Browse Articles

Boron Doping‐Induced Ultrahigh Ce ³⁺ Ratio in Amorphous CeO ₂ /GO Catalyst for Low‐Concentration CO ₂ Photoreduction

Abstract Direct utilization of diluted CO 2 enables sustainable CO 2 conversion into valuable products, with reduced CeO 2 emerging as an attractive candidate due to its exceptional redox flexibility. The catalytic efficacy of CeO 2 is intimately tied to the electronic structure of 4 f , yet the persistent challenge lies in maintaining a high and stable concentration of Ce 3+ . In this study, we propose a symmetry‐breaking‐induced amorphization strategy to achieve an exceptionally high Ce 3+ ratio by B doping, which facilitates the reduction of Ce 4+ to Ce 3+ in amorphous CeO 2 . First‐principles calculations and infrared spectroscopy reveal that B doping with three excess electrons induces the formation of planar triangular B–O₃ units by disrupting the original high‐symmetry structure of CeO 2 , facilitating the spontaneous transition to the amorphous phase. Electronic structure analysis confirms that even a modest 7.5% B doping can significantly elevate the Ce 3+ ratio to 85.7%. The resulting amorphous B‐doped CeO 2 /GO shows a remarkable CO 2 ‐to‐CO conversion rate of 249.33 µmol g −1  h −1 (under 15% CO 2 ) and 103.4 µmol g −1  h −1 (under 1% CO 2 ), with 100% selectivity in both cases. This performance highlights how amorphization stabilizes defect states, making amorphous CeO 2 /GO with high Ce 3+ an effective material for CO 2 photoreduction and addressing key challenges in CO 2 capture and utilization.

ATP‐Assisted Electron and Proton Transfer Boosting Redox Metabolism‐Induced Ferroptosis and Apoptosis for Cancer Therapy

Abstract Compared to the intractability of traditional apoptosis, the vulnerability exposed by cancer cell metabolic reprogramming provides an advantage for ferroptosis treatment. Herein, we developed vanadate and aurintricarboxylic acid coordination nanoparticles (VAP NPs) that synergistically trigger dual cell death pathways. This nanoplatform leveraged dual‐Russell mechanisms and Fenton reactions to generate singlet oxygen/hydroxyl radicals in the tumor microenvironment (TME) while depleting glutathione via vanadium redox cycling, thereby silencing glutathione peroxidase 4 and modulating the Kelch‐like ECH‐associated protein 1 (KEAP1)/nuclear factor erythroid 2‐related factor 2 (NRF2)/heme oxygenase 1 (HMOX1) axis. Notably, TME‐overexpressed adenosine triphosphate (ATP) acted as a biochemical catalyst, accelerating the transfer of protons and electrons during reactive oxygen species generation to amplify therapeutic efficacy. Therefore, VAP NPs could achieve outstanding efficacy for intrinsically stimulated synergy of ferroptosis and apoptosis in tumor therapy. This study provides reference for revealing the new function of ATP in enhancing the regulation of redox metabolism.

Short-term study fails to capture negative impacts of livestock intensification on wildlife

Ionized Water Facilitates the Sustainable Radical‐Mediated Reduction of CO ₂ to Multi‐Carbon Hydrocarbons and Oxygenates

Abstract The abiotic synthesis of organic compounds from CO 2 and water under prebiotic conditions is a fundamental yet unresolved challenge in understanding the origins of life. Here we demonstrate a radical‐mediated pathway for reducing CO 2 to C 1 ‒C 6 hydrocarbons and oxygenates driven solely by ultraviolet (UV) irradiation of water, mimicking early Earth environments. Using electron paramagnetic resonance (EPR), 17 O/ 13 C isotope labeling, and femtosecond transient absorption, we identify ionized water‐derived radicals (H 2 O •+ , • OH, e⁻ aq , • H) as the key redox mediators. e⁻ aq acts as a super‐reductant (−2.9 V) to activate CO 2 into CO 2 • ⁻, while • H enables sequential hydrogenation. Critically, oxidative radicals (H 2 O •+ and • OH) recycle recalcitrant oxygenates (formate and oxalate) back into active CO 2 • ⁻, sustaining a dynamic radical network. This process generates a diverse library of organic compounds, including methane, ethylene, and C 6 dimethyl succinate, via radical assembly mechanisms spanning hydrogen‐atom transfer (HAT), self‐coupling, and cross‐coupling. By integrating experimental validation with prebiotic simulations (formate‐mediated redox modulation), we resolve the paradox of inert CO 2 /H 2 activation in primordial environments and establish water not merely as a solvent but as a reactive matrix directing abiotic organic synthesis.

A Novel Tandem Reaction System for High‐Concentration Acetic Acid Production from Methane and Oxygen

Abstract Directly converting methane into high‐value products like CH 3 COOH poses significant challenges owing to the kinetic limitations of C─H activation and C─C coupling in traditional single‐catalysis methods. This work systematically studied the compatibility and effectiveness of plasma and thermocatalytic tandem systems. By optimizing the plasma process in a self‐designed dielectric barrier discharge (DBD) reactor, we enhanced methane conversion (68.0%), methanol concentration (5.2 mol L −1 ), and CO selectivity (56.9%), while preventing carbon deposition and CO 2 formation. In subsequent thermocatalysis, we developed the stearic acid‐modified ReRh/ZSM‐5‐S hydrophobic catalyst to avoid the separation of methanol and CO from the mixture and minimize the influence of by‐products (e.g., H 2 O). This innovative approach achieved 52.0% CH 3 COOH selectivity and 1.3 mol L −1 concentrations, three orders of magnitude than traditional methods, meeting the preliminary industrial criteria. This study demonstrates the potential of tandem catalysis, offering valuable insights for the efficient utilization of methane and other challenging catalytic reactions.

Why excluding regenerative grazing skews beef’s carbon profile

Predator–Prey Behavior of Droplets Propelling Through Self‐Generated Channels in Crystalline Surfactant Layers

Abstract Motile droplets provide an attractive platform for liquid matter‐based applications and protocell analogues displaying life‐like features. The functionality of collectively operating droplets increases by the advance of well‐designed (physico)chemical systems directing droplet–droplet interactions. Here, we report a strategy based on crystalline surfactant layers at air/water interfaces, which sustain the propulsion of floating droplets and at the same time shape the paths for other droplets attracted by them. First, we show how decylamine forms a closed, crystalline layer that remains at the air/water interface. Second, we demonstrate how aldehyde‐based oil droplets react to decylamine in the crystalline layer by forming an imine, causing the droplets to move through the layer while leaving behind an open channel (comparable to “Pac‐Man”). Third, we introduce tri(ethylene glycol) monododecylether (C 12 E 3 ) droplets in the crystalline layer. The crystalline layer suppresses the motion of the C 12 E 3 droplets, however, the aldehyde droplets create surface tension gradients upon depletion of surfactants from the air/water interface, thereby driving Marangoni flows that attract the C 12 E 3 droplets as well as the myelin filaments they grow: Causing the C 12 E 3 droplets to chase, and ultimately catch, the aldehyde droplets along the channels they have created, featuring a predator‐prey analogy established at an air/water interface.

Sprayed Microdroplets Architect a Polyoxometalate Framework

Abstract Although many past attempts have utilized micron‐sized droplets for breaking and forming organic bonds, their potential in promoting inorganic bond formation reactions remains largely unexplored. We report a promising approach to synthesizing a tungsten‐based Lindqvist‐type polyoxometalate (POM) in various organic and aqueous microdroplets under ambient conditions, eliminating the traditional need for hazardous or corrosive chemicals and high‐boiling solvents. When aerosolized, a simple tungstate (WO 4 2− ) solution spontaneously produces a metal‐oxo cluster (W 6 O 19 2− ), a valuable POM with broad applications, achieving yields up to 99% in less than a millisecond. Mass spectrometric detection of reactive intermediates unraveled the nucleation mechanism in microdroplets, leading to the formation of polyoxotungstate, which was then further characterized by X‐ray crystallography. Empirical observations collectively suggest that rapid solvent evaporation and subsequent enrichment of reactants in the confined volume of microdroplets likely facilitate the growth of the POM through partial solvation at the air–liquid interface.

Entropy‐Driven Competitive Adsorption Sites Tailoring Unlocks Efficient Hybrid Conversion Zn–Air Batteries

Abstract Hybrid conversion Zn–air batteries (HC‐ZABs) epitomize a typical integrated energy storage and conversion device that advances green chemistry and reduces carbon emissions. However, balancing efficiency and selectivity of electrocatalytic cathodic reactions remains the bottleneck in such batteries. Herein, we address this issue by designing a high‐entropy perovskite, La 0.6 Sr 0.1 Ca 0.1 Rb 0.1 Y 0.1 CoO 3 (HE‐LCO), which outperforms conventional perovskites in offering enhanced electrocatalytic activity, better selectivity, and outstanding stability for cathodic benzyl alcohol oxidation reaction (BAOR). Combined spectroscopy characterizations, operando measurements, and theoretic calculations reveal that the entropy‐driven modulation of the second coordination sphere in HE‐LCO balances the adsorption of nucleophile benzyl alcohol and OH − , while inhibiting competing oxygen evolution reaction (OER). Based on this rationalized HE‐LCO electrocatalyst, HC‐ZABs realized efficient energy storage and benzoic acid production, boasting a long lifespan of 900 cycles at 20 mA cm −2 and 6.7 mAh cm −2 per cycle. Further, practical ampere‐hour‐scale HC‐ZABs demonstrated a 62.8% energy efficiency improvement and an average benzoic acid yield of 0.85 g per cycle, highlighting the potential of this integrated device for simultaneous sustainable energy storage and green electrochemical synthesis.

Regiospecific Halogenation Modulates Molecular Dipoles in Self‐Assembled Monolayers for High‐Performance Organic Solar Cells

Abstract Halogenated carbazole‐derived self‐assembled monolayers (SAMs) are promising hole‐extraction materials in conventional organic solar cells (OSCs). While halogenation helps optimize the molecular dipole, intermolecular interactions, and energetics of SAM, the highly polarizable carbon‐halogen bonds can be reactive and prone to photocleavage depending on their regiochemistry. Herein, we study the regiospecific properties, including the intrinsic stability, electrostatic potential (ESP) distribution, and changes in molecular dipole of the brominated SAM molecules by brominating a helical 7 H ‐dibenzo[ c,g ]carbazole‐based SAM (CbzNaph) featuring a stronger dipole. Additionally, a correlation between the intrinsic molecular stability and the derived SAM surface stability is established to determine the performance and stability of the OSCs. Notably, the bromination at the chemically inert sites of 7 H ‐dibenzo[ c,g ]carbazole (JJ26) helps maximize molecular dipole while maintaining superior intrinsic stability. Together with dense assembly promoted by the synergistically enhanced intermolecular interactions and crystallinity, JJ26 can efficiently modulate the work function (WF) of indium tin oxide (ITO) and enhance the stability of SAM under external stress. Consequently, the JJ26 derived OSC shows significantly improved performance, achieving an efficiency of 19.35% along with notably enhanced stability. This work shows that the precise modulation of the regiochemistry of SAM molecules is critical for improving their quality and derived device performance.

Switchable Closed‐Shell and Open‐Shell Biradical States in Bis‐Palladium Complexes of Tetrathiadodecaphyrin via Coordination Rearrangement

Abstract A figure‐eight tetrathiadodecaphyrin ( 1 ), featuring two porphyrin‐like sub‐pockets separated by central carbazolylenes was synthesized. Metalation of the thiaporphyrinoid ligand with Pd(OAc) 2 produces two distinct bis‐Pd(II) complexes with different coordination environments. Complex 2 , adopting an {NNCS} metalation mode, exhibits a closed‐shell electronic structure, whereas complex 3 , with an {NNCC} coordination environment, exists as a ligand‐centered organic biradicaloid with two magnetically independent spins ( S  = 1/2). Biradical formation is attributed to single‐electron transfer from each ligand sub‐pocket to the Pd(II) center accommodated in a d 8 square‐planner coordination geometry. Notably, the complexes are interconvertible through doubly one‐electron redox processes, demonstrating a reversible metal coordination rearrangement via thiophene ring flipping within a porphyrinoid framework. This work establishes the first example of such tunable metal coordination, offering a precise strategy for modulating closed‐shell and open‐shell biradical states. In addition, while complex 2 displays intense absorption and photoacoustic responses to the first near‐infrared (NIR‐I) light in water after encapsulation within nanoparticles, the nanocomposites encapsulating biradicaloid 3 exhibits enhanced responsiveness in the second near‐infrared (NIR‐II) region.

Chen Wang

Solar‐Driven Reversible Hydrogen Storage of Sodium Cyclohexanolate/Phenoxide Pair

Abstract Reversible hydrogen storage is a key challenge for the implementation of hydrogen energy, with dehydrogenation being particularly difficult because of its endothermic nature, slow kinetics, poor selectivity, etc. Solar energy‐driven hydrogen uptake/release represents an interdisciplinary approach that provides an effective solution to those problems. Herein, we report the solar‐driven reversible hydrogen uptake of 4.9 wt.% over sodium cyclohexanolate/phenoxide pair, achieving over 99.9% conversion and selectivity in both hydrogenation and dehydrogenation via photocatalysis without external heating. Notably, the initial dehydrogenation rate reaches 23.4 that is ca. 2 orders of magnitude higher than thermocatalysis. The superior photocatalytic performance stems from the synergy between high‐ and low‐frequency light, i.e., low‐frequency light mainly provides heat, high‐frequency light drives the desorption of product from the catalyst surface. This approach offers a path toward a sustainable solar‐driven hydrogen energy system.

Selective Leaflet‐Anchored DNA Nanoprobes for Simultaneous Monitoring of Juxta‐Plasma Membrane Environments

Abstract The cell membrane functions as a bidirectional interface that coordinates the selective transport of substances and information between the interior and exterior of the cell. Simultaneous monitoring of both the inner and outer local environments surrounding this lipid bilayer is crucial for elucidating various cellular activities but significantly challenged by the lack of technologies capable of precisely engineering biosensing probes on both membrane leaflets. In this work, by developing fusogenic nanoliposomes with high cell fusion efficiency, we successfully anchored amphiphilic DNA tetrahedral probes onto the inner leaflet of the plasma membrane. By integrating this with the direct anchoring of amphiphilic probes on the outer leaflet, we achieved precise functionalization of both leaflets of the cell membrane, thus enabling simultaneous monitoring of localized targets within their respective juxta‐plasma membrane environments, avoiding signal contamination caused by the optical diffraction limit. Using selectively dual‐leaflet‐anchored tetrahedral DNAzyme probes, we revealed that the transmembrane ion channel SLC41A1 synergistically modulated the influx of Na + and the efflux of Mg 2+ in live cells. With a modular design, this membrane‐anchored DNA nanoplatform can be readily extended for the study of bilateral interface‐dominant cellular processes, shifting the paradigm toward a more localized and subtle perspective.

Mn(II)‐Based Hybrid Halide Ionogel Scintillator Film for Large‐Area and High‐Resolution X‐ray Imaging

Abstract Functionalized ionogels have attracted significant attention in chemical design of new materials and versatile applications, which are formed by polymer network as a matrix with introducing ionic liquids containing characteristic units as a dispersion medium. Here, we present an universal scheme to rapidly synthesize luminescent ionogels through the in situ formation of zero‐dimensional (0D) hybrid metal halides during the polymerization of monomer. In particular, Mn(II)‐based hybrid halide ionogels (Mn─IG) were formed by incorporating [C 20 H 20 P] + cations and [MnBr 4 ] 2− anions into the polymer network structure. Thanks to the amorphous nature of Mn‐IG and the homogeneous distribution of self‐trapped [MnBr 4 ] 2− light‐emitting units with [C 20 H 20 P] + cations, Mn─IG exhibits high transparency (nearly 90% transmittance at 550 nm‐1100 nm) and homogeneous highly‐efficient emission. Taking advantage of its processability, we fabricate an 18 cm × 12 cm scintillation film and successfully realize large‐area and high‐resolution X‐ray imaging. The straightforward and rapid synthesis method on such ionogels paves the way for the low‐process‐demand preparation of large‐area scintillators, and also opens up new routes for the in situ construction of uniform 0D metal halide polymer composites.

Aptamer‐Based Galvanic Potentiometric Sensor for Real‐Time Monitoring of Serotonin Signaling Under Psychosocial Stress

Abstract Psychosocial stress, a pervasive factor in mental health disorders, is tightly linked to serotonin (5‐HT) dysregulation. Real‐time electrochemical monitoring of 5‐HT in vivo is challenged by interference from vitamin C (Vc) and biofouling, requiring invasive pretreatments. We present a self‐powered aptamer‐engineered galvanic sensor (aptGRP 5‐HT ) that integrates phosphorothioate aptamers with a redox potentiometric mechanism, achieving 21.5‐fold higher selectivity and 98.3‐fold enhanced sensitivity against Vc over conventional sensors while resisting electrochemical biofouling. The aptGRP 5‐HT operates in complex biological environments without pretreatment, enabling direct monitoring in a rodent psychosocial stress model. Using this tool, we uncover a neurochemical signature of social hierarchy: high‐ranking mice exhibit elevated 5‐HT release in the medial prefrontal cortex (mPFC) and dorsal raphe nucleus (DRN), with region‐specific correlations to neuronal activity‐reduced spontaneous firing in the mPFC and increased activity in the DRN. This work resolves long‐standing challenges in neurochemical sensing and establishes aptGRP 5‐HT as a transformative platform for probing brain function and stress‐related disorders.

Alcohol Activation by Benzodithiolylium for Deoxygenative Alkylation Driven by Photocatalytic Energy Transfer

Abstract The 1,3‐benzodithiolylium (BDT) cation was identified as an efficient hydroxyl‐activating reagent for the photocatalytic deoxygenative radical functionalization of alcohols in the absence of any electron transfer process. A series of unprecedented photocatalytic energy transfer (EnT)‐driven deoxygenative radical coupling reactions of alcohols with bifunctional oxime carbonates have been developed based on the activation by BDT. Nickel‐catalyzed radical sorting followed by C(sp 3 )─C(sp 3 ) bond construction facilitates the heteroselective cross‐coupling of two distinct alkyl radicals originating from parallel radical relays. These reactions allow the versatile synthesis of diverse nitrogen‐containing molecules, including amino acid derivatives, imines, nitriles, and pyrrolines, by using ubiquitous alcohols as regiodefined alkyl building blocks.

Hopping Diffusion in Wiggling Nanopore Architecture of MOF Enabling Synergistic Equilibrium‐Kinetic Separation of Fluorinated Propylene and Propane

Abstract The separation of octafluoropropane (C 3 F 8 ) from hexafluoropropylene (C 3 F 6 ) is an industrially important yet challenging process due to their similar physicochemical properties and stringent purity demands in industrial applications. Herein, we address this task through precise pore architecture in a zirconium‐based metal‐organic framework (Zr‐PMA), which exhibits unique “wiggling nanopores” with narrow windows and large cavities. The narrow windows act as diffusion barriers, selectively restricting C 3 F 8 transport, while the large cavities provide strong adsorption sites for C 3 F 6 , enabling an equilibrium‐kinetic synergistic separation. This dual functionality results in a ∼450‐fold difference in diffusion rates and exceptional kinetic selectivity for C 3 F 6 over C 3 F 8 , as demonstrated by adsorption isotherms, time‐resolved kinetics, and dynamic breakthrough experiments. Theoretical calculations coupled with in situ spectroscopy elucidate the pore geometry‐dependent hopping diffusion mechanism responsible for the separation. This work establishes wiggling pore geometry as a versatile paradigm for advanced adsorbents targeting energy‐efficient separations of structurally similar fluorocarbon mixtures.

Site‐Selective Carbonylation of Azetidines via Copper‐Catalyzed Difluorocarbene Insertion

Abstract γ‐Lactams are privileged five‐membered pharmaco‐phores in numerous bioactive compounds, but access to these motifs typically relies on cycloaddition/substitution chemistry involving activated substrates or CO carbonylations under harsh conditions. Here, we report a new route to functionalized γ‐lactams through formal carbonylation of azetidines under nonprecious metal catalysis. The method leverages a copper‐stabilized difluorocarbene to promote site‐selective insertion followed by in situ hydrolysis to unmask the lactam group. In contrast to most difluorocarbene reactions that cause ring cleavage of saturated heterocycles in the presence of heat, the present system operates at a low temperature and retains the integrity of the cyclic structure. Synthesis of various drug‐like lactams and a therapeutic agent for diabetes highlights utility.

Gang Li