Browse Articles

Electrophile–Nucleophile Paired Heteronuclear Dual‐Site for Selective CO ₂ Photoreduction to Ethanol via Oxygen‐Tethered Asymmetric C–C Coupling

ABSTRACT Photocatalytic CO 2 reduction to valuable multicarbon products like ethanol is a promising strategy for solar energy conversion, yet remains challenged by kinetically constrained C–C coupling and competitive C–O cleavage toward ethylene. Herein, an electrophile‐nucleophile pairing strategy is developed by constructing atomically Cu–Zr heteronuclear dual sites within a porphyrinic framework, which can simultaneously reduce repulsion for C–C coupling and strengthen the C–O bond. The electron‐deficient Zr, as a strong oxygen‐affixed anchor, stabilizes critical *OCH intermediates via O‐coordination, while adjacent electron‐rich Cu sites drive *CO adsorption—inducing charge asymmetry between *OCH and *CO for kinetically favored dimerization. Subsequent hydrogenation selectively proceeds toward ethanol due to enhanced Zr–O stabilization that prevents C–O scission. The optimized catalyst achieved a near‐unity ethanol selectivity at 87.8 µmol·g −1 ·h −1 using water as a scavenger under a CO 2 pressure of 0.5 MPa, which further increased to 195.1 µmol·g −1 ·h −1 at 1.5 MPa. This work establishes mismatched electrophile‐nucleophile pairs as a versatile design principle for steering photocatalytic CO 2 reduction toward value‐added multicarbon products.

Acceptor Backbone Cationization via B ← N Functionalization Enables High‐Performance Porous n‐Type Organic Mixed Ionic‐Electronic Conductors for Biosensors

ABSTRACT The advancement of high‐performance n‐type organic mixed ionic‐electronic conductors (OMIECs) is pivotal to advancing organic electrochemical transistors (OECTs) for next‐generation bioelectronics. While current design strategies predominantly center on non‐ionic conjugated polymers, their inherently hydrophobic backbones lead to suboptimal ionic transport characteristics. To address this challenge, we introduce an ionic acceptor design strategy of backbone cationization via B ← N functionalization within bipyridine and bipyrazine frameworks. Leveraging these cationic acceptors, we synthesized two n‐type ionic polymer OMIECs, PBPyBF 3 , and PBPzBF 3 , which exhibit low‐lying LUMO levels as low as −4.0 eV, elevated backbone torsional barriers, and ordered microstructures. Most critically, backbone cationization via B ← N coordination significantly enhances hydrophilicity by inducing a distinct porous film morphology, facilitated by hydrogen bonding with processing solvents. This structural evolution translates to a dramatically improved volumetric capacitance of 581 F cm −3 . Consequently, OECTs based on cationic polymer PBPzBF 3 exhibit an exceptional normalized transconductance of 38.9 S cm −1 and figure of merit of 215.9 F cm −1  V −1  s −1 , ranking among the highest values reported for n‐type OMIECs to date. Notably, electrocardiogram sensors integrated with PBPzBF 3 ‐OECTs exhibit high signal‐to‐noise ratios and superior sensitivity. This work establishes fundamental structure‐property relationships governing ion‐electron coupled transport in conjugated polymers.

Harnessing Cation–Anion Synergistic Effect for High‐Performance Aqueous Zinc‐Ion Batteries

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) are promising for large‐scale energy storage due to environmental friendliness, inherent safety, and low cost. However, the practical deployment of AZIBs is hindered by notorious side reactions at the zinc (Zn) anode, which seriously deteriorate the battery stability and reversibility. Here, we propose guanidine sulfate (GS) as an electrolyte additive, leveraging a cation–anion synergistic mechanism to jointly inhibit side reactions. Both theoretical and experimental results confirm that the guanidine cation (CH 6 N 3 + ) preferentially adsorbs on the Zn anode surface, providing an electrostatic shielding effect that promotes uniform Zn deposition. Concurrently, the sulfate anion (SO 4 2– ) contributes to the formation of a robust solid electrolyte interface (SEI), effectively inhibiting dendrite growth and enhancing interfacial stability. Consequently, Zn||Cu asymmetric cells with GS deliver a high Coulombic efficiency of 99.6% over 1200 cycles, while Zn||Zn symmetric cells exhibit an extended lifespan exceeding 500 h at various current densities. Furthermore, the Zn||O d ‐NVO·nH 2 O full cells demonstrate outstanding cycling stability, retaining over 90% of initial capacity after 2000 cycles at current densities of 2 and 5 A g −1 . This research provides a viable electrolyte design strategy leveraging cation–anion synergy, offering new insights into electrolyte modulation and advancing the performance of AZIBs.

Electron‐Switching Astaxanthin Enables Programmable Triple‐Phase Interface Chemistry for High‐Loading All‐Solid‐State Lithium–Sulfur Batteries

ABSTRACT All‐solid‐state lithium–sulfur batteries (ASSLSBs) promise high energy density and intrinsic safety, yet their performance is fundamentally constrained by unstable triple‐phase interfaces among sulfur, conductive carbon, and solid electrolytes. Such instability leads to sluggish solid–solid sulfur redox kinetics, hindered charge transport, and severe chemo‐mechanical degradation. Herein, we demonstrate a biomolecular strategy using astaxanthin (AXT) as an electron‐switching interfacial regulator to simultaneously address these coupled challenges. Combined experimental and theoretical analysis reveal that AXT modulates electrolyte decomposition pathways in a coverage‐dependent manner via a localized “electron pocket” effect, favoring the formation of electrochemically active Li 2 S over insulating LiCl. Meanwhile, polar oxygen functional groups in AXT establish low‐potential corridors that facilitate Li + transport and stabilize key intermediates, thereby accelerating sulfur redox kinetics. In addition, the chain‐like molecular architecture of AXT acts as a flexible scaffold to buffer volume fluctuations and preserve interfacial contact integrity during cycling. Consequently, AXT‐modified ASSLSBs achieve exceptional electrochemical performance under high sulfur loading conditions, delivering an areal capacity of 16.56 mAh cm −2 at 9.49 mg cm −2 sulfur loading. This work establishes a biomolecule‐driven electronic engineering paradigm for programmable interface chemistry, offering a general strategy toward high‐energy‐density and durable solid‐state batteries.

RNA-triggered cell killing with CRISPR–Cas12a2

Alkali Cations Mediated Subnanochannels in MXene Membranes for Enhanced Selective Ion Transport

ABSTRACT Artificial ion nanochannels enabling precise discrimination between monovalent and multivalent cations are essential for resource recovery and ion separation. However, due to the inadequate differentiation of their transmembrane energy barriers, these nanochannels still face challenges in achieving high permeability alongside high selectivity. Herein, we report that a trisodium citrate‐mediated MXene laminar membranes (MLM‐CA‐3Na) possess highly permeable and selective Li + /Ca 2+ separation. As confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption spectroscopy, the uniform stacking of the citrate ligand/Na + synergistically modified MXene monolayer nanosheets has achieved highly ordered confined subnanochannels of MLM‐CA‐3Na membranes. Molecular dynamics simulations, potential of mean force calculations, and transport energy barrier analysis revealed that the confined subnanochannels of MLM‐CA‐3Na membranes efficiently regulate the dehydration and transport behaviors of Li + and Ca 2+ , leading to a pronounced differentiation in their transmembrane energy barriers. The obtained MLM‐CA‐3Na membranes exhibited a Li + permeation rate of 0.0725 mol m −2 h −1 , a Li + / Ca 2+ selectivity of 84, and long‐term durability over 100 h. This work identifies ligand‐cation interactions as key regulators for ion separation, providing a design paradigm for sustainable lithium extraction.

Quantitative Photoswitching of Spin States in <i>o</i> ‐Fluoroazobenzene‐Loaded Metal–Organic Frameworks

ABSTRACT The integration of photochromic guest molecules into spin‐crossover (SCO) metal‐organic frameworks (MOFs) offers a promising approach for optically regulating magnetic properties. Herein, we report a crystalline material, [Fe(bpn){Ag(CN) 2 } 2 ]· E ‐F 4 AB ( 1‐ E ) (bpn = 1,4‐bis(4‐pyridyl)naphthalene and E ‐F 4 AB = E ‐ o ‐tetrafluoroazobenzene), which displays an asymmetric three‐/four‐step SCO behavior. At room temperature, the material undergoes efficient (90%) and reversible E / Z photoisomerization of guest molecules upon alternating irradiation with green (530 nm) and blue (410 nm) light. Following green‐light irradiation, the crystal of 1‐ Z , containing 90% F 4 AB in the Z configuration, was obtained via a light‐induced single‐crystal‐to‐single‐crystal transformation. The E ‐to‐ Z isomerization of F 4 AB introduces steric constraints within the pores, effectively locking the host framework into the high‐spin (HS) state. Furthermore, by controlling the proportion of the Z isomer through variation of irradiation time, we achieve continuous and quantitative modulation of the HS fraction. This work provides the first direct structural evidence of guest‐driven light‐induced spin change (GD‐LISC), establishing a robust strategy for designing photoswitchable materials.

Recent Advances in Two‐Photon‐Activatable Metal Complexes for Photodynamic Therapy

ABSTRACT Photodynamic therapy (PDT) is a non‐invasive modality for cancer treatment, but its broader application remains constrained by two central limitations, that is, insufficient tissue penetration of excitation light and the limited performance of available photosensitizers (PSs). Two‐photon PDT (TP‐PDT) offers a powerful strategy by enabling near‐infrared excitation with deeper penetration, higher spatial precision, and reduced off‐target photodamage. In this context, metal complexes have emerged as particularly attractive TP PSs because their coordination frameworks allow precise control over spin–orbit coupling, excited‐state dynamics, redox reactivity, and reactive oxygen species generation through both Type I and Type II pathways. Recent advances show that ligand engineering, photo‐decaging strategies, supramolecular design, and nanostructuring can substantially enhance two‐photon absorption, charge separation, radical generation, and therapeutic efficacy, especially in hypoxic tumors. This review overviews recent progress in two‐photon‐activatable metal complexes for PDT, highlighting design principles and therapeutic advances across ruthenium‐, iridium‐, platinum‐, and related metal‐based complexes. Particular emphasis is given to how coordination design governs photophysical properties, biological performance, and treatment outcomes. Current challenges and future opportunities for the clinical translation of these systems are also discussed.

A 98-qubit trapped-ion quantum computer with all-to-all connectivity

In Situ Quantification of Hydrogen Radicals Disentangles Direct and Hydrogen‐Radical‐Mediated Pathways in Green Ammonia Electrosynthesis From Nitrate

ABSTRACT The electrochemical reduction of nitrate (ERN) to ammonia (NH 3 ) has attracted increasing attention as a sustainable route for nitrogen recovery and green ammonia production, enabled by major advances in electrocatalyst design over the past decade. Two mechanistic pathways are generally well‐recognized: direct electron transfer and a hydrogen radical (H*)‐mediated mechanism. However, the latter remains difficult to quantify under practical electrochemical conditions, limiting mechanistic comparison across catalyst configurations. Herein, Ni/Co, Ni/Pt, and Ni/Pt/Co electrocatalysts were investigated to elucidate the interplay between direct and indirect ERN pathways. Quantitative electron spin resonance (ESR) measurements of H* under ERN‐relevant conditions, combined with bulk electrolysis in the absence and presence of an H* scavenger, enabled direct correlation between H* availability and NH 3 production. Ni/Co predominantly follows direct electron transfer, whereas Ni/Pt transitions to an H*‐mediated regime above a threshold current density. In contrast, Ni/Pt/Co exhibits synergistic behavior in which both pathways coexist. Moreover, the H* role varies with electrocatalyst chemical composition, facilitating either NO 3 − activation or NO 2 − hydrogenation. These findings establish a quantitative framework for resolving H*‐mediated contribution in ERN and provide mechanistic design principles applicable to other electrocatalytic hydrogenation reactions.

Asymmetric Zn─N ₂ O‐Coordinated Hydrogen‐Bonded Organic Frameworks for Electrochemical Hydrogen Peroxide Production and Wastewater Purification

ABSTRACT Hydrogen‐bonded organic frameworks (HOF) demonstrate significant potential in the electrocatalytic synthesis of hydrogen peroxide. However, their practical application is severely hindered by the uncontrollable structural evolution of their skeletons during material synthesis which poses a challenge for constructing well‐defined active sites. In this study, Zn was incorporated into the HOF to fabricate Zn‐functionalized HOF (Zn‐HOF) with asymmetric Zn─N 2 O coordination configuration. Theoretical calculations and screening reveal that compared with common transition metal (Mn, Fe, Co, Ni, and Cu) systems, this asymmetric Zn─N 2 O coordination effectively regulates the electronic structure, achieving optimal adsorption on the *OOH intermediate for the 2‐electron oxygen reduction reaction. Experiments confirm the Zn‐HOF catalyst achieves 96% maximum H 2 O 2 selectivity, enabling efficient H 2 O 2 production in unpurified tap or natural lake water with 89% Faradaic efficiency. Moreover, Zn‐HOF can degrade various antibiotic pollutants, the Zn‐HOF‐loaded sandwich reactor exhibits only 0.87 kWh·m −3 energy consumption, with its single‐electrode cost merely 1/32 that of platinum‐coated electrodes. Our work provides a viable pathway for the application of HOF‐based materials in environmental remediation.

Author Correction: Ontogeny and transcriptional regulation of Thetis cells

Photocatalytic Cascade Nitrogen Fixation for Selective Purification of Methane‐Rich Coal‐Bed Gas Over a Bimetallic MOF

ABSTRACT CH 4 ‐rich coal‐bed methane (CBM) is often contaminated with N 2 , but their similar properties make conventional separation energy‐intensive and inefficient. Herein, we report a photocatalytic strategy for selective N 2 conversion over CH 4 , achieving simultaneous CBM purification and nitrogen valorization. A Co‐Ni metal‐organic framework (CoNi‐PYZ) features isolated bimetallic sites, where ligand/Co units donate electrons to Ni, establishing spatially separated reduction and oxidation centers. This structural motif drives a photocatalytic cascade nitrogen fixation that N 2 is first reduced to NH 3 at the Ni sites; subsequently, the generated NH 3 outcompetes CH 4 for the Co sites, leading to its oxidation to NO 3 – . This remarkable selectivity is governed by the high polarity and lone‐pair electron donation of NH 3 , favoring its adsorption over nonpolar CH 4 . Notably, the optimal catalyst achieves high activity under mild conditions without sacrificial agents, delivering NH 4 + and NO 3 – production rates of 599.8 and 199.8 µmol g − 1 h − 1 , respectively. Mechanism analysis reveals that ligand engineering optimizes the d‐band center to balance adsorption and desorption, thereby minimizing the rate‐determining step barriers for both half‐reactions, consistent with the Sabatier principle. This work provides a reaction‐driven alternative to traditional phase‐separation, establishing a novel paradigm for CBM upgrading coupled with selective N 2 transformation.

Cobalt Nanoparticles Confined in Defective Carbon Matrices for Robust Intermittent CO ₂ Methanation

ABSTRACT The development of robust catalysts for CO 2 methanation under intermittent operating conditions is key to harnessing renewable energy sources such as wind and solar. However, this pursuit faces two major obstacles. The heating‐cooling cycles induce prolonged thermal stress, resulting in catalyst deactivation. Moreover, the temperature‐sensitive selectivity hampers the ability to maintain high methane yield, leading to undesired by‐products. Herein, we report cobalt nanoparticles confined within carbon matrices, which achieved 82.3% CO 2 conversion and &gt; 99% CH 4 selectivity over multiple heating‐cooling cycles toward intermittent CO 2 methanation. The catalyst robustness arises from the low coefficient of thermal expansion and high thermal conductivity of the carbon matrix, which effectively mitigates thermal stress during temperature fluctuations. Mechanistic studies confirm that the reaction proceeds via a formate pathway, which contributes to the high CH 4 selectivity across a wide temperature range. These insights provide a design framework for developing robust catalysts, advancing CO 2 methanation performance, and the efficient use of fluctuating renewable energy sources.

Covalent Confinement of AuCu Nanoclusters in Metal‐Organic Frameworks for Photocatalytic CO ₂ Reduction to C ₂ Hydrocarbons

ABSTRACT Bimetallic alloy nanoclusters provide an ideal platform for photocatalytic CO 2 reduction owing to their synergistic, charge‐polarized electronic effects that facilitate C─C coupling. However, their application is hindered by three major challenges: poor stability associated with their ultrasmall size, difficulty in precise multi‐metal composition control, and the lack of universal ligand‐anchoring strategies. Herein, we report the first family of covalently stabilized, composition‐tunable AuCu alloy nanoclusters confined within an N‐heterocyclic carbene (NHC)‐functionalized metal‐organic framework (MOF, UiO‐68‐NHC‐Au x Cu 10‐x , 4 ≤ x ≤ 10) via robust metal‐NHC covalent bonds. The porous framework spatially confines ∼2 nm alloy nanoclusters to prevent aggregation while enabling precise modulation of the Au:Cu composition. Among the series, UiO‐68‐NHC‐Au 4 Cu 6 exhibits the highest photocatalytic performance, achieving a C 2 hydrocarbon evolution rate of 42.5 µmol g −1 h −1 with a C 2 selectivity of 77% (electron‐based), outperforming the vast majority of MOF/metal heterojunction and metal nanocluster‐based photocatalysts. In situ spectroscopic investigations and computational studies reveal that the synergistic Au─Cu sites promote C─C coupling via the formation of *COCOH intermediates, a pathway that is thermodynamically unfavorable over monometallic Au─Au sites. This work establishes a robust strategy for constructing MOF‐confined bimetallic nanoclusters with synergistic active sites, achieving efficient and selective CO 2 photoreduction to high‐value multi‐carbon products.

Fundamentals, Measurement and Regulation of the Conductance of Single Molecule Junctions

ABSTRACT The miniaturization of conventional silicon‐based devices is one of the pinnacles of achievement of the 20 th century which evolved according to Moore's prediction, demanding a higher number and smaller size of electronic components each year. One path forward is the incorporation of atoms and molecules as small, low‐cost, and stable structures in electronic circuits and their integration into complex architectures which have been a desire of the nanoscale community for many decades. At the quantum physics scale, the unique physical and chemical properties of single molecules could lead to numerous new and interesting phenomena that are not accessible using conventional approaches, resulting in the emergence of a wide variety of device functionalities and applications, for example, nano‐switches, single‐molecule sensors, and spin filters. Although single‐molecule electronics is still at an early phase, the investigation of charge transport through molecules and their dynamics at the nanoscale is fundamentally important to understand the relevant scientific concepts and technological applications. We briefly review the history of molecular electronics as well as the fundamentals and theories required to understand charge transport through molecules. We provide an overview of methods to fabricate single‐molecule junctions with a focus on STM‐based approaches, their advantages, and limitations. The review highlights new insights and the latest progress on the structure‐property relationship of single‐molecule junctions that includes the effect of anchoring groups, molecular orientation in the junction (anisotropy of conductance), molecule‐electrode binding (denticity), and the role of solvent on charge transport at the nanoscale. We also highlight how advances in machine learning and molecular dynamics techniques have impacted theoretical and computation‐based approaches to studying molecular electronics. We then summarize the contribution of advanced statistical analysis and machine‐based approaches to the analysis of single‐molecule conductance data. We wrap up the review with a discussion on new materials for molecular electronics, as well as current challenges and the outlook in the development of practical molecular electronics.

Supramolecular Chloride Reservoirs Enable Homogeneous Halide Distribution and Near‐Unity Blue Luminescence in Cs ₄ PbBr ₆ ‐CsPbBr ₃ Heterostructured Perovskites

ABSTRACT Blue‐emitting metal halide perovskites remain difficult to stabilize because mixed‐halide compositions suffer from halide heterogeneity, defect formation, and rapid phase segregation. Here, we report a supramolecular host engineering strategy that stabilizes mixed‐halide perovskites using a quaternary ammonium chloride‐functionalized cationic β‐cyclodextrin (C‐βCD). The cyclodextrin host simultaneously functions as a chlorine reservoir, defect passivator, and supramolecular stabilizer, enabling homogeneous halide incorporation and strong host–guest interactions with the Cs 4 PbBr 6 ‐CsPbBr 3 heterostructured perovskite surface. This cooperative regulation effectively suppresses halide segregation and non‐radiative recombination, yielding tunable blue emission with exceptional color purity and a near‐unity photoluminescence quantum yield (PLQY) of 99.9%, among the highest values reported for blue‐emitting perovskites. The resulting supramolecular perovskite luminescent membranes further exhibit remarkable stability against water exposure (93.3% of initial PL intensity retained after 626 h) and ambient environmental stress (a PLQY half‐life of 27457 h), establishing a new benchmark for environmentally robust blue emitters. Integration of the supramolecular perovskites within porous membranes enables multifunctional operation, including foldable display, white light‐emitting diodes, as well as pioneer application of fluorescence detection and visible‐light‐driven degradation of perfluorinated pollutants. These results highlight supramolecular host–guest chemistry as a powerful molecular strategy for stabilizing mixed‐halide perovskites and engineering robust luminescent materials.

Layered Copper‐Anthraquinone Coordination Polymer Cathode Leveraging Dual‐Redox Sites and Facilitated Ion Diffusion for High‐Performance Lithium‐Ion Batteries

ABSTRACT Organic electrode materials often face challenges of low electronic conductivity and high solubility in electrolytes. To address this, we synthesized Cu‐DHAQ, a layered metal‐organic coordination polymer using 1,4‐dihydroxyanthraquinone (DHAQ) as the ligand and Cu 2+ as the metal center. Coordination polymerization effectively suppresses DHAQ dissolution and enhances cycling stability. The extended π‐conjugated framework promotes charge delocalization, improving conductivity, while the layered structure facilitates Li + diffusion. Cu‐DHAQ features dual redox‐active centers (Cu 2+ /Cu + and C═O/C─O − ), enabling a three‐electron transfer reaction. Benefiting from these synergistic effects, the Cu‐DHAQ cathode delivers a high discharge capacity of 260.5 mAh g −1 with 81.2% retention after 100 cycles, and maintains 119.4 mAh g −1 at 0.5 A g −1 . Furthermore, both coin and pouch full cells using Cu‐DHAQ cathode and pre‐lithiated hard carbon (Li‐HC) anode were successfully demonstrated, highlighting its potential as a high‐performance organic cathode material for lithium batteries.

Expression of Concern: Targeting tumor-associated genes, immune response, and circulating tumor cells in intrahepatic cholangiocarcinoma: Therapeutic potential of Atractylodes lancea (Thunb:) DC

From knowledge to judgment: A three-year longitudinal analysis of artificial intelligence large language model performance on the Chinese national nurse licensing examination

Background The rapid advancement of Large Language Models (LLMs) presents unprecedented opportunities for healthcare education and professional credentialing. However, comprehensive longitudinal analyses of their evolving capabilities in nursing contexts remain limited. Objective To conduct a three-year longitudinal performance analysis of major international and Chinese-native LLMs on the Chinese National Nurse Licensing Examination (NNLE) from July 2022 to June 2025, examining performance trajectories, comparative effectiveness, and domain-specific competencies. Methods We curated a comprehensive corpus of 9,800 multiple-choice questions from NNLE examinations (2022–2025) through validated educational resources. Fifteen leading LLMs were evaluated using standardized zero-shot prompting protocols, with temporal fidelity ensuring models were tested only on examinations administered after their release dates. Performance was measured as raw accuracy and benchmarked against the approximate 300-point passing threshold. Statistical analyses included trend analysis, comparative performance testing, and qualitative error categorization. Results LLM performance demonstrated a steep upward trajectory, with top-tier models achieving accuracy rates from 47.0% in 2022 to 78.8% in 2025. Chinese-native models consistently outperformed international counterparts. The mean Chinese-native advantage decreased from 6.1 percentage points in 2023 to 3.0 percentage points in 2025, while the top-model advantage remained present but non-monotonic, measuring 4.5, 3.0, and 3.8 percentage points in 2023, 2024, and 2025, respectively. Models exhibited superior performance in the knowledge-oriented Professional Practice section (81.6% average accuracy) versus the application-oriented Practical Skills section (70.9% average accuracy). Clinical reasoning failures, particularly in nursing intervention prioritization, constituted 43% of errors among top-performing models. Conclusion While state-of-the-art LLMs demonstrate substantial codified nursing knowledge sufficient to achieve approximate passing thresholds on professional licensing examinations, significant deficiencies in complex clinical judgment persist, defining the current boundary between artificial intelligence capabilities and human professional competence. Critically, examination performance should not be interpreted as evidence of clinical readiness or autonomous practice capability.