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Prevailing views of cell senescence overlook its biological complexity

Stabilizing Water Dissociation Sites via Ethylenediamine Coordination for Industrial‐Current‐Density Alkaline Hydrogen Evolution Reaction

ABSTRACT Incorporating water dissociation sites into electrocatalysts significantly boosts the catalytic activity for the alkaline hydrogen evolution reaction (HER), yet the reconfiguration of these sites under industrial‐level current densities—an issue that has received limited prior attention—severely impairs catalytic stability. Herein, we construct a highly active and ultra‐stable hybrid electrocatalyst composed of metallic nickel and a hydroxy(ethylenediamine)nickel(II) complex (Ni[(OH) 2 en x ]/Ni) via a scalable cathodic alkalization strategy. The interface‐coupled Ni[(OH) 2 en x ] complex, featuring high oxophilicity and enhanced thermodynamical stability against reduction, not only accelerates the water‐dissociation step but also renders long‐term catalytic durability. The resulting hybrid catalyst delivers a low overpotential of 35.2 mV at 10 mA cm −2 and a small Tafel slope of 43.68 mV dec −1 , outperforming the benchmark Ni(OH) 2 /Ni and Ni(OH) 2 /Pt catalysts. When integrated into an anion‐exchange membrane water electrolyzer, the electrode delivers 500 mA cm −2 for 3000 h in 1.0 M KOH at 25°C. This work demonstrates the great potential of coordination complexes as robust active sites for Volmer step, a concept that can be extended to other electrocatalytic reactions involving water dissociation.

RiskSetDP: session-level differential privacy for survival analysis with risk-set–aware sensitivity control

In-cell chemistry enables discovery of cyclic peptide transcription factor inhibitors

Unassisted Electrocatalytic Hydrogenation Coupled With Aldehydes Oxidation on Bifunctional Pd–Cu Synergistic Sites

ABSTRACT Paired electrolysis enhances energy utilization efficiency by coupling anodic oxidation with cathodic reduction reactions, enabling the simultaneous production of high‐value chemicals. However, achieving the transition from electricity consumption to electricity generation in paired electrolysis remains a huge challenge due to mismatched potentials of anodic and cathodic reactions and lack of highly efficient active sites. Herein, we designed an electrochemical system that couples cathodic hydrogenation of various unsaturated compounds with anodic aldehydes oxidation reactions at a synergistic Pd–Cu bifunctional site. The paired hydrogenation and oxidation reactions were demonstrated to produce valuable products at both electrodes simultaneously without electrical energy input. Experimental studies and theory calculations indicate a Pd–Cu cooperative mechanism, which optimizes hydrogen transfer kinetics in both hydrogenation and oxidation reactions. Specifically, the Pd site promotes water dissociation to generate active hydrogen, which then spillover to the adjacent Cu site to catalyze hydrogenation, while the Pd site modulates the electronic structure of the Cu site, promoting C─H bond cleavage and facilitating H 2 generation during aldehydes oxidation. This study demonstrates that precise catalyst design and reaction system optimization can achieve efficient synergy between oxidation and reduction reactions in paired electrolysis, offering new insights and technological pathways for electrochemical synthesis of high‐value chemicals.

A resurrection experiment reveals the evolution of jack-and-master plasticity in a Mediterranean shrub

Facile B–N Covalent Bond Fusion in <i>N</i> , <i>N′</i> ‐Diaryldihydrophenazines: Achieving Efficient Narrowband Electroluminescence and Controlled Redox Activity

ABSTRACT Covalently fusing multiple B–N units into redox‐active polycyclic aromatic hydrocarbons (PAHs) offers a powerful strategy for creating π‐extended systems with novel functionalities, but it remains a formidable challenge. Here, we report a facile, one‐pot, and lithium‐free NH‐directed borylation to construct a series of 5,10‐dihydro‐5,10‐diphenylphenazine (DPPA) derivatives fused by two or four B–N covalent bonds. Such a multiple B–N locking is found not only to enforce molecular rigidity and suppress excited‐state structural relaxation, but also to profoundly modulate the electronic structure and antiaromaticity of the central DPPA core. Interestingly, the resultant quadruply fused system (4BN‐Ph) can function as an unprecedented narrowband orange‐red thermally activated delayed fluorescence (TADF) emitter, enabling efficient electroluminescence with a record‐high external quantum efficiency of 31.2% and a notably small full‐width at half‐maximum of 32 nm at an emissive peak of 595 nm. Also, 4BN‐Ph displays intriguing redox‐controlled properties, since a stepwise oxidation generates near‐infrared‐absorbing open‐shell radical cations and closed‐shell dications. This work establishes a modular route to PAHs incorporating multiple B–N covalent bonds, with exceptional optoelectronic and spintronic properties.

Comprehensive assessment of the occurrence, temporal and spatial changes, and ecological risks of heavy metals in the Northern Pearl River Estuary, China

Constructing Durable High‐Voltage PVDF‐Based Solid‐State Lithium Metal Batteries via an All‐in‐One Design

ABSTRACT Poly(vinylidene fluoride) (PVDF)‐based solid electrolytes represent a compelling frontier for solid‐state lithium metal batteries. Unfortunately, their practical implementation is severely impeded by high Li + migration energy barrier and pronounced interfacial instabilities, arising from α‐phase‐rich conformations and undesired Li + ‐solvation environments. In this study, an ‘all‐in‐one’ regulation strategy enabled by N‐methylimidazolium bis((trifluoromethyl)sulfonyl)imide (MimTFSI) is proposed, which synergistically engineers a β‐phase polymer matrix for shortened pathways and constructs an anion‐rich solvation sheath for lowered energy barriers, ultimately unlocking fast and stable Li + transport coupled with exceptional interfacial compatibility. Consequently, this integrated solid‐state electrolyte demonstrates a high ionic conductivity of 0.84 mS cm − 1 , supports stable cycling of Li symmetric cells for over 4000 h at 0.1 mA cm − 2 , and delivers outstanding cycling performance in Li/LiNi 0.8 Co 0.1 Mn 0.1 O 2 full cells, retaining 93.8% of its initial capacity after 930 cycles at 0.5 C and 95% over 500 cycles at 1 C. Even under expanded voltage windows, it retains 80% after 580 cycles at 4.4 V and 84% after 160 cycles at 4.5 V. Furthermore, the pouch cell is capable of delivering a discharge capacity of 3.26 mAh cm −2 , demonstrating the strong applicability for next‐generation solid‐state lithium metal batteries.

Immune cell landscape and metabolic gene activity distinguish triple negative from luminal A-like ductal carcinoma in situ

π‐Radical Cascades to <i>Peri</i> ‐Fused Triangulene Dimers

ABSTRACT Open‐shell molecular graphene fragments represent versatile synthons of graphene‐based carbon nanostructures because of their ability to undergo multi‐step π‐radical cascades that enable the formation of multiple bonds and rings in a single step. However, the use of graphene‐based π‐radicals in synthesis remains limited due to our incomplete understanding of their reactivity. This limitation primarily arises from the inherent difficulty of controlling reactions involving multiple reactive centers, as is the case with π‐delocalized radicals. To address this challenge and advance research on π‐radical reactivity, we establish reaction control in a system that can formally feature multiple unpaired π‐electrons. Specifically, we examine oxidative peri ‐fusion of the dihydro‐precursor of the prototypic non‐Kekulé hydrocarbon triangulene. By investigating the reactive intermediates that dictate selectivity, we demonstrate that monoradical, rather than diradical, intermediates play a key role. Through the precise placement of steric bulk around the periphery, we modulate reactivity at specific positions, steering selectivity toward doubly or singly peri ‐fused dimeric products. Our study demonstrates that, when controlled, the reactivity of open‐shell molecular graphene fragments can serve as a step‐economic and synthetically valuable tool.

Leaf anatomical plasticity of Robinia pseudoacacia in response to slope-related soil water heterogeneity on granite slopes

Structure–Selectivity Relationship Study of IDPi Using Fragment and Remote Site Descriptors

ABSTRACT Imidodiphosphorimidate (IDPi) has emerged as a powerful chiral organocatalyst featuring a specially designed cavity constructed by aryl group‐substituted BINOL units. Despite extensive applications of IDPi in asymmetric reactions, the understanding of its structure–selectivity relationship (SSR) remains underdeveloped. In this study, we employed aryl fragment descriptors for the statistical modeling of IDPi‐catalyzed asymmetric reactions, offering a cost‐effective and efficient approach to explore the SSR of IDPi. Specifically, site parameters of remote sp 2 carbon atoms were defined to capture the features of the distal ring of the aryl substituents. The established statistical models of IDPi‐catalyzed cyanosilylation reactions align well with the mechanistic understandings of the crucial role of C‐H···π and cation‐π interactions between the distal ring of IDPi and substrate in stereo‐control. More selective catalysts for the challenging cyanosilylation reaction of 3‐hexanone were successfully identified by using these descriptors to define and screen the chemical space of IDPi catalysts. This work not only enriches our understanding of the SSR of IDPi catalysts but also highlights the potential application of aryl fragment and remote site parameters as universal descriptors for IDPi in statistical modeling.

A semantically enhanced two-stage framework for few-shot named entity recognition

Crystal Facet‐Dependent Metal‐Support Interaction for Stabilizing Cu ^δ+ Species Toward Efficient CO ₂ Electroreduction

ABSTRACT Cu δ+ species are recognized as optimal active sites for the electrocatalytic CO 2 reduction reaction. While metal‐support interactions (MSIs) modulate the local microenvironment of Cu δ+ , the intrinsic contribution of support crystallographic facets to these interactions remains obscured by interfering oxygen vacancies. In this work, we present a definitive study decoupling the facet effect from vacancy‐related variables by utilizing CeO 2 supports with comparable oxygen vacancy concentrations. Our findings reveal that Cu single atoms supported on various CeO 2 facets follow a pronounced facet‐dependent stability order of Cu/CeO 2 ‐(110) &gt; Cu/CeO 2 ‐(100) &gt; Cu/CeO 2 ‐(111), yet exhibit facet‐independent methane Faraday efficiency (∼80% at −200 mA/cm 2 ). Mechanistic studies unravel this dichotomy, revealing that identical Cu coordination environments drive the uniform initial activity, whereas distinct surface electronic structures dictate long‐term stability by modulating facet‐dependent MSIs. Specifically, the (110) facet exhibits the strongest MSI, acting as a robust “electron buffer” that securely anchors high‐valent Cu δ+ species and effectively retards their irreversible reductive agglomeration into clusters. By establishing an unambiguous structure–performance relationship under single‐variable conditions, this study provides a rational geometric descriptor for designing long‐lasting CO 2 conversion catalysts.

Measuring agritourism sustainability with coupling coordination: a spatio-temporal study of agriculture-culture-tourism interactions in Chinese underdeveloped regions

Abstract The limited capacity for integration and innovation in rural industries continues to undermine the sustainability of underdeveloped regions. Scientifically assessing the coupled and coordinated development of multi-sector systems has therefore become essential to advancing rural resilience and sustainable transformation. This study introduces the Agriculture-Culture-Tourism Integration System (ACTIS) and captures the dynamic interactions among agriculture, cultural resources, and tourism. Drawing on panel data from representative underdeveloped rural areas during the period 2011–2023, it applies system coupling theory in combination with methods such as entropy-weighted TOPSIS, the coupling coordination model, the standard deviation ellipse, the Theil index, and the geographical detector to construct a comprehensive indicator system for evaluating ACTIS development, spatiotemporal evolution, and driving factors. The results reveal marked spatial and temporal heterogeneity, with uneven sectoral patterns and evolving regional disparities. Coupling coordination shows distinct phases of development and is shaped primarily by internal differences rather than interregional gaps, while infrastructure, geographical indications, human capital, and technological innovation emerge as key drivers. By examining the dynamics and driving mechanisms of ACTIS, this study extends system coupling theory to multi-sector rural contexts. The findings offer important theoretical insights and practical references for promoting industrial transformation, policy innovation, and sustainable development in underdeveloped regions globally.

Systemic epigenetic dysregulation as a driver of ageing and a therapeutic target

Toward Practical Design of High‐Entropy Catalysts for Chlorine Evolution Reaction via Pareto‐Guided Multi‐Objective Bayesian Optimization Enabled by a Robotic AI‐Chemist

ABSTRACT The electrocatalytic chlorine evolution reaction (CER) is essential to modern chlor‐alkali industry, yet conventional RuO 2 catalysts suffer from parasitic oxygen evolution. High‐entropy ruthenium oxides (Ru‐HEO) are promising alternatives, but their practical design is hindered by complex composition‐structure‐performance relationship. Herein, we construct a Pareto‐guided multi‐objective Bayesian optimization framework to enable autonomous high‐throughput exploration of quinary Ru‐HEO system. Through this trade‐off strategy, we identify compositions that efficiently balance mass activity, Cl 2 selectivity and material cost. The leading Ru‐HEO catalyst with only 8.4 at% Ru achieves a remarkable activity of 5083 A g −1 Ru at 1.50 V versus RHE and maintains excellent 100‐h stability, outperforming commercial RuO 2 and the state‐of‐the‐art catalysts reported. Integrated into a photovoltaic‐electrochemical (PV‐EC) prototype device and tested under simulated diurnal illumination, it sustains &gt;95% selectivity, a maximum solar‐to‐chemical (STC) efficiency of 14.6% and projected Cl 2 production costs as low as $0.177 per kg. Our work establishes a closed‐loop, AI‐accelerated research paradigm that integrates multi‐objective optimization with robotic experimentation, offering a generalizable and expedited pathway toward high‐performance electrocatalysts for sustainable chemicals manufacturing.

A transformer and large-kernel convolution-based detection model for Red Turpentine Beetle infestation in pine trees

Abstract Infestation by the Red Turpentine Beetle is one of the key factors threatening the ecological stability of pine forests, while traditional manual inspection methods are inefficient and easily influenced by subjective factors. UAV-based detection methods can significantly improve monitoring efficiency; however, small target scales, blurred details, and complex backgrounds in UAV imagery pose great challenges to detection algorithms. To address these issues, This paper proposes TLK-YOLO, a UAV-based method for detecting pine trees infested by the Red Turpentine Beetle, which integrates a Transformer mechanism with a large-kernel selection strategy. A Local Window Cross-Attention (LWCA) upsampling module is introduced to enhance small-object detail modeling by fusing high- and low-resolution information within local windows. A Dynamic Combined Large Selective Kernel (DCLSK) module adaptively adjusts the receptive field to balance global context and local details, improving small-object feature discriminability and robustness. Furthermore, a redesigned network architecture, TLK-NA, mitigates redundancy in shallow-to-deep feature propagation by reversing the information flow from deep to shallow layers, achieving a better trade-off between detection accuracy and computational efficiency. Experimental results demonstrate that TLK-YOLO exhibits remarkable performance in detecting Red Turpentine Beetle infestations from UAV imagery, achieving an mAP50 of 89.3%. Compared with the baseline model, TLK-YOLO attains comprehensive improvements in both detection precision and recall, with precision increases by 4.4%, recall precision by 9.6%, while mAP50 and mAP50-95 improve by 7.9% and 8.3%, respectively, while maintaining relatively low computational overhead. This network provides an efficient and reliable technical foundation for UAV-based forestry pest and disease monitoring.

Enantioselective Total Syntheses of (+)-Aconicarmichinium C and (+)-Pendulumine I: Strategic Use of a Bridgehead Enone via a Kinetic-Resolution-Enabled Intermolecular Diels–Alder Reaction