional theory calculations, while obtaining moderate affinity towards hydroxylamine intermediate and isoxazole product illustrated from the adsorption measurements. This strategy demonstrates exceptional universality across various nitrogen sources (NO 3 − , NO 2 − , NO, NO 2 ), carbon sources (1,3‐dicarbonyls), and a series of M–Zn–NC catalysts, establishing a novel paradigm for synthesizing structurally complex N─O heterocycles directly from inorganic nitrogen wastes and creating a new platform for sustainable molecular manufacturing.