Browse Articles

Investigating the Risk of Arrhythmogenesis Associated With Fentanyl Abuse Using Human and Mouse Cardiomyocytes

Oxic microbial ferrihydrite reduction rates of Shewanella oneidensis and the potential for Fe mobilization in oxic sediments

Abstract Microbially mediated reduction of ferrihydrite (Fe(III) oxyhydroxide) plays a crucial role in Fe cycling, and hence nutrient and contaminant cycling, in subsurface environments. This process is typically considered a strictly anaerobic process confined to anoxic microsites within oxic subsurface environments. However, recent findings suggest that microbes can also mediate ferrihydrite reduction under oxic conditions. Here, we quantified cell-specific rates of ferrihydrite reduction by the model organism Shewanella oneidensis MR-1 under oxic and anoxic conditions. We used these rates to assess the relative contribution of oxic and anoxic pore spaces to Fe(II) mobilization in a previously published laboratory analog of oxic aquifer sediments. Oxic reduction proceeded persistently, albeit at a per cell rate 100 times more slowly than anoxic reduction, yet still generated appreciable Fe(II). Modeling suggests that when anoxic microsites are absent or occupy a minor fraction of the pore space, oxic Fe(III) reduction can account for a significant share of total Fe(II) release. Such conditions are common in shallow aquifers, well-drained soils, and capillary fringes. We conclude that oxic Fe(III) reduction is a persistent background process that has been underestimated in current biogeochemical frameworks.

Unveiling the Power of Dark State Photocages: An Efficient Pathway to Triplet State Under Near‐Infrared Light Irradiation

Abstract The photocage platform provides a synergistic approach to photodynamic therapy (PDT) and chemotherapy. Before light activation, both pro‐photosensitizers and pro‐drugs remain inert, ensuring safety. Upon near‐infrared (NIR) light irradiation, they undergo photoactivation and controlled release in deep tissues. However, the low photolysis efficiency of conventional singlet‐state photocages limits their in vivo applications, necessitating an exploration of how excited‐state dynamics influence photolysis. In this study, we introduce the concept of a “dark state photocage” and establish a photocage platform responsive to NIR light by incorporating phenoxazine or phenothiazine groups. Mechanistic investigations reveal that the dark state enhances triplet‐state formation and facilitates intersystem crossing, thereby promoting photolysis. These photocages achieve functional molecule release under low‐power NIR light (15 mW cm⁻ 2 ), with an efficiency of up to 90%. This advancement enables a sharp transition from an “OFF” to an “ON” tumor imaging signal and significantly enhances the therapeutic efficacy against triple‐negative breast cancer under NIR light irradiation, effectively integrating PDT and chemotherapy.

Merging Photocatalysis with Chiral Lewis Acid Catalysis for Enantioselective Hydrosilylation/Hydrogermylation of Electron‐Deficient Alkenes

Abstract Organosilicon compounds demonstrate widespread applications in many fields. Transition‐metal‐catalyzed asymmetric hydrosilylation represents one of the most common and effective methods to synthesize chiral organosilicon compounds, but it largely relies on electron‐rich alkenes and structurally specific hydrosilanes. Visible light photocatalysis has emerged as a promising new platform for hydrosilylation. However, the enantiocontrol of photoinduced asymmetric hydrosilylation concerning highly reactive radical species is a great challenge. Herein, we report a synergistic catalytic strategy for enantioselective hydrosilylation of electron‐deficient alkenes by merging anthraquinone as a dual‐tasked photocatalyst with a chiral Lewis acid catalyst. This protocol shows broad hydrosilane scope with efficient chemo‐, regio‐ and enantioselectivities, delivering diverse enantioenriched organosilicon compounds, which could be readily converted into a series of medicine molecules. Mechanistic studies reveal that the π–π interaction between the photocatalyst and the alkene is crucial for enantiocontrol. Additionally, enantioselective radical hydrogermylation was also achieved under the visible light photoinduced synergistic catalysis.

Dynamically Dual‐Center Coupled Synergistic Catalysis for Highly Efficient Oxygen Reduction

Abstract The oxygen reduction reaction (ORR) suffers from inherent kinetic limitations arising from the competitive adsorption behavior of *OOH intermediates and their divergent conversion pathways toward either the 4e⁻‐dominant route or the 2e⁻‐peroxide byproduct. Conventional single‐component catalysts fundamentally lack temporal‐spatial control to simultaneously accelerate O─O bond cleavage while suppressing *H 2 O 2 desorption. To overcome this kinetic dilemma, herein, we propose a dynamically dual‐center coupled synergistic (DCCS) catalytic mechanism enabled by precisely engineered PdRh─Pt nanosheet binary‐component interfaces. Multidimensional in situ synchrotron radiation spectroscopy and theoretical studies reveal that the activated 4e⁻ pathway primarily occurs at PdRh sites. Additionally, Pt centers selectively reduce *OOH to *O and *H 2 O 2 , whereas neighboring PdRh sites facilitate ultrafast *H 2 O 2 migration and dissociation, effectively complementing the 4e⁻‐dominant pathway. Hence, the DCCS catalysis redirects traditionally divergent product pathways toward a singular target product. This interfacial kinetic synergy achieves ultrahigh 4e⁻ kinetics, demonstrated by a six‐fold increase of turnover frequency compared to that of commercial Pt/C. Moreover, the derived rechargeable Zn‒air batteries demonstrate exceptional stability over 200 h, establishing a new design principle for breaking kinetics trade‐offs in heterogeneous catalysis through molecularly scheduling reaction pathways.

Regulate the Singlet–Triplet Energy Gap by Spatially Separating HOMO and LUMO for High Performance Organic Photovoltaic Acceptors

Abstract Reducing the single‐triplet energy gap (∆ E ST ) for organic photovoltaic (OPV) molecules has been proposed to be able to reduce the nonradiative recombination by tuning the low‐lying triplet state (T 1 ) and/or the excited state (S 1 ), thus reducing the energy loss ( E loss ) and increasing the open‐circuit voltage in their devices. However, how to design the non‐fullerene acceptor (NFA) with small ∆ E ST and high performance is challenging. Aiming to address this issue, YDF , YTF , and YTF‐H were synthesized. Among them, a device based on YDF with partially spatially separated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) exhibits a much higher power conversion efficiency (PCE) of 20.04%, which is one of the most efficient efficiencies for binary systems. For YTF and YTF‐H , their completely spatially separated HOMO and LUMO indeed lead to a much reduced ∆ E ST caused by the low‐lying S 1 state, together with excellent charge mobility and light absorption, required for higher performance OPV. But their low S 1 state causes several non‐radiative recombinations due to strong S 1 ‐S 0 coupling (PCE < 1.5%). These results indicate that future designs to have high performance molecules with small ∆ E ST should avoid the sharp decrease in S 1 , and the ideal scenario would be to elevate the T 1 state, thereby mitigating the energy gap law.

Site‐Blocking Strategy Boosts H ₂ S Tolerance in Platinum‐Based Hydrogen Oxidation Catalysts

Abstract Proton exchange membrane fuel cells (PEMFCs) show great potential for energy conversion, but their platinum‐based hydrogen oxidation reaction (HOR) catalysts are easily and irreversibly poisoned by trace impurities like H 2 S, causing performance degradation with unclear mechanisms. Here, combining in situ Raman spectroscopy with theoretical calculations, we found that on pure Pt surfaces, H 2 S dissociates into S* and HS* intermediates that occupy active sites of continuous Pt atoms in an acidic solution under 50 ppm H 2 S/H 2 atmosphere. However, on PtRu alloy surfaces, while *OH species were observed on Ru sites, no sulfur‐containing species were detected on Pt sites. Comparative experiments revealed that the sulfur‐related Raman peaks of PtRu exhibited a redshift compared to Pt, indicating that Ru alloying weakens the *S adsorption on Pt sites through electronic effects. These results demonstrate that Ru not only creates discontinuous Pt sites to block sulfur adsorption but also significantly weakens sulfur binding through electronic modulation. Based on these insights, small‐sized site‐blocking PtRu/C catalysts were developed, exhibiting only 9.2% activity decay after 700s in 50 ppm H 2 S/H 2 atmosphere, a 4.3‐fold improvement over commercial Pt/C catalysts (39.3% decay). This work provides fundamental understanding of H 2 S poisoning mechanisms and practical guidelines for designing robust, poison‐resistant catalysts.

NiH‐Catalyzed Enantio‐ and Regioselective Hydroarylation of Unactivated Alkenes Enabled by Outer‐Sphere Electron Transfer with Diaryliodonium Salts

Abstract Asymmetric hydroarylation of unactivated alkenes provides a direct route to enantiomerically enriched C─C bonds in aryl‐containing compounds, a key transformation in pharmaceutical and natural product synthesis. While recent advances have achieved high regio‐ and enantioselectivity with terminal alkenes, controlled hydroarylation of unactivated internal alkenes remains challenging. Here, we report a nickel‐hydride‐catalyzed protocol that overcomes this limitation through a mechanistic paradigm shift. By employing diaryliodonium salts as dual‐function reagents, our method achieves high enantio‐ and regioselectivity in the hydroarylation of both internal and terminal unactivated alkenes. These salts enable a transition from concerted to stepwise oxidative addition via dissociative single‐electron transfer (DSET), generating a cationic alkyl‐nickel intermediate prone to fragmentation and aryl radical addition. Mechanistic studies, including a key experiment in 1,4‐dioxane yielding an enantiomerically pure solvent‐functionalized product, establish migratory insertion as the enantio‐ and regio‐determining step. This approach not only expands the scope of asymmetric hydroarylation but also provides a new mechanistic framework for selective hydrofunctionalization reactions.

EDTA‐Mg Nano‐Chelators Amplify Ferroptosis by Artificially Simulating the Epithelial‐Mesenchymal Transition Process and Endogenous Iron Deprivation

Abstract Epithelial‐mesenchymal transition (EMT) is a key step in initiating tumor metastasis. Commonly, researchers focus on inhibiting EMT to prevent tumor metastasis. However, they ignore that tumor cells undergoing EMT are more vulnerable to disturbance from the external environment. Tumor cells in this period are a potential therapeutic target, yet precisely regulating the EMT of tumor cells remains a challenging problem to be solved. Here, based on metal chelation therapy, we propose a strategy of artificially mimicking EMT, integrating ferroptosis and immunotherapy to inhibit tumor growth and metastasis. The prepared ethylene diamine tetraacetic acid‐magnesium (EDTA‐Mg), on the one hand, chelates Ca 2+ on the surface of tumor cells to form EDTA‐Ca, causing the dissociation of tumor cells. Meanwhile, E‐cadherin is downregulated, while Vimentin and matrix metalloproteinase 2 (MMP‐2) are upregulated, indicating the occurrence of EMT. On the other hand, after EDTA‐Ca is endocytosed by tumor cells, it deprives Fe in the lysosomes to form EDTA‐Fe, which induces ferroptosis through a Fenton reaction. Ferroptosis, combined with the initially released Mg 2+ , synergistically amplifies the immune response, thereby inhibiting tumor metastasis. To the best of our knowledge, such a strategy of artificially simulating EMT for tumor treatment has hitherto not been reported.

Entire Near‐Infrared‐I Electrochemiluminescence Enhancement of Gold Nanoclusters

Abstract Herein, entire near‐infrared‐I (NIR‐I) electrochemiluminescence (ECL) enhancement of gold nanoclusters (Au NCs) is achieved by continuously regulating the plasmon resonance absorption wavelength of gold nanorods (Au NRs) to precisely match ECL emission wavelength of Au NCs (abbreviated as Au NCs/Au NRs), which challenges the drawbacks of traditional single wavelength ECL enhancement strategy. Interestingly, within the range of 670–820 nm, the ECL intensity of Au NCs/Au NRs is 3–4 times higher than that of individual Au NCs due to the acceleration of electron‐hole recombination and radiation transition rate through high energy electromagnetic field. As a proof of concept, the Au NCs/Au NRs with the ECL emission of 670 nm is employed as high‐efficiency ECL emitter to achieve high‐resolution ECL image and construct biosensor for realizing ultrasensitive detection of matrix metalloproteinase‐2 (MMP‐2) related to liver failure. Significantly, the proposed ECL enhancement strategy effectively enhances the ECL emission of metal nanoclusters (M NCs) over a wide wavelength range and advances a new path for other tunable nanomaterials to enhance the ECL emission of M NCs, which is expected to be applied to in the field of multispectral ECL imaging, multimodal optoelectronic devices, and spectrum‐resolved multiplexed biosensing systems.

Outside Back Cover: Light‐Driven Ratchet Mechanism Accelerates Regioselective Metal‐Cation Exchange in a Heterobimetallic Helicate (Angew. Chem. Int. Ed. 35/2025)

Tuning Encodable Tetrazine Chemistry for Site‐Specific Protein Bioorthogonal Ligations

Abstract Using genetic code expansion (GCE) to encode bioorthogonal chemistry has emerged as a promising method for protein labeling, both in vitro and within cells. Here, we demonstrate that tetrazine (Tet) amino acids incorporated into proteins are highly tunable and have extraordinary potential for fast and quantitative bioorthogonal ligations. We describe the synthesis and characterization of reaction rates for 29 Tet amino acids (20 of which are new) and compare their encoding ability into proteins using evolved tRNA/RS pairs. For these systems, we characterized on‐protein Tet stability, reaction rates, and ligation extents as the utility of a bioorthogonal labeling group depends on its stability and reactivity when encoded into proteins. By integrating data on encoding efficiency, selectivity, on‐protein stability, and in‐cell labeling for Tet tRNA/RS pairs, we developed the smallest, fastest, and most stable Tet to date. This was achieved by introducing fluorine substituents to Tet4, resulting in reaction rates at the 10⁶ M⁻¹s⁻¹ level while minimizing degradation. This study expands the toolbox of bioorthogonal reagents for Tet‐sTCO‐based, site‐specific protein labeling and demonstrates that the Tet is a uniquely tunable, highly reactive, and encodable bioorthogonal functional group. These findings provide a foundation to further explore Tet encoding and reactivity.

Suppressing Halide Segregation of Wide Bandgap Perovskite by Interface Molecular Coordination for High‐Performance All‐Perovskite Tandem Solar Cells

Abstract Hole transporting layers made by self‐assembled molecules (SAMs) are emerging as promising hole transporting materials (HTMs) for perovskite‐based tandem solar cells, owing to their reduced parasitic absorption and effective carrier extraction. However, perovskite films grown on HTM substrates typically exhibit a high defect density, which adversely affects device performance. In this study, we investigated the film growth kinetics of wide‐bandgap perovskite on monolayer material substrates and uncovered a halide phase segregation in the initial nucleation stage during crystal growth kinetics at the interface, which brings small grain sizes and significant lattice strain within the perovskite film. To address this issue, we introduced a biphosphate‐substituted molecule on the HTM surface to coordinate with PbBr 2 that suppresses halide phase segregation, leading to improved crystallographic orientation and a reduction in defect density. As a result, the wide‐bandgap (1.77 eV) perovskite solar cells (PSCs) achieved a power conversion efficiency (PCE) of 19.5% with an open‐circuit voltage of 1.35 V, while tandem devices reached an impressive efficiency of 28.65%.

Asymmetric, Corner‐Sharing CuO ₅ and CuO ₆ Motifs in Cu‐Based Metallic Perovskite Oxides Boosting Asymmetric C─C Coupling for CO ₂ Electroreduction to C ₂₊

Abstract Cu‐based perovskite oxides feature significant potential for CO 2 electroreduction (CO 2 RR) but encounter insufficient C 2+ selectivity primarily due to the inherent symmetric charge distribution at Cu sites hindering asymmetric C─C coupling. Here we report a unique type of Cu‐based metallic perovskite oxides with asymmetric, corner‐sharing CuO 5 and CuO 6 motifs to boost asymmetric C─C coupling for efficient CO 2 ‐to‐C 2+ conversion. For the proof‐of‐concept catalyst of La 0.8 Ba 0.2 CuO 3‐δ , their ordered, corner‐sharing CuO 5 pyramids and CuO 6 octahedra feature localized charge density redistribution, creating abundant asymmetric Cu─Cu dual sites with distinct electronic structures and also strengthening Cu─O covalency. In CO 2 RR (in both alkaline and acidic media), La 0.8 Ba 0.2 CuO 3‐δ greatly promotes C 2+ formation while producing negligible CH 4 , showing a Faradaic efficiency ratio (C 2+ to CH 4 ) of up to 180. Moreover, La 0.8 Ba 0.2 CuO 3‐δ , achieving a remarkable C 2+ Faradaic efficiency of 85.0% at 400 mA cm −2 , together with well‐boosted stability, outperforms previously reported Cu‐based‐perovskite catalysts. Our experiments and theoretical calculations attribute the superb performance mainly to the following factors: the asymmetric CuO 5 ─CuO 6 sites promoting differentiated *CO adsorption/hydrogenation to favor asymmetric *CO─*CHO coupling; the strengthened Cu─O covalency stabilizing the Cu sites. Extending this strategy to two additional pairs of Cu‐based perovskite oxides generates similarly successful results.

Symmetry Breaking Enabled Stable Oxygen Redox in Li‐Rich Cathodes via π‐Type Interaction

Abstract Effectively stabilizing oxygen redox is the most challenging task for the practical applications of high‐energy‐density Li‐rich cathode materials. However, how to accurately tune the oxygen energy level to achieve reversible redox remains puzzling so far. In this work, we achieve stable oxygen redox in layered Li‐rich materials over the whole voltage range without irreversible O 2 release by adjusting the interlayer metal cation environment adjacent to the ligand. Combining synchrotron X‐ray absorption spectroscopy and theoretical analysis of metal‐ligand orbital combinations, we confirm the obvious charge transfer from O to Ni due to the π‐type interaction between Ni 3 d spin‐down t 2g orbitals and O 2 p orbitals. Furthermore, Ab initio molecular dynamics simulations reveal the spontaneous symmetry breaking of the Ni coordination environment after Li extraction under the π‐type interaction, which enhances the intrinsic competition between anion and cation oxidation, keeping π* state (from O 2 p splitting) below the metal band to avoid over‐oxidation. As a result, the modified material shows improved electrochemical performance and stable structural/interface evolution. This work provides new insights into the relationship between the adjacent metal environment and the ligand O redox reactions.

Remote and Spatiotemporal Modulation of Supramolecular Self‐Assembly of Croconaine Dyes via NIR Laser Irradiation

Abstract Supramolecular polymerization holds great promise for the fabrication of well‐defined nanostructures. However, achieving precise spatiotemporal control over the dynamic assembly of supramolecular polymers using external stimuli remains a significant challenge. Here, we present a near‐infrared (NIR) laser irradiation strategy that exploits the intrinsic photothermal properties of croconaine‐based molecular building blocks to modulate the aggregation–dissociation equilibrium of seeds, thereby enabling the formation of supramolecular polymers and copolymers. Light irradiation provides enhanced tunability through adjustments in laser power, irradiation time, and wavelength. Notably, the spatial precision afforded by laser irradiation allows for localized seed dissociation, offering a new approach for spatially controlled supramolecular polymerization. This method also enables efficient light‐mediated gel formation, spatially selective sol–gel transitions, and healing in supramolecular organogels. These findings demonstrate a light‐responsive strategy for regulating supramolecular polymerization and open new avenues for constructing nanomaterials with programmable structures and functions.

A Bifunctional Organic Photocatalyst for Efficient Single‐Electron and Energy Transfer Activation

Abstract Bifunctional photocatalysts capable of mediating both single‐electron transfer (SET) and energy transfer (EnT) processes are rare and typically metal based. Here, we present 3‐thioaryl‐4‐hydroxycoumarins, a new family of cost‐effective organic photocatalysts that leverage a stabilized charge‐transfer (CT) excited state to achieve both strong reducing power and efficient energy transfer. The spatial separation of the HOMO and LUMO stabilizes the CT state, enhancing SET reactivity ( E * red  = −3.08 V vs. SCE) while maintaining a sufficiently high triplet energy ( E T  = 67 kcal mol −1 ) for EnT‐driven transformations. This dual reactivity enables the activation of redox‐inert substrates ( E red  < −2.8 V vs. SCE) via SET reduction, generating radicals suitable for diverse C─S, C‐─P, C─B, and C─C bond‐forming transformations, alongside EnT‐based processes such as E / Z olefin isomerization and [2 + 2] photocycloadditions. Mechanistic studies, supported by photophysical and theoretical analyses, confirmed the catalyst's bifunctionality.

Selective and Energy Efficient Electrocatalytic CO ₂ ‐to‐Ethanol Conversion through Anion Modulation

Abstract Ethanol, with its high market value and stable global demand, stands out as an attractive product of electrocatalytic CO 2 reduction. However, achieving high ethanol selectivity and energy efficiency at industrial current densities remains challenging. In this study, we employed a blended anion modulation strategy to enhance the selectivity and energy efficiency of CO 2 ‐to‐ethanol conversion. The Cu 2 (OH) 3 F pre‐catalyst achieved Faradaic efficiencies of 50% and 93% for ethanol and C 2+ , respectively, at 700 mA cm −2 in a blended electrolyte consisting of 2 M KOH and 1 M KCl. Comprehensive electrochemical tests, combined with in situ characterizations and theoretical analysis, revealed that chloride and hydroxide increased *CO coverage for efficient C─C coupling. Moreover, hydroxide stabilizes the *CHCOH intermediate through hydrogen bonding with the adsorbed hydroxide on the catalyst surface, while Cl synergistically enhances its reactivity by promoting water dissociation toward the ethanol pathway.

Acetone Derivatives for Nickel‐Catalyzed Methylation, Trideuteromethylation, and ¹³ C‐Methylation of (Hetero)Aryl Chlorides

Abstract The development of low‐cost, readily available, and broadly applicable reagents for the methylation, trideuteromethylation, and 13 C‐methylation of aryl chlorides is crucial. Using acetone and its isotopic derivatives as feedstocks, we have prepared the methylating, trideuteromethylating, and 13 C‐methylating agents TDTP (2‐(1,5,5‐trimethyl‐4,5‐dihydro‐1H‐1,2,4‐triazol‐3‐yl)pyridine), TDTP‐CD 3 , and TDTP‐¹ 3 CH 3 . Under nickel catalysis and without any additional redox reagent, these reagents efficiently methylate a wide range of (hetero)aryl chlorides, chlorine‐containing complex molecules and phenolic derivatives, showing efficient functional‐group tolerance and scalability; they, therefore, hold great promise for drug discovery and complex molecule synthesis. Mechanistic studies indicate that the reaction begins with nickel‐catalyzed generation of a methyl radical, followed by radical cross‐coupling.

Long‐Range Electronically Polarized Fe‐N ₅ Catalysts Redirect Polymerization‐Driven Phenolic Pollutant Removal Toward Sustainable Carbon Sequestration

Abstract A sustainable strategy for simultaneous pollutant removal and carbon sequestration is offered by the peroxymonosulfate (PMS)‐mediated electron transfer mechanism. However, it remains challenging to achieve catalysts with durable and high activity. A novel catalyst design strategy leveraging boron doping that induces long‐range electronic polarization to precisely modulate PMS complexation dynamics on single‐atom catalysts (SACs) is proposed in this study. It is demonstrated that B‐doping induces asymmetric Fe‐N 5 coordination at the atomic iron centers (Fe SA ‐BNC) while creating electron‐enriched carbon auxiliary sites. The electron distribution is synergistically optimized by this dual‐site configuration through lowering the d‐band center and establishing a polarized charge transfer pathway. Complexes with enhanced oxidation potential are generated by the engineered Fe SA ‐BNC/PMS, redirecting bisphenol A degradation from conventional radical‐mediated mineralization to an interfacial polymerization pathway via outer‐sphere electron transfer. Remarkably, >3 times higher total organic carbon (TOC) removal activity compared to state‐of‐the‐art catalysts and 4 orders of magnitude higher reactivity than conventional carbon nitride (CN) catalyst are exhibited by the optimized catalyst. Excellent operational stability (>1700 h continuous operation) with >120 L actual wastewater treatment capacity is demonstrated by practical implementation in a continuous‐flow microreactor. This work advances electronic modulation strategies for sustainable water purification technologies.