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Benchmarking the prediction of responding cells to perturbations affecting both gene expression and cellular abundance using scRNA sequencing
Spiro‐Buckybowl‐Structured Hole‐Transporting Materials Toward High‐Efficiency and Stable p–i–n Perovskite Solar Cells
ABSTRACT In p–i–n structured perovskite solar cells (PSCs), uniform distribution of underlying hole‐transporting materials (HTMs) and its interfacial interaction with perovskite defects are crucial for device efficiency and long‐term stability. Here, we developed two spiro‐buckybowl‐shaped HTMs by introducing chalcogen elements (Se and S) into the π‐frameworks of sumanene named as Sp–Se and Sp–S, respectively. The unique 3D orthogonal‐geometry induced by spiro‐fusion reduces intermolecular π–π interactions, hindering molecular aggregation, improving surface coverage and facilitating efficient hole extraction. Additionally, the bowl‐shaped π‐system plays a critical role in deep‐level defects (Pb 2+ , V I ) passivation, leading to effective perovskite crystallization. Specifically, the Sp–S enables superior hole transport and a stabilized buried interface, yielding a champion efficiency of 25.54% (certified at 25.36%) and exceptional operational stability with 92.5% retention over 1250 h under continuous light illumination at 65°C (ISOS‐L‐2). The spiro‐buckybowl molecular structure establishes a new design paradigm for organic semiconductors, offering a versatile platform for perovskite photovoltaics.
Preparation and properties of a hydrophobically associating friction reducer for fracturing in low-permeability gas reservoirs
Fused Ring Engineering Induced Topology Control in Covalent Organic Frameworks: Unlocking Promoted Photocatalytic H <sub>2</sub> O <sub>2</sub> Production and Selective Methane Oxidation
ABSTRACT Efficient solar‐to‐chemical energy conversion and the selective activation of methane remain grand challenges in artificial photosynthesis. Here, we report the rational design of two covalent organic frameworks (COFs), Phen‐TTA and O‐TTA, in which framework topology and π‐conjugation are regulated by pairing a triazine‐based acceptor with either a rigid 1,10‐phenanthroline or a twisted 2,2′‐bipyridine donor. The results show that the Phen‐TTA, bearing a rigid kgd‐v topology, features a narrowed bandgap, reduced exciton binding energy, and accelerated charge‐carrier kinetics relative to O‐TTA with an hcb topology. Consequently, Phen‐TTA delivers a high photocatalytic H 2 O 2 production behavior (21.5 mmol h −1 g −1 and an apparent quantum yield of 5.45% at 450 nm), placing it among the most active COF‐based photocatalysts ever reported. Notably, Phen‐TTA further enables selective photocatalytic methane oxidation to ethanol (30.1 µmol h −1 g −1 , 365 nm irradiation) in the absence of noble‐metal cocatalysts. Mechanistic investigations indicate that the enhanced framework rigidity promotes sequential one‐electron oxygen reduction to H 2 O 2 , while the sustained H 2 O 2 supply undergoes photolysis to yield • OH that drive C─H activation. This work establishes topology engineering as an effective strategy to overcome excitonic and charge‐transport limitations in polymeric photocatalysts and demonstrates a rare single‐component organic framework for tandem solar‐driven methane valorization.
Risk-based sensitivity analysis of urban gas infrastructure in new district planning
Abstract Urban gas infrastructure resilience is critical for public safety, yet rapidly expanding networks face increasing vulnerability. This study develops a system dynamics-based framework to identify key leverage points for enhancing gas infrastructure resilience in new urban districts. Using a three-tier indicator system of 32 risk factors across four dimensions, analytic hierarchy process weighting is integrated with system dynamics modeling in a case study of a new district in China. Sensitivity analysis reveals that system’s inherent resilience contributes most significantly, with the proportion of high-pressure pipelines exhibiting the highest sensitivity, followed by population-infrastructure spatial coupling and building seismic resistance. These findings demonstrate that planning-phase interventions targeting high-sensitivity indicators offer the most efficient pathway to enhancing urban gas infrastructure resilience, challenging conventional priorities that emphasize emergency response over foundational design considerations.
Molecular Engineering of an Isomeric Raman Reporter Palette With Synergistic Multidimensional Enhancement for Point‐of‐Care SERS Screening of Respiratory Pathogens
ABSTRACT Surface‐enhanced Raman scattering (SERS) combines molecular‐specific fingerprints and signal amplification, making it ideally suited for multiplexed point‐of‐care (POC) diagnostics. Yet, the translation of SERS into practical use has been hindered by the empirical screening of Raman reporters without rational spectral tunability and the lack of rigorous validation in large clinical cohorts using handheld instrumentation. To this end, we introduce a principle‐driven molecular engineering approach to create a palette of tunable isomeric Raman reporters with clinical validation through large‐scale respiratory pathogen screening. Guided by molecular symmetry principles and electronic effects, we construct an isomeric palette of 24 Raman reporters with unique vibrational signatures. These reporters are enhanced by a multilayer Ag‐on‐Cu reporter structures (MARS) and a sub‐10 nm engineered nanogap SERS enhancer (SENSE) array to maximize signal amplification. The integrated isomeric‐MARS‐SENSE platform enables the simultaneous identification of six respiratory pathogens in 139 clinical nasal swab samples using a handheld Raman spectrometer, achieving satisfactory sensitivity, specificity, and accuracy comparable to RT‐PCR. By combining rational molecular design with robust clinical validation, we expect this work to advance next‐generation multiplexed SERS diagnostics at the POC.
Tobacco rattle virus triggers local defense and systemically coordinates taxoid biosynthesis in Taxus baccata revealed by integrated metabolic analysis
Regulating Dynamic Solid Electrolyte Interfacial Evolution via α‐H Methyl Substitution Carboxylate Ester Electrolytes Toward 20 Ah Wide‐Temperature (−60°C∼70°C) Li‐Ion Pouch Cells
ABSTRACT High reactivity of the α‐H sites in carboxylates is the root cause of inert interfacial evolution, where the resultant solvent co‐intercalation and α‐H‐mediated oxide hydrogenation contribute to non‐recover capacity loss and limited calendar cycle life, especially for wide‐temperature‐range applications. Herein, to regulate dynamic interfacial evolution, we ingeniously designed an ethyl isobutyrate (EI) based electrolyte via α‐H methyl substitution for practical LiCoO 2 /graphite (LCO||Gr) pouch cells. By replacing the strongly electron‐withdrawing α‐H group with an inert methyl group, the inherent solvent nucleophilicity is preserved, while the ESP min is significantly enhanced. Such specific solvation structure evolution can facilitate the involvement of EI in inner solvation sheath and further induce a dense, stable interface which can suppress the hydrogenation‐initiated capacity loss of delithiated LCO cathodes. Employing electrochemical DRT and ToF‐SIMS techniques, we demonstrate that EI can interrupt the solvent co‐intercalation process at Gr anode by stabilizing interfacial dynamics and suppress anodic self‐discharge. Consequently, the 2 Ah LCO||EI||Gr pouch cell retains approximately 96.4% capacity after 700 cycles at −20°C and exhibits overseeding 250 cycles at 45°C. Furthermore, the commercial 20 Ah LCO||EI||Gr pouch cells deliver high energy densities of 160.3 Wh kg −1 at −60°C and 229.1 Wh kg −1 at 70°C, which exhibit superior temperature resistance.
Chitosan and its derivatives in Lady Rosetta potatoes:In vivo gene expression modulation driving growth, yield, quality, and antibacterial defense
Abstract This study examines how different forms and concentrations of chitosan affect the growth, minituber yield, and processing quality of the ‘Lady Rosetta’ potato variety. Using a two-way ANOVA method, we assessed the effects of chitosan, chitosan acetate, chitosan lactate, and N, O-Carboxymethyl chitosan, along with their interactions at various concentrations. The results show that the type of chitosan is the main factor for improvement. Specifically, chitosan lactate significantly accelerated germination to 4.1 days in Season 1 and 4.67 days in Season 2, while increasing shoot length to 37.8 cm and 35.5 cm, respectively—nearly double the height of the control group. Regarding physiological traits, a significant interaction between chitosan form and concentration was observed for all photosynthetic pigments. Notably, 0.01% chitosan acetate maximized chlorophyll a (28.8 mg/g), while 0.03% N, O-Carboxymethyl chitosan resulted in the highest carotenoid accumulation (8 mg/g). For yield, chitosan lactate achieved the highest results, reaching an average of 3.78 minitubers per plant and a weight of 21.33 g in Season 2, greatly surpassing other forms. Molecular analysis showed that chitosan lactate treatments significantly reduced AS1 and POT32 gene activity (up to 75% and 73% reduction, respectively), explaining the lower enzymatic browning and reduced acrylamide precursors. Additionally, 0.05% chitosan lactate showed strong antibacterial activity against Pectobacterium carotovorum and Ralstonia solanacearum , with inhibition zones reaching 24.66 mm. These results indicate that chitosan lactate serves as a dual-purpose biostimulant and bioprotectant, greatly enhancing both productivity and quality in potato farming.
Engineering Ferroelectric Dipole Superstructure via Phase Transformation for Stable Zinc Anodes
ABSTRACT The commercialization of aqueous zinc ion batteries (AZIBs) is severely hindered by the thermodynamic instability of the Zn anode interface, which leads to uncontrollable dendrite growth and parasitic side reactions. While ferroelectric polymers like poly(vinylidene fluoride) (PVDF) show promise for regulating ion flux via their built‐in electric field, the common α‐phase PVDF exhibits random dipole alignment, resulting in a negligible macroscopic polarization effect. This work demonstrates that incorporating zinc sulfide (ZnS) as a multifunctional filler is an effective strategy to actuate a crucial phase transformation from the non‐polar α‐phase to the highly polar β‐phase within the PVDF matrix. The resulting dipole‐enhanced hybrid layer (DEHL) features a structure where β‐phase nanocrystalline domains are aligned akin to “dipole superstructures,” generating a strong and homogeneous built‐in electric field. This field functions as an intelligent regulator, steering Zn 2+ ions toward uniform nucleation and dense deposition while simultaneously repelling SO 4 2− anions, thus synergistically suppressing zinc dendrites and inhibiting byproduct formation. Consequently, the DEHL‐protected Zn anode (DEHL@Zn) achieves exceptional cycling stability over 1800 h in a Zn//Zn symmetric cell at 5 mA cm −2 . When paired with NVO and I 2 cathodes, the full batteries also deliver remarkable longevity, exceeding 2300 and 11 000 cycles with high specific capacities, respectively.
Digital literacy equity in AI-enhanced English learning: Access, participation, and implications for language education policy
Photocatalytic Radical‐Polar Crossover Enables Modular Access to Bicyclo[2.m.n]Alkane Alcohol Bioisosteres
ABSTRACT The strategic replacement of aromatic rings with saturated bioisosteres has become a pivotal strategy in medicinal chemistry, offering a proven path to improve the metabolic stability and safety profiles of drug candidates. Conventional access to these valuable saturated scaffolds, however, heavily relies on strain‐release strategies that mandate the use of highly strained, synthetically challenging precursors. Herein, we report a general platform based on a visible‐light‐induced radical–polar crossover (RPC) manifold. This method employs bench‐stable γ‐ and δ‐keto acids as radical precursors, which, upon activation, engage in cross‐coupling with a diverse array of π‐systems. This straightforward approach provides direct and efficient access to a wide range of synthetically elusive saturated bicyclic alcohol bioisosteres. By circumventing the need for pre‐strained intermediates, our strategy delivers the target architectures in high yields with excellent functional group tolerance. Furthermore, successful product derivatizations underscore the synthetic utility of this method, while mechanistic investigations corroborate the proposed RPC pathway. Together, these findings establish our platform as a practical and robust alternative to current paradigms.
Modulations of the P3b effect as a function of bilingual language experience
Abstract Recent theoretical accounts propose that variability in bilingual language experience can drive neuroplastic modifications in attentional systems. In the present study, we empirically evaluated this proposition by examining whether continuous variation in bilingual language experience predicts neural activity associated with the allocation of attention to salient environmental stimuli. To this end, we recorded electroencephalography (EEG) and response time data from young adults with diverse language backgrounds as they completed an active visual oddball paradigm known to elicit the P3b component. Language experience was quantified using composite factor scores derived from the Language and Social Background Questionnaire, which served as an index of participants’ cumulative bilingual language engagement. Because childhood family socioeconomic status (SES) is known to influence neural development and adult cognitive functioning, we also controlled for childhood family SES. Although neither bilingualism nor childhood family SES was associated with behavioral performance, greater bilingual language experience was positively associated with the magnitude of the P3b effect. These findings indicate that, even after accounting for childhood family SES, lifelong bilingual language engagement may shape the neural mechanisms supporting attention allocation during dynamic stimulus tracking.
Solid‐State Red Carbon Quantum Frameworks With Narrowband Thermally Activated Delayed Fluorescence for Undoped LEDs With High‐Temperature Operational Stability
ABSTRACT High color purity and efficiency of red light‐emitting diodes (LEDs) are essential for true‐color displays. Solution‐processable undoped emission layers represent the ideal device architecture to enhance operational lifetime and reduce fabrication complexity. However, it remains challenging to achieve narrowband emission in solid‐state, which requires reducing vibrational coupling and suppressing the π–π stacking interactions between aromatic structures. Herein, we developed solid‐state red carbon quantum frameworks (SSR‐CQFs) that exhibit narrowband thermally activated delayed fluorescence (TADF) with a peak at 635 nm, a small full width at half maximum of 39 nm, and a high photoluminescence quantum yield of 64% in neat films. This exceptional optical performance originates from the designed undulating two‐dimensional framework of SSR‐CQFs, in which chromophores are covalently interconnected by flexible alkyl chains. The structure simultaneously confines π‐electrons within individual chromophore units, prevents charge‐transfer state formation, and suppresses interlayer π–π stacking. Consequently, solution‐processed undoped LEDs based on SSR‐CQFs achieve high‐color‐purity red emission (CIE: 0.658, 0.326) with a maximum external quantum efficiency (EQE max ) of 8.04%, and demonstrate exceptional stability ( T 85 of 116 h) under high‐temperature operation. This paper presents a novel strategy to achieve solution‐processable undoped carbon‐based LEDs that achieve combination of narrowband emission, high efficiency, and high operational stability.
Distinct psychophysiological biomarkers and risk stratification models for irritable bowel syndrome with constipation (IBS-C) and diarrhea (IBS-D)
Tunable Electronic Honeycomb and (Breathing) Kagome Lattices Through Molecular Orbital Design in 2D Metal‐Organic Frameworks
ABSTRACT The pursuit of quantum materials with honeycomb and Kagome lattices hosting flat and Dirac bands has predominantly focused on inorganic crystals, where electronic tunability is constrained by the rigidity of atomic orbitals. Metal‐organic frameworks (MOFs) offer an alternative paradigm, enabling band structure engineering through molecular orbital design, yet experimental realization remains elusive due to synthetic challenges. Here, we demonstrate the bottom‐up fabrication of two‐dimensional MOFs with precisely engineered frontier molecular orbitals (FMOs). By employing ligands with three‐fold rotational symmetry, we construct electronic honeycomb, Kagome, and breathing Kagome lattices through an on‐surface coordination chemistry approach, with the resulting structures directly resolved by scanning tunneling microscopy. Combined scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations reveal local density of states and projected‐band features that are consistent with tunable Dirac‐like and flat‐band‐like electronic states in the designed honeycomb and Kagome nanostructured lattices, establishing a solid‐state platform for band‐structure engineering. This work establishes MOFs as a versatile platform for exploring correlated quantum phases, bridging the gap between theoretical band engineering and experimental materials design.
Defect-mediated n-type to p-type transition and enhanced thermoelectric performance in Bi1.8−xNixSb0.2Te3 alloys
Abstract A systematic investigation pertaining to the low temperature (10–350 K) thermoelectric properties of Ni substituted Bi 1.8− x Ni x Sb 0.2 Te 3 alloys ( x = 0–0.08), it was synthesised employing solid state reaction method. X-ray diffraction studies verified the presence of phase pure rhombohedral structures. FESEM micrographs showed a morphological transition from hexagonal platelets to granular networks as the Ni content increased. Electrical transport measurements revealed a transition from n-type to p-type conduction for the sample x ≥ 0.06. This transition is attributed to the formation of acceptor defects, which increases the hole concentration as a majority charge carriers. The thermal conductivity decreased systematically from 1.7 to 1.0 Wm −1 K −1 at 350 K with substitution of Ni concentration, as a result of the increased phonon scattering due to the mass disorder and strain fields. The optimal composition ( x = 0.04) unveiled a maximum $$PF$$ and $$ZT$$ of 335 μW/mK 2 and 0.09 respectively at 350 K, $$ZT$$ has 125% increment over the pristine sample. These results validates that Ni doping effectively decouples thermal and electronic transport properties via controlled defect engineering. This controlled doping represents a viable strategy for advancing thermoelectric performance of Bi–Sb–Te system.
Profiling the Structural Heterogeneity of Monomeric α‐Synuclein From the Single‐Molecule Level Using MspA Nanopores
ABSTRACT Parkinson's disease (PD) is closely associated with the misfolding of α‐synuclein (αSyn) proteins, which remains obscure due to the long‐standing challenge to elucidate monomeric αSyn structure. Here, we present a novel single‐molecule technique to efficiently analyze αSyn monomer with Mycobacterium smegmatis porin A (MspA) nanopores. The nanopore signals elicited by αSyn consist of three distinct, reproducible current levels. Notably, through systematic measurement of αSyn fragments, reference peptide with α‐helical structure and molecular dynamics simulation study, we demonstrate that these current levels correspond to α‐helical and random‐coil structures within the protein. The α‐helical structures are successfully assigned to the specific αSyn subdomains. A biophysical parameter figure matrix derived from the αSyn signals is further generated and readily applied to profile the structural heterogeneity of monomeric αSyn variants. These results establish that MspA nanopores can directly sense the formation of α‐helical structure in individual αSyn monomer, which advances our capability to investigate this highly flexible pathological protein and may contribute to elucidating its misfolding mechanism.
Millisecond Aliphatic Iodonium‐Claisen Rearrangement Enabling Dual Functionalization of Alkenyl Iodanes
ABSTRACT The evolution of Claisen rearrangements through expansion of the central atom from classical oxygen to sulfur, nitrogen, and phosphorus has reshaped the reaction manifold by redefining substrates, enabling new modes of selectivity control, and enriching product diversity. Here we report an aliphatic iodonium Claisen rearrangement of alkenyl iodanes with suitable nucleophiles. Substitution of the classic oxygen center by an iodine(III) moiety enables allyl alkenyl iodonium species to undergo rearrangement at −78 °C with completion in less than 0.1 s, while broadening the scope of rearrangement partners to include allyl/propargyl silanes, α‑stannyl nitriles, TMSN 3 , TMSOAc, and phenols, thereby expanding the structural diversity of accessible products. Beyond furnishing conventional rearrangement products, the rearrangement intermediates can be intercepted intra‐ or intermolecularly by diverse carbon‐ and heteroatom‐based nucleophiles, enabling dual functionalization of alkenyl iodanes. Mechanistic studies rationalize the unusually rapid kinetics of the rearrangement and reveal a pronounced trans influence exerted by the hypervalent iodine center, which not only governs the assembly of reactive partners but also facilitates the rearrangement.