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Br‐Mediated Pd Catalysis Promotes Intermediates Stabilization and Coupling for Anodic Electrosynthesis of Dimethyl Carbonate
ABSTRACT Electrosynthesis of dimethyl carbonate (DMC) from methanol (MeOH) and CO on a Pd‐based catalyst has shown high selectivity; however, most of the corresponding total current densities ( j total ) are still too small to support industrial applications. In this study, we built a Pd‐Br electrocatalytic system in a flow cell to produce DMC with both high selectivity and high reaction rate. Remarkably, up to 89.4% of the DMC Faradaic efficiency (FE DMC ) was achieved at j total of 100 mA cm −2 . Mechanism studies suggest that the in situ generation of active sites with a proper distribution of Br‐modified Pd(I) sites and PdBr 2 for the coadsorption of CO and MeOH is vital for this reactivity. Under Br mediation, the excessive formation of high‐valence Pd species was inhibited, while the DMC formation was substantially facilitated in thermodynamic terms. These findings shed vital methodological and mechanistic insights for developing efficacious electrocatalytic systems for DMC synthesis.
Identification and characterization of the virome in cell-free DNA from peripheral blood of pregnant women in Shaanxi Province, China
Effect of ethyl methane sulfonate mutagenesis on phenological, yield-related and yield traits in cowpea (Vigna unguiculata (L.) Walp)
This study investigated the mutagenic effects of ethyl methane sulfonate (EMS) on the M₁ generation of cowpea (Vigna unguiculata (L.) Walp.) cultivar ‘Wang Kae.’ A total of 275 M₀ seeds were treated with EMS concentrations of 20 mM, 40 mM, and 80 mM (75 seeds per treatment) by soaking for six hours, while 50 untreated seeds served as the control (0 mM). Phenological, yield-related and yield traits were recorded, and data were analysed using Jamovi 2.7.15 and JASP 0.95.4.0 through one-way ANOVA with post hoc contrast, principal component biplot, and cluster analyses. No optimal mutagenic concentration (LD50) was identified. Seed germination and seedling survival rates increased with increasing EMS concentration, ranging from 70.00% and 62.00% in the control (0 mM) to 89.33% and 74.67% at 80 mM, following the trend 0 mM < 20 mM < 40 mM < 80 mM. Significant differences (P < 0.05) were observed among treatments for all phenological traits, pod length, locule number, seed traits, and yield per plant. Yield was significantly higher (P = 0.047) at 20 mM (61.19 ± 3.34 g) compared to the control. Contrast analysis identified genotypes B33 and D56 as the most productive mutants, with yields of 125.44 g and 111.85 g, respectively. Principal component analysis extracted eighteen components, with the first four cumulatively explaining 50.60% of total variation. Biplot analysis of PC1 and PC2 captured all phenological traits, key seed traits, and yield attributes, highlighting the superior performance of B33 and D56. Cluster analysis partitioned the 190 genotypes into six groups, with B33 and D56 constituting distinct clusters. EMS mutagenesis effectively induced heritable phenotypic variation, with putative superior genotypes identified for advancement to M 2 and evaluation in replicated multi-environment trials toward the development of farmer- and consumer-preferred cowpea varieties.
Reversing the Hydrogenation Pathways of Nitrogen‐Containing Intermediates for the Kinetics‐Matched Urea Electrosynthesis
ABSTRACT Urea electrosynthesis from carbon dioxide (CO 2 ) and nitrate (NO 3 − ) is a promising sustainable route. However, the kinetic mismatch between key intermediates remains the major challenge for achieving selective C‒N coupling. Herein, indium‐doped titanium dioxide (In‐TiO 2 ) nanofibers were developed to regulate the hydrogenation pathway for realizing kinetics‐matched urea electrosynthesis. In situ spectroscopic analysis and theoretical calculations reveal that In doping reverses the hydrogenation pathway of nitrogen‐containing intermediates from the Eley‐Rideal (E‐R) to the Langmuir–Hinshelwood (L–H) mechanism. This shift is attributed to the sufficient *H supply guaranteed by the regulated interfacial water structure. Such reversed hydrogenation pathway balances *H utilization between CO 2 and NO 3 − reduction, enabling well‐matched formation kinetics of key intermediates for efficient C‒N coupling. Owing to the above merits, In‐TiO 2 achieved the remarkable average urea yield rate of 56.5 mmol h −1 g −1 with a Faradaic efficiency of 32.8%. This work provides mechanistic insights into the hydrogenation pathways regulation for efficient urea electrosynthesis.
Preliminary pharmacokinetic investigations of hydroxylated metabolites after controlled inhalative and oral consumption of hexahydrocannabinol (HHC)
Abstract The pharmacokinetics of the semisynthetic cannabinoid hexahydrocannabinol (HHC) and its 11-nor-carboxy- as well as 11-hydroxy-metabolites has already been the subject of research in various recent publications. However, further metabolism studies showed the presence of other, especially (side-chain-)hydroxylated metabolites in urine and serum. This study aimed to investigate the pharmacokinetics of these metabolites after oral (25 mg fruit gum) and inhalative (three puffs from vape) consumption, using serum and urine samples from a previous study. Serum (up to 48 h) and urine (up to five days) samples of six participants (three per consumption group) were collected at different time points and analyzed by LC-QqTOF and LC-QqLIT. Three metabolites (M1: side-chain-hydroxylated; M2: hydroxylated on alicyclic moiety; M3: 8-OH-HHC) were further investigated. The peak area ratios of analytes and internal standards were plotted against the time after consumption to obtain pharmacokinetic information. Overall, this study proved the presence of these metabolites in biological samples and provided pharmacokinetic insights for the first time. Differences between serum and urine, oral and inhalative consumption as well as inter-individual differences were observed. The investigated metabolites could partially serve as unambiguous consumption markers for HHC, as they are unlikely to be formed in vivo from corresponding Δ 9 -tetrahydrocannabinol (THC) metabolites.
Expansion of the exotic macroalga Batophora occidentalis in Posidonia oceanica meadows and other native benthic habitats
Marine invasive macroalgae can be detrimental to native ecosystems. The exotic green macroalga Batophora occidentalis was first reported in 2020 in Estany des Peix lagoon in Formentera (Spain). In 2023 and 2024, our surveys revealed that it had spread to 100% of the surveyed locations within the lagoon. In 2024, B. occidentalis, reached an average cover of 30% in Cymodocea nodosa meadows and 26% in Caulerpa prolifera meadows, with respective biomasses of 52 g m ⁻ 2 and 44 g m ⁻ 2 , making it the most abundant macrophyte in these two native benthic habitats. We also found exotic B. occidentalis growing epiphytically on the leaves and rhizomes of Posidonia oceanica within the lagoon, with an average cover of 12% in 2023 and 16% in 2024, and a biomass of 3 g m ⁻ 2 in 2024. Notably, it covered nearly 25% of the P. oceanica leaf surface and reached up to five times the weight of individual leaves. Alarmingly, we report the presence of a B. occidentalis specimen on a P. oceanica shoot in a nearby meadow outside the lagoon, signalling a potential spread beyond its current range. Additionally, the exotic macroalgae colonized various natural and hard substrates, including boat hulls, as it was growing on nearly 20% of boats anchored in the only marina in the lagoon. With this study, we aim to encourage prompt action from local and regional governments. We may be witnessing the early stages of a broader expansion of this exotic alga, highlighting a critical moment to implement early management measures such as monitoring, and, where possible, containment within the lagoon.
Novel Non‐Cytotoxic Acylphosphinates and Acylphosphine Oxides Photoinitiators
ABSTRACT This study focused on the design and synthesis of a series of novel acylphosphine oxide (APO) and acylphosphinate photoinitiators based either on diphenylphosphine oxide (DPO) or 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO), systematically investigating the structure–property relationships in terms of photochemical performance, polymerization efficiency and cytotoxicity. Polymerization experiments demonstrated that DPO‐based photoinitiators exhibit excellent photopolymerization efficiency, while the structurally optimized DOPO‐based Type I photoinitiators also exhibit good reactivity. Biocompatibility experiments indicate that acylphosphinates (e.g., the (6‐oxidodibenzo[c,e][1,2]oxaphosphinin‐6‐yl)(2,4,6‐trimethoxyphenyl)methanone (TMO‐DOPO) derivative) exhibit no significant toxicity toward C3H10 T1/2 mouse mesenchymal stem cells, significantly outperforming the traditional 2,4,6‐trimethylbenzoyldiphenylphosphine oxide (TPO) photoinitiator. These results highlight the DOPO role as a functional core in Type I initiation systems, providing an effective strategy for developing novel, efficient, and low‐toxicity photoinitiators.
Wavelet coherence-aware multi-branch deep ensemble for fault identification in centrifugal pumps
Chronic oral cannabidiol delays seizure onset and reduces seizure burden in a mouse model of CLN2 disease
A growing body of literature describes the anti-inflammatory, neuroprotective, and anti-epileptic properties of the cannabis sativa constituent cannabidiol, suggesting that it might play a useful role in the treatment of neurodegenerative diseases. Late infantile neuronal ceroid lipofuscinosis (CLN2 disease) is a rare pediatric neurodegenerative disorder resulting from an inherited dysfunction of the lysosome. CLN2 disease, and its representative animal models, display neuroimmune response, neuroinflammation, neurodegeneration, and epileptic seizures, and these symptoms are all touted as potential targets of cannabidiol therapeutic benefit. Here, we treated a valid model of CLN2 disease with long-term daily cannabidiol (300 mg/kg) from 1 month of age until disease end stage and evaluated epileptic seizures, lifespan, and markers of neuroimmune response. Chronic cannabidiol treatment significantly delayed or fully eliminated seizures in CLN2 model mice compared to those treated with vehicle only, and the treatment led to a non-significant extension of lifespan. These effects occurred in the absence of any therapeutic benefit to physiological markers of disease such as GFAP, CD68, and cytokine/chemokine reactivity. Taken together, we show that chronic treatment with cannabidiol confers significant anti-seizure benefit to the mouse model of CLN2 disease, and that it does not appear to do so by altering the inflammatory and neuroimmune markers traditionally used to track CLN2 disease progression.
Correction to “Borohydride Oxidation as Counter Reaction in Reductive Electrosynthesis”
Stabilizing the Hexacyanotrimethylenecyclopropane Electron Acceptor—Structural and Photophysical Characterization
ABSTRACT Hexacyanotrimethylenecyclopropane ( CN6CP ) is an exceptionally strong organic electron acceptor in its neutral form, and widely applied for molecular doping to induce charge transfer processes and enable electrochemical systems. Yet, its fundamental molecular properties have remained largely unknown. Here, we show the first comprehensive structure‐analytical characterization of CN6CP , enabled by an improved, low‐temperature synthesis and the first solid‐state structure of the neutral compound. The resulting procedure affords isolable, crystalline CN6CP that is stable for weeks at –30°C and can be recrystallised. Across all redox states, combined IR/Raman, UV–Vis and NMR measurements, together with NICS calculations, reveal an oxidation‐state‐dependent redistribution of electron density. These data show that CN6CP possesses a σ‐aromatic cyclopropane core with tunable π‐delocalisation, which is enhanced upon reduction while the additional charge is predominantly localised on the exocyclic acceptor framework. Cyclic voltammetry experiments unveil two reversible one‐electron processes and an exceptionally low LUMO energy of –5.85 eV, which is the lowest reported for small organic molecules being significantly lower than those of benchmark acceptors such as F 4 TCNQ or F 6 TCNNQ. All together, these findings establish CN6CP as a structurally unique, extremely strong electron acceptor and provide the molecular basis underlying its performance in organic electronics and redox‐active materials.
Psychological and structural drivers of farmers’ pro-environmental behavior toward integrated pest management adoption in high-pesticide contexts
Exosomal gene-based predictive model and therapeutic target identification for Alzheimer’s disease: A bioinformatics analysis
Background Alzheimer’s disease (AD) is a degenerative central nervous system disorder characterized by progressive cognitive and behavioral impairment. As nanoscale intercellular communication vesicles that carry AD-related pathological molecules, exosomes are promising biomarkers and therapeutic carriers for AD. In this study, we downloaded AD-related gene expression profiles and clinical data from the Gene Expression Omnibus (GEO) database (datasets GSE138260, GSE29378, GSE36980, and GSE5281). Through a series of bioinformatics analyses, clinical predictive model construction, pharmacological network analysis, and molecular docking simulations, we developed an exosomal gene-based predictive model for AD pathogenesis and identified potential pharmacological networks and molecular docking targets for AD treatment. Materials and methods AD-related gene expression and clinical data were retrieved from the GEO database. Bioinformatics analyses, clinical model construction, drug-gene network analysis, and molecular docking were subsequently performed to explore exosomal gene models for predicting AD pathogenesis, as well as potential pharmacological networks and molecular docking targets for AD therapy. Results A five-exosomal-gene predictive model was established, comprising CD44, CXCR4, TUBB, PSMA5, and PSMB3. Pharmacological network analysis of these five genes revealed their significant associations with chelidonine, 2-chloro-1,4-dinitrobenzene, oxazolone, phencyclidine, thioridazine, and etodolac. Further molecular docking simulations identified key binding targets, including R41, Y42, R78, Y79, C77, I88, C97, A98, I96, I72, L70, E67, G103, I91, and T102. Conclusions Our comprehensive analyses successfully established a reliable exosomal gene-based model for predicting AD pathogenesis, and identified relevant pharmacological networks and core molecular docking targets, providing novel insights for AD diagnosis and targeted therapy.
Tailored Nanogel Network Topology Enables Clinical Ultrasound‐Induced Mechanochemical Activation for In Vivo Therapy
ABSTRACT Polymer mechanochemistry enables the selective mechanophore activation for precise molecular release. However, this field has long relied on the strong cavitation effects of low‐frequency ultrasound, which are incompatible with clinically high‐frequency ultrasound (> 1 MHz), hindering its biomedical applications. Herein, we report a nanogel network topology‐programmed mechanochemical strategy, enabling iterative activation of mechanophores under high‐frequency (up to 2.4 MHz) and low‐intensity (down to 2 W/cm 2 ) ultrasound. By introducing network topology as a design parameter, we established the relationship between nanogel topology, ultrasound frequency, and mechanochemical activity, revealing that distinct network topologies selectively accumulate mechanical forces under different ultrasound frequencies. Meanwhile, the thermal effect of high‐frequency ultrasound lowers the activation barrier of mechanophores, further promoting their efficient activation. Remarkably, under high‐frequency ultrasound, nanogels achieve an activation rate of 12.6%/min, placing it among the most efficient activation systems reported to date. Importantly, combining nanogels with clinical low‐intensity focused ultrasound, we developed a new ultrasound‐mediated therapeutic paradigm—synergistic sonothermal and mechanochemical therapy, achieving complete elimination of advanced tumors with a single short treatment. This work establishes network topology engineering as a general strategy for programming mechanochemistry, and opens new opportunities for the in vivo biomedical applications of polymer mechanochemistry.
First observation of novel satellites using high-resolution XR-HERFD measurement of Zn Kα emission
Abstract We discover satellites in Zn at emission energies of 8670–8675 eV. The satellite is detected with a significance exceeding 51.6 $$\sigma _{se}$$ per pixel, enabled by the exceptional signal-to-noise ratio of the new dataset and novel technique. We have created the eXtended-range high-energy-resolution fluorescence detection (XR-HERFD) technique and applied it to Zn (Z = 30) using a novel 14-crystal analyser spectrometer. For this current work, data collection developed the first DOSE-S collection macros for Discovery-Onset-Spectrometry-Evolution of new Satellite processes. The energy dependence of the discovered satellite is tracked from the onset of the process at approximately 10791.7 eV through its evolution to higher energies. The satellite exhibits a clear manifold structure, consistent with multiple shake-off processes. We develop and apply Principal Component Analysis (PCA) and independently isolate the manifold of the satellite and prove the incident-energy evolution. We also fit the evolution to theoretical quantum mechanical models of such processes to provide strong confirmation of the physical origin. These findings demonstrate XR-HERFD’s capability to resolve weak many-body features and suggest new opportunities for studying shake processes and the many-body reduction factor $$S_{0}^{2}$$ . By resolving these satellites in what many people believed was a nominally simple $$d^{10}$$ metal and revealing rich many-body behaviour, this work opens a pathway to a physically grounded understanding of many-body effects in X-ray spectroscopy.
The strip-shaped deep white matter hyperintensities may be related to neurodegeneration: A study based on diffusion tensor imaging
Purpose This study investigated the properties of strip-shaped white matter hyperintensities (WMHs) by examining the relationship between their principal axes and maximum diffusion direction, and comparing their diffusion tensor metrics with punctate and early confluent WMHs to explore their pathological features and potential link to chronic axonal injury. Methods Eighty-seven participants with isolated WMHs were included and received diffusion tensor imaging (DTI) using a 3.0-T MR scanner. Lesions were classified by elongation (strip-shaped: ≥ 2; punctate: < 2). We recorded the maximum diffusion direction of punctate, strip-shaped, and early confluent WMHs and evaluated their consistency with the principal axial direction. Additionally, the diffusion tensor metrics of strip-shaped WMHs were measured and compared with those of punctate and early confluent WMHs. Results Among 996 WMHs, 57.5% of strip-shaped lesions showed principal axis alignment with the maximum diffusion direction, significantly higher than punctate (44.7%) and early confluent (42.1%) lesions (P < 0.05). Mixed-effects models showed significant lesion type effects on FA, MD, AD, and RD (all P < 0.05). Post-hoc comparisons revealed that stripe lesions had higher FA but lower MD and RD than confluence lesions (all P < 0.05), with no significant differences between stripe and punctate groups for MD or RD. No AD differences were found among groups. Fiber tracking confirmed alignment in most strip-shaped lesions. Conclusion Strip-shaped WMHs exhibit unique diffusion metrics and fiber alignment, suggesting chronic axonal injury due to neurodegeneration. These findings underscore the importance of morphological and microstructural analysis in understanding WMH heterogeneity and clinical significance.
Matching the Coupling of Valence Electrons in the Oxide Interface to Perturb the Magnetic Order Enhancing Oxygen Reduction in Zinc–Air Batteries
ABSTRACT The inherently locked spin state between the metal sites and oxygen‐containing intermediates imposes an intrinsic limitation on the maximum achievable oxygen reduction reaction (ORR) activity. Herein, we construct the sub‐5 nm Fe 2 O 3 /Sm 2 O 3 heterojunctions immobilized in N‐doped carbon nanofibers (denoted as sub‐5 nm Fe 2 O 3 /Sm 2 O 3 @N‐CNFs), where coupled Fe (3d)‐O (2p)‐Sm (4f) orbitals can regulate the interfacial spin order, thereby attenuating the Fe–OH binding. Operando spectroscopy and density functional theory calculations reveal that the super‐exchange interaction across the Fe–O–Sm bond induces an antiparallel magnetic alignment, which suppresses the spin interaction with OH* at the surface, thereby accelerating OH* desorption and enhancing ORR activity. In 0.1 M KOH, the catalyst delivers excellent ORR performance with a half‐wave potential of 0.94 V and a Tafel slope of 92.4 mV dec −1 , along with long‐term stability. Furthermore, the liquid‐ and all‐solid‐state rechargeable zinc–air batteries (ZABs) assembled with sub‐5 nm Fe 2 O 3 /Sm 2 O 3 @N‐CNFs also exhibit marked device performance, surpassing Pt/C + RuO 2 benchmarks. These results demonstrate that interfacial spin regulation via Fe–O–Sm coupling is an effective strategy to enhance ORR activity and stability of catalysts by reconfiguring local magnetic ordering to tune oxygenated‐intermediate adsorption. More broadly, this intrinsic‐property modulation can be extended to other anion‐bridged compounds and spin‐involved electrocatalytic reactions.
Thermo-hydraulic and second-law analysis of a shell-and-tube heat exchanger using water, propylene glycol, and glycerol mixtures in the laminar–transition regime
Abstract This study presents a comprehensive experimental investigation of the thermo-hydraulic and second-law performance of a shell-and-tube heat exchanger operating under counter-flow conditions. Water, propylene glycol/water (PG/water), and glycerol/water mixtures at different concentrations were employed as working fluids to evaluate the influence of thermophysical properties on heat-transfer, hydraulic, and exergy characteristics. A total of 105 experimental runs were conducted over a Reynolds number range of 400–4800, covering laminar and transitional flow regimes. The overall heat transfer coefficient, pressure drop, Nusselt number, friction factor, entropy generation, and exergy efficiency were systematically analyzed and compared under identical operating conditions. The results demonstrated that increasing Reynolds number significantly enhances heat-transfer performance, resulting in higher overall heat-transfer coefficients and Nusselt numbers. However, this improvement is accompanied by increased pressure losses and entropy generation, reflecting the thermodynamic trade-off between heat-transfer enhancement and irreversibility. Among the investigated fluids, water exhibited the highest thermal and exergy performance, whereas glycerol/water mixtures produced the lowest performance due to their higher viscosity and associated flow resistance. To provide practical predictive tools, empirical correlations were developed for both the Nusselt number and friction factor based on the complete experimental dataset. The proposed correlations were expressed as Nu = 2.43*Re^0.30*Pr^0.094 and f = 5.47 Re^-0.62*Pr^-0.08, showing satisfactory agreement with the experimental measurements. Validation against established literature correlations confirmed the capability of the proposed models to predict thermal and hydraulic performance within the investigated Reynolds number range. The novelty of the present work lies in the comparative experimental assessment of water, propylene glycol/water, and glycerol/water mixtures under identical operating conditions, together with the simultaneous evaluation of thermal, hydraulic, and second-law performance metrics and the development of predictive correlations based on an extensive experimental database. The findings provide reliable benchmark data and engineering correlations that can support the design, optimization, and exergy-based evaluation of heat exchangers operating with viscous heat-transfer fluids in industrial thermal systems.