Browse Articles

RETRACTION: Manganese(I) Catalyzed Ortho C−H Allylation of Benzoic Acids

Metal‐Free Scission of the NO ⁺ Triple Bond

ABSTRACT We report the facile and direct room temperature unimolecular scission of the N≡O + triple bond, one of the strongest known chemical bonds with a bond dissociation energy of 1049 kJ mol −1 . The reaction of NO[Al(OR F ) 4 ] (R F  = C(CF 3 ) 3 ) and PNP t Bu (2,6‐bis(di‐ tert ‐butylphosphinomethyl)pyridine) in CH 2 Cl 2 yields the 1,2,3‐diazaphospholo[1,5‐ a ]pyridinium derivative [DAPP t Bu ] + [Al(OR F ) 4 ] – ( 1 ), featuring the complete cleavage of the N≡O + bond. At −30°C, the reaction intermediate [PNOP t Bu ] + [Al(OR F ) 4 ] – ( 2 ), which contains the novel bridging P═N−O−P + motif, can be isolated. Mechanistic insights were gained through quantum chemical calculations, which elucidated the formation pathways of 1 and 2 , while NMR spectroscopic kinetic studies quantified the conversion rate from 2 to 1 .

Dual‐Polarized Donor–Acceptor Polymer Unlocks Long‐Lived Triplet Excitons for High‐Efficiency H ₂ O ₂ Photosynthesis

ABSTRACT Long‐lived triplet excitons in polymers are crucial for driving oxygen reduction reaction (ORR) in photocatalytic H 2 O 2 production, but their formation is typically limited by weak spin‐orbit coupling (SOC) and a large singlet–triplet splitting energy (Δ E ST ). Here we present a “dual‐polarized” strategy in a novel donor–acceptor (D–A) polymer (MQDP) containing S═N─C and C═N─C linkages. MQDP polymer was prepared via supramolecular precursor polymerization of acenaphthenequinone (AQ), dibenzothiophene‐5‐oxide (DPO), and melem (ME). Compared to the single‐polarized analogue MQP ( τ p = 672 µs), the dual‐polarized units in MQDP enhance SOC and reduce Δ E ST , thereby generating multiple singlet‐to‐triplet intersystem crossing (ISC) transfer channels to produce long‐lived triplet excitons ( τ p = 868 µs). In addition, the dual‐polarized MQDP enriches surface−active sites for O 2 adsorption, effectively reducing the energy barrier for ORR. The MQDP achieves a remarkable H 2 O 2 generation rate of 15.38 mmol g −1  h −1 under visible light irradiation and ambient air, nearly 1.9 times higher than that of MQP (8.13 mmol g −1 h −1 ). These findings demonstrate the effectiveness of the dual‐polarized design in tuning exciton dynamics and surface reactivity of D–A polymers for enhanced photocatalysis.

The Precise Modulation of Probe Effective Charges by Debye Length for Enhancing Performance of Aptamer–FET Biosensors

ABSTRACT Field–effect transistor (FET) biosensors have garnered significant interests in disease diagnosis. The electrostatic interaction between channel materials and probes/targets is important to the performance. However, the modulation of electrostatic interaction is difficult because it was severely attenuated in real environment, which is common in practical bioanalytical detection. With small size, aptamer possesses programmable base composition, which is unlimited by the binding sites. Herein, we systematically investigate the precise modulation of Debye length (λ D ) on the effective charge quantity of aptamer probe to regulate electrostatic interaction. We discovered that the performance achieves the optimum due to the largest quantity difference of aptamer probe effective charges when λ D approaches the minimum between aptamer probe lengths before and after binding with targets. This precise modulation is highly effective for both signal–on and signal–off detection of biomolecules such as serotonin and dopamine, exhibiting a wide linear detection range, spanning from 10 fM to 1.0 nM (10 5 ), and an ultra–low limit of detection (<10 fM). Importantly, this precise modulation exhibits practical detection improvement of dopamine secretion from living PC12 cells. Our findings provide a pioneering guideline for enhancing performance of aptamer–FET biosensors and offer in–depth understanding of probe molecular structure.

Anion‐Immobilized Polar Nanochannels in Metal‐Organic Frameworks Enable Ion‐Decoupled Transport for High‐Performance Solid‐State Sodium Batteries

ABSTRACT The development of all‐solid‐state polymer sodium metal batteries (ASSP‐SMBs) is hindered by insufficient salt dissociation and imbalanced ion migration in polymer electrolytes. Herein, we propose an atomic level precise pore engineering strategy that integrates pore confinement with surface polarization in a metal‐organic framework (MOF) CAU‐10‐PyDC. The electron‐withdrawing effect of the pyridinic nitrogen atoms induces a localized positively charged microenvironment, which strongly anchors anions, promotes NaTFSI dissociation and establishes ion‐decoupled transport pathways with low energy barriers. Simultaneously, the optimized pore size offers a low‐energy‐barrier pathway for efficient Na + migration. Importantly, CAU‐10‐PyDC synergistically promoted polymer electrolyte (PyDC‐MSPE) induces the formation of stable, inorganic‐rich SEI and CEI layers, effectively suppressing dendrite growth and interfacial side reactions. The PyDC‐MSPE electrolyte demonstrates a high ionic conductivity of 3.37×10 −4 S cm −1 and a Na + transference number of 0.75. Na|PyDC‐MSPE|Na 3 V 2 (PO 4 ) 3 ASSP‐SMB maintains a specific capacity of 111.2 mAh g −1 after 1000 cycles at 2C. The corresponding pouch cell achieves an energy density of 325.7 Wh kg −1 , with high‐capacity retention of 87.7% after 100 cycles. This study unveils a novel mechanism where pore confinement synergizes surface polarization to regulate ion transport, offering an effective approach to addressing sodium salt dissociation and ion transport challenges in ASSP‐SMBs.

Molecular epidemiology and structural diversity of O101/O162 O-antigen variants among Escherichia coli bacteremia isolates

Abstract Most human invasive infections caused by extraintestinal pathogenic Escherichia coli (ExPEC) are associated with a limited number of O-serotypes and O-serogroups, including O101/O162. Here, we examined E. coli O101/O162 O-serogroup epidemiology among bacteremia isolates and performed genetic, biochemical and structural analyses. We demonstrate that the O101/O162 O-serogroup is globally widespread and highly associated with multidrug resistance (MDR). Dominant lineages belonged to clonal complex 10, including the high-risk clone ST167. Most O101/O162 ExPEC isolates contained an unusual O101 rfb locus previously identified as Onovel32, of which 30% harbored disruptions in the methyltransferase (MT) encoding gene. These disruptions resulted in alteration of the polysaccharide composition, and we identified two major O101 variants. Additionally, we found that an intact MT is a prerequisite for O -methylation of the polysaccharide, indicating terminal capping. Our data supports a model of a co-polymeric O101 O-antigen structure, which is unique for E. coli . Finally, we established that the two clinically relevant O101 O-antigen variant structures are highly immunogenic as polysaccharide-protein conjugates but differ in their ability to elicit opsonophagocytic antibodies. Altogether, our data provides important insights into O-serotype epidemiology and O-polysaccharide variation within E. coli O101/O162 isolates associated with bacteremia.

Quantifying functional vision in a mouse model of oculocutaneous albinism type 1

Corrigendum to “Cascade in Situ Self‐Assembly and Bioorthogonal Reaction Enable the Enrichment of Photosensitizers and Carbonic Anhydrase Inhibitors for Pretargeted Cancer Theranostics”

Persistence of vestibular function in the absence of glutamatergic transmission from hair cells

Abstract Quantal synaptic transmission in vestibular endorgans is glutamatergic. Here, we investigated the vestibular phenotype of deaf Vglut3 −/− ( Slc17a8 −/− ) mice from the cellular to behavioral levels. In Vglut3 −/− mice, quantal synaptic transmission in utricular calyces was reduced in rate and amplitude by > 95%. In vivo recordings of spontaneous activity in the vestibular nerve revealed no significant effect of VGLUT3 deletion on afferent rate and regularity, suggesting a divergent underlying mechanism compared to the silent Vglut3 −/− auditory nerve. In behavioral studies, Vglut3 −/− mice did not exhibit considerable sensorimotor or balance deficits. Type-II vestibular hair cells (VHCs) in Vglut3 +/+ mice were strongly immunoreactive for VGLUT3, while type-I VHCs showed weak immunoreactivity. Collectively, these data support the view that non-quantal transmission is the predominant mode of neurotransmission between type-I VHCs and vestibular calyceal afferent neurons. We propose that non-quantal transmission is sufficient to support vestibular nerve physiology and behavioral function in Vglut3 −/− mice.

Remote Molecule Activation in Living Mice Triggered by Therapeutic Ultrasound

ABSTRACT Remote, noninvasive chemical activation of bioactive molecules holds transformative potential for both biomedical research and therapeutic applications. Here, we report a deboronative hydroxylation reaction triggered by therapeutic ultrasound (termed dBus), in which boronic acid moieties are selectively converted into hydroxyl groups under clinically relevant, biocompatible conditions. We demonstrate that dBus enables spatiotemporally precise activation of diverse functional molecules, including fluorophores, bioactive small molecules, covalent labeling probes, peptides, and proteins, in both cellular systems and living animals. Mechanistic studies identify hydroxyl radicals, generated via ultrasound‐induced acoustic cavitation, as the reactive species driving this transformation. Notably, dBus facilitates ultrasound‐controlled prodrug activation in tumor‐bearing mice, resulting in significant tumor growth inhibition without systemic toxicity. With its simplicity, compatibility with existing ultrasound platforms, and broad molecular scope, dBus establishes a generalizable chemical foundation for noninvasive therapeutic intervention, precision diagnostics, and spatially resolved biological modulation.

Structural and lithological controls on landfill site suitability in Tenth of Ramadan City, Egypt using remote sensing and machine learning

Abstract The study area, located east of Tenth of Ramadan City, represents a vital urban center on the desert fringes of the eastern Nile Delta. In accordance with governmental regulations for landfill construction in new developments, this study aims to identify optimal landfill sites by integrating environmental and geotechnical considerations. Remote sensing and machine learning techniques (K-means and Support Vector Machine (SVM)) were applied to Landsat 5 TM imagery for lithological mapping. The SVM classification achieved an overall accuracy of 82.49% and a Kappa coefficient of 0.7235, providing a significant spatial refinement over the regional geological map by identifying localized lithological variations and recent urban expansion. Additionally, structural analysis using PCA yielded a 25% increase in detected lineament lengths 19.3 km compared to legacy data 15.4 km. Furthermore, ASTER GDEM data were used to generate a digital elevation model to visualize topographic variations and support structural analysis. The results revealed clear delineation of lithological units and highlighted zones of high lineament density, with dominant NE–SW (Syrian Arc) and NW–SE (Clysmic) structural trends influencing hydrogeological and geotechnical stability. Multi-criteria decision analysis (MCDA) was employed to map suitability, indicating that approximately 16.2% of the study area is highly suitable for landfill siting. These findings provide a practical framework for urban planners, providing a reliable decision-support framework for landfill selection based on integrated lithological and structural evidence.

Effectiveness of the coping and parental competence intervention on mental well-being in parents of preschool children with special educational needs: A randomized controlled trial

Machine learning modelling of a nonlinear environmental index with sensitivity analysis for groundwater assessment

Self‐Biased Electro‐Mineralization via Programmable Field Engineering for Energy‐Efficient Ocean Carbon Removal

ABSTRACT Gigaton‐scale carbon removal demands geologic permanence at low land, water, and energy cost. Ocean pathways are promising, but many electrochemical routes require large pH swings, membranes/sorbents, and suffer from fouling. We report the self‐biased electro‐mineralization as a practical route to ocean carbon removal. Porous core‐shell electrodes program interfacial fields that direct Ca 2+ /CO 3 2− transport and trigger in‐pore crystallization in simulated seawater, without membrane stacks or large bulk pH swings. Field strength is tunable via core/shell ratio, polymer chemistry, and fixed‐charge density, enabling the architecture to deliver long‐duration, fouling‐resistant operation (>2000 h), ∼25% DIC conversion under flow. A 400 cm 2 cell and a simple 100‐liter stirred reactor show that the microscale, uniform field both preserves performance under geometry area scale‐up and enables low‐overhead capacity expansion. Techno‐economic analysis projects an energy consumption of 44 kJ mol −1 CO 2 and a cost of $139 t −1 CO 2 . Extending beyond CaCO 3 , we precipitate additional sparingly soluble phases (CaF 2 , BaSO 4 , PbSO 4 ) from complex brines, establishing a platform also supporting resource recovery. These results shift ocean mineralization from bulk‐solution manipulation to programmable reaction‐environment design, advancing a scalable, cost‐effective pathway to climate relevant carbon removal.

Evaluating the propagation process of meteorological, hydrological, and agricultural drought dynamics in the Yellow river basin

A pattern-growth approach for mining maximal fault-tolerant frequent itemsets

Abstract Mining fault-tolerant (FT) frequent itemsets in noisy datasets is more challenging than conventional frequent itemset mining due to the high cost of evaluating fault-tolerance conditions. Consequently, mining maximal fault-tolerant frequent itemsets (FT-MFIs) is particularly important, as they provide a concise representation of all frequent patterns while eliminating redundancy, which is crucial in noisy datasets where error tolerance must be considered. Existing approaches for mining FT-MFIs are predominantly based on Apriori-style candidate generation and test, which suffer from exponential candidate growth, multiple dataset scans, and limited scalability. As a novel contribution, this work is the first to propose a pattern-growth framework for mining FT-MFIs. We introduce an algorithm that constructs a fault-tolerant FP-tree (FT-FP-tree) to compress transactions with common prefixes and evaluate tolerance conditions in a single pass. Additionally, new techniques for transaction mapping and conditional pattern extraction enhance the efficiency and scalability of the mining process. Experimental results on benchmark datasets demonstrate that the proposed approach achieves substantial reductions in execution time compared to all existing algorithms, while also showing improved memory efficiency relative to other pattern-growth based algorithms. This establishes pattern growth as a practical and scalable solution for fault-tolerant frequent itemset discovery.

Genomic convergence of multidrug resistance, virulence-associated loci, and phage defense systems in Klebsiella pneumoniae from pharmaceutical wastewater in Bangladesh

In Situ Bismuth Exsolution‐Driven Controllable Bi/Bi ₄ Ti ₃ O ₁₂ Heterointerface Catalysts for Enhanced Photocatalytic CO ₂ ‐to‐HCOOH Conversion

ABSTRACT Heterointerface engineering based on built‐in electric field (BIEF) has emerged as a promising route for regulating interfacial charge transfer and the electronic structure of active sites to achieve efficient photocatalytic CO 2 reduction. However, constructing strongly coupled heterointerfaces to maximize BIEF effects remains challenging. Herein, an off‐equilibrium solvothermal strategy is employed to induce the in situ exsolution of bismuth (Bi) nanoparticles from Bi 4 Ti 3 O 12 , yielding tight and homologous Bi/Bi 4 Ti 3 O 12 (Bi/BTOVs) heterointerface catalysts. Both experimental and theoretical analyses reveal a volcano‐type relationship between the intensity of BIEF and the size of the exsolved Bi nanoparticles. Strengthened BIEF facilitates directional interfacial charge transfer and shifts the Bi p‐band center toward the Fermi level. The optimized p‐band center strengthens the adsorption and activation of CO 2 , thus lowering the formation barrier of the *OCHO intermediate. Moreover, the Bi nanoparticles also induce a localized photothermal effect, raising the reaction temperature to accelerate CO 2 reaction kinetics. As a result, the 8 Bi/BTOVs catalyst with the optimal BIEF achieves a high HCOOH yield of 4126.25 µmol·g −1 ·h −1 with near‐unity selectivity. This study provides a generalizable strategy for the rational design of BIEF‐based strongly coupled heterointerfaces, offering a transferable design principle for photocatalytic CO 2 reduction.

Interfacial Electronic Nanoarchitectonics for Sustainable Zn─I ₂ Batteries

Abstract Aqueous zinc‐iodine batteries (AZIBs) are intrinsically safe and cost‐effective, yet their performance is limited by sluggish iodine redox kinetics, poor conductivity, and severe polyiodide shuttling. Herein, we design a heterostructure cathode by depositing titanium nitride (TiN) onto biomass‐derived porous nitrogen‐doped carbon (PNC), forming a tailored PNC@TiN interface that markedly enhances electronic conductivity and regulates iodine electrochemistry. Density functional theory (DFT) calculations reveal pronounced interfacial charge redistribution with an upward shift of the Ti d ‐band centeri, enabling strong Ti─I bonding through orbital coupling among Ti 3 d , C/N 2 p , and I 5 p states, as well as improved iodine affinity with suppressed polyiodide shuttle. Accordingly, the AZIB with the PNC@TiN cathode exhibits a high reversible capacity of 166.9 mAh g −1 after 21,000 cycles at 2.0 A g −1 (95.4% retention), and exceptional durability over 66,000 cycles at 5.0 A g −1 with an ultralow capacity decay of 0.00028% per cycle. Furthermore, the as‐assembled pouch cells achieve 176.1 mAh g −1 with negligible degradation, highlighting their practical viability. This work underscores the crucial role of interfacial electronic nanoarchitectonics in modulating iodine chemistry, and presents a sustainable strategy to repurpose biomass into advanced energy‐storage materials.

The role of land weathering in carbon consumption and its impact on global carbon cycling since the Last Interglacial period