Browse Articles

NonCovalent Aggregation‐Driven D‐Band Engineering in Nickel Cocatalysts for Efficient CO ₂ Photoreduction

Abstract Efficient CO 2 activation remains a pivotal challenge in photocatalytic CO 2 reduction, necessitating precise electronic modulation of catalytic centers to overcome kinetic limitations. In this work, we engineer Ni(bpy) 3 Br 2 cocatalyst aggregates via noncovalent self‐assembly and systematically unravel the role of aggregation in governing photocatalytic performance. A synergistic combination of experimental and theoretical analyses demonstrates that symmetry disruption within the aggregates induces localized charge redistribution. Such a charge redistribution triggers a 0.6 eV upshift in the Ni d‐band center, which delivers lower Gibbs free energies for the formation of *CO 2 and *COOH. The optimized aggregates achieve a record‐high quantum yield of 26.84% at 450 nm with 99.3% CO selectivity, representing the highest performance reported to date for visible‐light‐driven CO 2 ‐to‐CO conversion systems. Importantly, the d‐band center of the Ni sites can be precisely modulated by varying the aggregation degree of Ni(bpy) 3 Br 2 . This work not only advances a novel d‐band center modulation strategy for electronic configuration engineering but also provides in‐depth atomic‐level insights into the aggregation‐induced symmetry‐regulated d‐band center.

Topochemical Polymerization of Retro‐Isomeric Peptides for Tuning the Polymer Structure and Properties

Abstract Peptidomimetic polymers containing hydrophobic amino acids and nonpeptidic linkages are interesting for various applications, particularly hydrophobic coatings. We synthesized two retro‐isomeric peptide monomers decorated with azide and alkyne, viz . N 3 ‐L‐Phe‐L‐Val‐NHCH 2 CCH ( M1 ) and its retro‐isomer N 3 ‐L‐Val‐L‐Phe‐NHCH 2 CCH ( M2 ), for topochemical azide–alkyne cycloaddition (TAAC) polymerization. On heating the crystals at 100 °C, both monomers underwent TAAC polymerization, yielding isomeric “difficult peptide” polymer mimics. The monomers showed stark differences in reactivity and regiochemistry of the product formed. Monomer M1 yielded polymer P1 having a 1:1 ratio of 1,4‐ and 1,5‐triazolyl‐linkages, and monomer M2 reacted regiospecifically, giving 1,4‐triazolyl‐linked polymer P2 . We investigated the hydrophobicity of these isomeric polymers by measuring water contact angles (WCA) of surfaces coated with these polymers; P1 and P2 showed WCA of 120° and 132°, respectively. Our study demonstrates that sequence reversal is a novel approach for accessing structurally and functionally different polymers via topochemical polymerization.

Revealing the Correlation of Loading‐to‐Performance of Single Atom Catalysts

Abstract The correlation between metal loading and overall catalytic performance remains elusive for single‐atom electrocatalysts (SACs), which hinders the oriented optimization of active site densities and scalable synthesis of them. To effectively address this issue, Ru single atoms with different loading are anchored on the graphene‐like framework and tungsten carbide substrate (WC 1‐x ) to investigate the synergistic effect among different local configurations. X‐ray absorption spectroscopy demonstrated that the loading of Ru atoms critically governs the interatomic distance between adjacent metal active sites at second shell coordination. In situ Raman spectroscopy shows that WC 1‐x nanoparticles can break the hydrogen bond network by reorienting H 2 O molecule adsorption and promoting the availability of active H 2 O among electrode‐electrolyte interface. Density functional theory (DFT) calculations demonstrated that the moderate distance between active sites could further lower the reaction barrier and enhance the catalytic activity. Consequently, the optimal sample Ru‐WC 1‐x with 0.76 wt% Ru loading exhibits a low overpotential of 7 mV at 10 mA⋅cm −2 and the anion exchange membrane electrolyzer to stably operate for 100 h at 1 A⋅cm −2 . Such correlation of spatial effects between different active sites were universally demonstrated in similar systems anchored with either Pt, Ir, or Co elements.

Framework Nucleic Acid‐Mediated DNAzyme Chaperoning for Sensitive Trace Metal Ion Mapping on Live Neuronal Cell Membranes

Abstract The transient release of metal ions at neuronal cell membranes holds significant implications in neurophysiology and pathology. Consequently, there is a pressing need for sensitive methodologies capable of quantitatively mapping local metal ion concentrations in live cells, aiming to unravel potential mechanisms underlying neurological disorders. DNAzymes have emerged as versatile tools for metal ion detection in live cells, owing to their specificity and other inherent advantages. Efforts to broaden their utility have focused on enhancing the stability and sensitivity of DNAzymes. Inspired by the beneficial effects of molecular chaperones on the stability and functionality of proteins, we present in this study the development of tetrahedral DNA frameworks (TDF) as chaperones for DNAzymes, aiming at enhancing the stability and activity of DNAzymes. Integration of TDF with DNAzymes is shown to significantly enhance metal ion detection performance, resulting in elevated stability and a two‐fold increase in sensitivity, attributed to alterations in the local net charge induced by TDF. In vitro investigations demonstrate that the nanodevice developed here faithfully maps Cu 2+ concentrations within a range of 0–10 µM on the membrane of neuronal cells, meeting the requirements for Cu 2+ sensing under both physiological and pathological conditions. This work presents an easily adaptable approach to enhance the performance of DNAzymes and lays the foundations for the development of other DNAzyme‐based sensitive detection nanodevices.

Sulfur Mediated Interfacial Proton‐Directed Transfer Boosts Electrocatalytic Nitric Oxide Reduction to Ammonia over Dual‐Site Catalysts

Abstract Electrocatalytic nitric oxide reduction reaction (NORR) for ammonia (NH 3 ) synthesis represents a sustainable strategy that simultaneously realizes the nitrogen cycle and resource integration. The key issue hindering the NORR efficiency is accelerating proton (*H) transfer to facilitate NO hydrogenation while inhibiting the hydrogen evolution reaction (HER). Herein, we demonstrate an interface‐engineered sulfur‐mediated Cu@Co electrocatalyst (S‐Cu@Co/C) that boosts NORR performance through dual modulation of electronic structure and proton transfer on active sites. A comprehensive program of experimental and theoretical calculations was employed to discover that sulfur incorporation induces electron redistribution in the Cu–Co interface, creating electron‐rich sulfur and electron‐deficient metals. This electronic configuration synergistically enhances NO adsorption on Cu sites and promotes water dissociation on Co sites. More critically, sulfur could direct the rapid transfer of *H from Co to Cu sites, thereby accelerating the NO hydrogenation and suppressing HER. Consequently, S‐Cu@Co/C achieves an NH 3 yield rate of 655.3 µmol h −1  cm −2 in a flow cell and a Faradaic efficiency of 92.4% in an H‐cell. Remarkably, the catalyst could maintain continuous electrolysis tests and steady NH 3 yield up to 100 h. This work provides innovative insights into the fabrication of efficient electrocatalysts via heteroatom‐mediated interfacial engineering strategies.

Local Electric Field Microenvironment‐Induced Dynamic Spatial Confinement to Stabilize I ⁺ Toward High‐Mass‐Loading and Stable Zinc–Iodine Batteries

Abstract Four‐electron iodine conversion chemistry (I −/ I 2 /I + ) endows zinc–iodine batteries with competitive energy density. The stability of I + conversion relies on its interaction with sufficient nucleophilic species (e.g., Cl − , Br − ). However, under high iodine loading, nucleophilic species fail to afford sufficient coordination strength and number within thick iodine cathode to stabilize I + , thus compromising the high‐voltage plateau and capacity. Here, we effectively spatially confine nucleophilic species (Cl − ) on the cathode by ─C─N + ‐induced localized electric field (LEF) microenvironment in polyquaternary ammonium iodide (PDDA‐I). Spatial confinement maximizes Cl − concentration on the cathode ensuring highly reversible I 0 /I + conversion, even in the low‐concentrated ZnCl 2 addition and high iodine loading. Importantly, the dynamically regulated Cl − maintains a balance with iodine species at the ─C─N + sites during cycling, effectively limiting the shuttling effect of polyiodides. Consequently, even adopting a high iodine loading of 16.03 mg cm −2 , the PDDA‐I still maintains a distinct four‐electron‐conversion dual voltage plateau with a remarkable capacity of 4.97 mAh cm −2 . An impressive lifespan of 10 000 cycles is achieved at 12.6 mg cm −2 with a capacity decay of 0.0012% per cycle, exceeding conventional iodine cathodes by 20‐fold. This work provides an important reference for high‐performance four‐electron conversion zinc–iodine batteries at high iodine loading.

Inside Back Cover: Confining Asymmetrically Coordinated Cobalt Single‐Atoms/Clusters on Holey MXene for Ultrafast Fenton‐Like Catalysis (Angew. Chem. Int. Ed. 35/2025)

Reductive N ₂ Cleavage and Nitride Insertion Reactivity at Molybdenum Complexes Supported by a Rigid PNP Pincer

Abstract Metal‐nitride species represent key reactive intermediates in reductive N 2 cleavage and functionalization. Toward a better understanding of nitride transfer reactivity, we present a series of Mo‐nitride complexes supported by a rigid diphosphino‐acridane pincer ligand. Notably, the stepwise reduction of a Mo IV Cl 3 complex under N 2 allows the isolation of a bridging diazenido intermediate as well as a dinuclear Mo‐nitride species ( 4 ) accommodating a bridging N 2 moiety. This is the first example of a Mo(IV) nitride‐N 2 species, and extensive 15 N‐labeling studies were performed to characterize the bridging dinitrogen, diazenido, and nitride moieties. The structure of 4 adopts two orthogonal π‐backbonding interactions between N 2 and two structurally rigidified Mo IV (N) fragments featuring a filled d π orbital. Effective π‐backbonding from such a Mo IV (N) fragment leads to the isolation of PMe 3 , CO, and CN t Bu substituted analogues. Further, reactivity of the Mo‐nitride species with π‐acidic CO and isocyanide leads to the formation of Mo II ‐isocyanate and ‐carbodiimide species, respectively. Computational studies suggest that nitride carbonylation proceeds via an associative nitride insertion pathway, encouraging further studies in direct N 2 fixation to value‐added products via nitride functionalization.

Unlocking the Power of Lewis Basicity in Oxide Lattice Oxygens: A Regulating Force for Enhanced Oxygen Evolution Kinetics in Li‐O ₂ Batteries

Abstract Lithium‐oxygen batteries (LOBs) require fast oxygen conversion kinetics to achieve good cycling performance and high energy efficiency. In the text of catalysts for LOBs, the Lewis basicity of lattice oxygens (O L ) in common transition metal oxides is often underestimated due to the weak electron donor characteristic of O L . In this work, a new spinel‐type high entropy oxide with Lewis basicity (LB‐HEO) was synthesized through a Joule‐heating method. O L was activated by regulating the tetrahedral site‐O L ‐octahedral site (M Td ‐O L ‐M Oh ) units in the spinel‐type HEO, enhancing the LB. Used as a cathode catalyst for LOBs, LB‐HEO could attract Li + and increase the disorder in discharge product, lithium peroxide (Li 2 O 2 ), promoting the delithiation process and the interfacial charge transfer at the LB‐HEO|Li 2 O 2 interface. The activation energy of interfacial charge transfer was significantly reduced from 63.5 to 22.4 kJ mol −1 . As a result, a low charging overpotential of 0.97 V and a long cycling lifespan of 135 cycles at 100 mA g −1 were achieved with a capacity limitation of 1000 mAh g −1 . The strategy based on the regulation of Li + behavior through its interaction with Lewis bases provides a promising prospect for the design of non‐noble metal catalysts for high‐performance LOBs.

Boosting Performance of Quasi‐Solid‐State Zinc Ion Batteries via Zincophilic Solubilization

Abstract Hydrogel electrolytes hold great promise in tackling severe issues facing aqueous zinc‐ion batteries (AZIBs). However, to satisfy the quest of flexible and eco‐friendly batteries, developing low‐cost and high mechanical durability hydrogel electrolyte remains a challenge. Here, employing the zincophilic solubilizer urea, we break the classical concentration limits of the low‐cost Zn(Ac) 2 salt and introduce it into the hydrogel skeleton. The “salting out” effect give the polymer chain sediments a tighter bundle and twist effect. The as‐formed hydrogel electrolyte can endure 557% high elongation and 3.7 MPa compressive strength to resist repeated zinc plating/striping process and external physical stimuli. The in situ polyurea solid electrolyte interphase (SEI) layer leads to thermodynamically stable anode/electrolyte interface. Utilizing the hydrogel electrolyte, the zinc anode shows high reversibility, leading to an average Coulombic efficiency (CE) of 99.93% for 150 cycles on the Zn//Cu battery. When assembled with NH 4 V 4 O 10 cathode (NVO), the full battery delivers a high capacity of 253.8 mAh g −1 beyond 1000 cycles longevity at 1 A g −1 . The pouch battery also shows a high capacity of 280.7 mAh g −1 at 500 mA g −1 and operate steadily for 90.13% retention after 200 cycles, and maintained a stable voltage even experienced bending and folding.

Nuclear Quantum Confinement Enables Robust Deuterium Bonds for Highly Reversible Aluminum Anodes

Abstract The hydrogen evolution reaction (HER) fundamentally limits aluminum electroreduction in aqueous electrolytes by dominating interfacial charge transfer. Here, we suppress HER by engineering deuterium bonds (D‐bonds) through nuclear quantum effects, confining D between D₂O and DMF molecules. This quantum confinement weakens hydrogen delocalization and restructures the Al 3+ solvation sheath, reducing water activity kinetically and thermodynamically. The regulated electrolyte enables uniform aluminum nucleation and dense plating layers, achieving 569 h (0.05 mA cm −2 ) and 379 h (0.1 mA cm −2 ) cycling stability in the 2D 2 O/1DMF electrolyte, which outperforms traditional sulfate electrolytes by 3.6 and 6.1 times, respectively. Our work uniquely leverages nuclear quantum confinement to engineer robust D‐bonds, simultaneously suppressing HER and enabling atomic‐level control over aluminum ion solvation structures for unprecedented Al redox reversibility in sulfate electrolytes. This exemplification pushes the electrolyte engineering from extensive component adjustment to quantum precision engineering, which provides an innovative solution for the high‐activity water‐based battery system

Solution‐Processed Amorphous Zero‐Dimensional Organic Metal Halide Hybrid Films for Direct X‐Ray Detectors

Abstract Zero‐dimensional (0D) organic metal halide hybrids (OMHHs) are emerging materials with significant potential for optoelectronic applications, including direct X‐ray detectors. While 0D OMHH single crystals exhibit excellent X‐ray detection properties, their scalability remains a significant challenge due to the time‐intensive growth process and difficulty in producing large single crystals exceeding a few centimeters. This limitation hinders their practicality for large‐area detector applications. Here, we report for the first time the development of amorphous 0D OMHH films via solution processing for efficient direct X‐ray detection. By reacting a non‐crystalline organic halide, triphenyl(9‐phenyl‐9H‐carbazol‐3‐yl)phosphonium bromide (TPPCarzBr), with zinc bromide (ZnBr 2 ), we have successfully produced amorphous 0D (TPPCarz) 2 ZnBr 4 films with controlled thickness via facile solution processing. The organic cations (TPPCarz⁺) feature a lower bandgap than the ZnBr 4 2− anions, enabling efficient molecular sensitization, where ZnBr 4 2− anions serve as X‐ray absorbers and TPPCarz⁺ cations as charge transporters. Direct X‐ray detectors based on 0D (TPPCarz) 2 ZnBr 4 films demonstrate outstanding performance, achieving a stable X‐ray detection sensitivity of 2,165 µC Gy air ⁻ 1 cm⁻ 2 at 20 V   mm⁻¹ and a detection limit of 6.01 nGy air   s⁻¹. The amorphous nature of these films enhances their processability, allowing for fabrication in various sizes and shapes, and making them highly adaptable for scalable detector applications.

Vacancy‐Induced Atomic Diffusion in a Molecular Metal Cluster Complex

Abstract The presence of atomic vacancies in a close‐packed material is believed to allow the migration of atoms adjacent to the vacancies, which induces dynamics of atoms. However, it is not known whether atoms in discrete molecules can undergo vacancy‐induced dynamics. We describe herein the generation of a close‐packed Pd 12 cluster complex [Pd 12 (C 7 H 7 ) 6 ][B(Ar F ) 4 ] n ( n  = 2, 3) with a Pd‐atom vacancy, and the observation of the diffusion of Pd atoms. Variable‐temperature NMR analysis, X‐ray structure analysis, and theoretical calculations indicate that an atomic vacancy is located at the surface sites of the Pd 12 core, and that it migrates rapidly on the NMR timescale. This means that all 11 palladium atoms at the surface undergo self‐diffusion with a low energy barrier. These results demonstrate, for the first time, that atomic diffusion occurs within a molecule through the vacancy mechanism.

The impact of green infrastructure on ecosystem quality based on explainable machine learning: a case study of Shanxi Province, China

Photocatalytic Reduction of CO ₂ to CO in 100%: The Synergistic Effect of Nickel and Europium in Heterometallic Clusters

Abstract Heterometallic transition‐rare earth metal (3d‐4f) clusters with synergistic catalytic activity are rarely identified. Herein, two families of closely related 3d‐Eu clusters were designed to analyze the role of Eu(III) ions during the photocatalytic reduction of CO 2 into CO. The [M 24 Eu 8 ] family, where M = Co or Ni, shows much lower activity (CO production < 2078  µ mol g −1 h −1 ) compared to the [M 24 Eu 10 ] family (CO production > 5838  µ mol g −1 h −1 ). This is due to the two additional Eu(III) ions in the apical position of the latter which are very active for converting CO 2 into CO. Moreover, we found the nickel analogues are better than the cobalt ones, especially for [Ni 24 Eu 10 ] which exhibits 100% CO selectivity and very high efficacy of 6545.3  µ mol g −1 h −1 , while the [Co 24 Eu 10 ] only shows 55% CO selectivity. Therefore, the coexistence of both apical Eu(III) and Ni(II) ions has been experimentally revealed to be critical for this exceptional catalytic performance of the [Ni 24 Eu 10 ] cluster. As such, this work unambiguously reveals a synergistic effect of bimetallic catalysts and may open a new avenue for more sophisticated reaction design by using the heterometallic coordination clusters.

Exploring patient experiences of pain fatigue and physical activity in syndromic heritable thoracic aortic disease using mixed methods

Tandem‐Activatable PROTAC Prodrug for Tumor Biomarker‐Driven Near‐Infrared Opto‐Proteolysis

Abstract Tumor‐specific protein degradation is crucial for successful cancer treatment by proteolysis‐targeting chimera (PROTAC), which however still remains challenging. Here, we report a tandem‐activatable PROTAC prodrug (TAP) strategy for precise on‐tumor proteolysis in vivo. TAP is constructed by caging PROTAC with a tumor‐homing cyclopeptide through a tandem‐locking linker, which comprises a singlet‐oxygen ( 1 O 2 ) cleavable moiety, a near‐infrared (NIR) photosensitizer (PS) and a Cathepsin B (CatB)‐cleavable dipeptide substrate. The proteolytic activity of TAP is initially turned off but can be sequentially switched on by tumor biomarker enzyme CatB and NIR light. Such a tandem‐lock design ensures that PROTAC exclusively degrade oncoprotein target in tumor. The results revealed that TAP carried out a tumor‐selective degradation of bromodomain‐containing protein 4 (BRD4) under the cooperative action by CatB and NIR light, which further synergized with photodynamic therapy (PDT) by the PS to suppress tumor growth. This work thus presents the first tandem‐activatable approach for spatiotemporally controlled proteolysis to minimize the off‐tumor toxicity of PROTAC.

HIF-1α regulates the proliferation and differentiation of mouse cranial base sphenoid-occipital synchondrosis chondrocytes via PI3K/Akt signaling

Flame monitoring and anomaly detection in steel reheating furnaces based on thermal video using a hybrid AI computer vision system

Abstract Reheating furnaces are essential in steel manufacturing, ensuring steel reaches the optimal temperature for hot-rolling. Burners within these furnaces produce flames to maintain the necessary thermal conditions. However, inconsistent burner performance can result in irregular or extreme flames, compromising steel quality and production safety. Traditionally, flame monitoring has relied on human supervision, which is inefficient and prone to errors. To overcome these limitations, we propose a computer vision-based system for automated flame monitoring and anomaly detection. The system analyzes the video stream from a thermal camera that continuously monitors the furnace interior. Our methodology involves three steps: (1) detecting flames and furnace keypoints using a deep learning model, (2) quantifying flames across burner regions with traditional computer vision techniques, and (3) identifying anomalies using an interpretable machine learning model. Validation with real-world data from a large steel manufacturing facility demonstrates that the system achieves an F1 score above 80% in detecting anomalies across various burner zones. To support operators, the results are presented in a dashboard that provides both real-time and historical insights into furnace performance. This enables timely anomaly detection and intervention, ensuring safe, efficient, and high-quality steel production.

Chiral Cryptographic Key‐Based Fluorescence Encryption Enabled by Stimuli‐Responsive Metal–Organic Frameworks

Abstract Increasing threats of data forgery breaches necessitate the development of advanced encryption strategies beyond traditional cryptographic methods. Fluorescence encryption has emerged as a promising alternative, yet current systems suffer from low security due to simple, reversible stimuli responses. Here, we introduce a novel lock‐and‐key encryption system using a chiral cyclodextrin metal–organic framework (CDMOF), termed Zole@CDMOF (Zole = acetylated benzoimidazole), for enantioselective discrimination of phenylethylamine (PEA) enantiomers.Confined Zole serves as the lock, while PEA enantiomers act as the key, selectively triggering fluorescence turn‐on via acetyl─O bond cleavage and restoring excited‐state intramolecular proton transfer (ESIPT) of deacetylated Zole. Mechanistic studies reveal that enantioselectivity arises from thermodynamic differences and distinct hydrogen‐bonding interactions between PEA enantiomers. To enhance practical application, Zole@CDMOF is fabricated into a flexible sensor via scotch tape strategy, enabling visual indexing of enantiomeric excess. Additionally, we propose a barcode chiral encryption model, establishing a quadruply encrypted system with ultra‐high security—allowing only one out of approximately two million keys to decrypt. This study pioneers the first chiral cryptographic key in fluorescence encryption, paving the way for ultra‐secure encryption, advanced chiral sensing, and stimuli‐responsive materials.