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A Label‐Free Phosphate‐Transfer DNAzyme for the Cost‐Effective Point‐of‐Care Detection of Influenza Virus
Abstract DNAzymes have significantly enriched the toolbox for point‐of‐care testing (POCT); however, their inferior biostability and reliance on costly chemical labeling limit their broader applicability in high‐throughput viral sample analysis. Herein, we constructed a label‐free DNAzyme POCT platform for the accurate detection of influenza virus, with low cost (approximately US$0.20 per test). The simple yet robust viral detection system consists merely of a phosphate‐transferase‐mimicking DNAzyme (P‐Dz) with a newly discovered highly‐efficient small‐molecule substrate, 6,8‐difluoro‐4‐methylumbelliferyl phosphate (DiFMUP). Target viral RNA could specifically restore the catalytically active conformation of P‐Dz for initiating the phosphate transfer reaction from DiFMUP and for producing a high fluorescence signal. Without the prerequisite of laborious and expensive chemical labeling of DNA substrate, a readily accessible test filter strip (TFS) was introduced into the system, enabling the interpretation of fluorescence readout via smartphone visualization and thereby achieving the amplified detection of various viral RNA targets. This label‐free DNAzyme platform provides a cost‐effective and portable platform for bioanalysis, with considerable potential in epidemiological diagnostics and therapeutic monitoring.
Engineering Multicellular Inter‐Communication Systems Using a Synthetic Conformation Inducible Kinase Receptor
Abstract Synthetic multicellular inter‐communication systems are essential for understanding multicellular behaviors and developing cell‐based therapeutics. Synthetic receptors that allow programming of multicellular intercommunications through spatiotemporal control with light or chemical ligands are highly desirable but remain challenging. Here we propose a new strategy for designing multicellular inter‐communication systems using a synthetic conformation‐inducible kinase receptor (synCIKER). The synCIKER system is developed by engineering the extracellular domain of a tyrosine kinase receptor with domains responsive to inputs of chemical ligand, light or soluble protein, and rewiring the endogenous intracellular signaling pathways for prescribed transgene expression. The synCIKER system is demonstrated to sense these inputs, and generate customized secretory proteins for programming receiver cell behaviours such as surface receptor degradation and T cell‐mediated lysis in target cells. We also demonstrate the ability of synCIKER to construct cascade systems and reconfigure intelligent intercellular Boolean logic gates of OR, AND and INHIBIT for activating gene editing in receiver cells. The synCIKER platform is further exploited to modulate bi‐directional polarization of macrophages in a multi‐cellular system, highlighting its potential for designing synthetic intercellular communication systems for programming multicellular behaviors.
Inner‐Axial Chlorine Engineering Enables Efficient and Selective Phenol Electrocatalytic Upcycling to Benzoquinone on Noble‐Metal‐Free Catalysts
Abstract Electrocatalytic upcycling of aqueous phenol into value‐added para ‐benzoquinone ( p ‐BQ) provides a promising route for synergistic wastewater treatment and sustainable chemical synthesis. Nevertheless, previous attempts have primarily relied on noble metal‐based (e.g., Pd, Ru) electrocatalysts, but struggled with high costs and low selectivity. We, herein, report a noble‐metal‐free catalyst comprising carbon nanotube (CNT)‐supported CoN 4 sites coordinated with inner‐axial chloride atoms (Co‐CNT‐Cl), delivering 92.4% phenol conversion and 83.7% p ‐BQ yield under mild conditions. The superior electrocatalytic performance stems from inner‐axial coordination of Cl, which fine‐tunes the CoN 4 site microenvironment and electronic structure. This modification enhances charge‐transfer capacity, optimizes oxidation thermodynamics, and facilitates phenol adsorption and p ‐BQ desorption. The proposed electrocatalytic system with the Co‐CNT‐Cl catalyst, maintains > 80.3% phenol conversion and > 70.7% p ‐BQ yield over 10 consecutive cycles. Furthermore, integrating the Co‐CNT‐Cl catalyst into a continuous‐flow electrolyzer enables efficiently operational stability. This work establishes a potential and cost‐effective electrocatalytic approach to valorize phenolic wastewater through resource recovery.
Molecular Design of Nitrile Electrolytes Enabling Lithiated Silicon–Sulfur Batteries with Quasi‐Solid‐State Sulfur Reaction
Abstract The development of lithium–sulfur (Li−S) batteries is hindered by the polysulfide dissolving, cross‐over and the inherent lithium metal anode instability. We herein instead describe a lithiated silicon−sulfur (LiSi−S) battery enabled by molecular engineering of highly solvating nitrile electrolytes toward weakly solvating to fundamentally decouple the reactions of the two electrodes and eliminate their cross‐talk. Specifically, by controlled fluorination of the ethoxy‐nitrile base solvent, the charge distribution on the solvent is manipulated which suppresses the solvation for polysulfides promoting a quasi‐solid‐state sulfur reaction (QSSSR) mechanism. The promoted anion participation in Li + solvation, along with the fluoroethylene carbonate additive, further stabilizes the interphases at both sulfur cathode and LiSi anode mitigating the mechanical degradations. The QSSSR‐based LiSi−S cell shows a high capacity of 1499.0 mA h g sulfur −1 at 0.1C, and achieves a high capacity retention of 90.2% over 100 cycles at 0.2C with an average Coulombic efficiency of 99.9%. This work highlights the essence of molecular engineering for manipulating the primary reactions and interphasial behaviors at both electrodes toward high performance sulfur batteries.
CO/H <sub>2</sub> S Dual Prodrugs Activated by Proximity‐Enhanced Chemiexcitation for Suppression of Tumor Growth and Metastasis
Abstract Carbon monoxide (CO) and hydrogen sulfide (H 2 S) both exhibit significant therapeutic potential in antitumor therapy, highlighting the importance of developing dual prodrugs for combinatorial gas therapy. However, such dual prodrug systems remain largely unexplored. This study designed a series of CO/H 2 S dual prodrugs based on a proximity‐enhanced chemiexcitation mechanism. By directly conjugating a chemiexcitation‐triggering module with a photosensitive CO‐releasing moiety (3‐hydroxythioflavone), we constructed unimolecular prodrugs capable of light‐independent CO release specifically in response to H 2 O 2 . Leveraging the proximity effect between these modules, exceptional CO release efficiency exceeding 90% was achieved. Surprisingly, H 2 O 2 ‐induced chemiexcitation also facilitated H 2 S release from the 3‐hydroxythioflavone scaffold. Two representative prodrugs demonstrated simultaneous CO and H 2 S release in 4T1 cancer cells. Notably, in a 4T1 murine tumor model, these prodrugs effectively suppressed tumor growth and lung metastasis without inducing observable adverse effects. This work presents the first report of chemiexcitation‐triggered CO/H 2 S dual prodrugs, providing a promising strategy for combinatorial gas therapy in cancer treatment.
Radiation‐Responsive Coacervates Through Controlled Self‐Immolative Demembranization
Abstract Coacervates formed through liquid–liquid phase separation (LLPS) have been utilized to emulate the dynamic organization of membraneless organelles in biological systems. These structures exhibit broad application prospects in biomedicine, especially as microreactors for biochemical reactions. However, membraneless coacervates tend to coalesce easily in ambient condition and lack the ability to achieve precise, stimulus‐responsive release, which presents significant challenges for their biomedical applications. To address this, we developed a self‐immolative polymer (SIP)‐membranized coacervates to tune enzyme cascade kinetics using radiotherapeutic γ‐ray. The SIP‐membranized coacervates exhibited enhanced kinetic stability and fusion‐resistance. When exposed to radiation, the SIP membrane undergoes depolymerization, resulting in increased fluidity and enhanced transmembrane transport. This, in turn, regulated enzyme cascade reactions within the coacervates. Specifically, we used radiation‐responsive coacervates to precisely modulate the generation of NO in living cells and exploited NO‐mediated radiosensitization to enhance cytotoxicity. Our findings advance the development of radiation‐responsive LLPS constructs, and pave the way for innovative applications in cellular bioengineering, and combined radio‐chemotherapy.
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Spatially Separated C–C Coupling and Protonation on Cl‐Bridged Ti–Ag Dual‐Site Catalysts for Efficient Photocatalytic CO <sub>2</sub> Reduction to C <sub>2</sub> H <sub>4</sub>
Abstract Solar‐driven selective reduction of CO 2 to C 2 H 4 conversion is bottlenecked by the concurrent demands for intermediate protonation and C–C coupling. Herein, we constructed a chlorine (Cl)‐bridged Ti–Ag dual‐site catalysts to overcome above issues. The introduction of Cl on Ti‐Ag dual sites spatially separates C–C coupling and intermediate protonation, making *CO dimerization thermodynamically more favorable than *CO hydrogenation. In situ characterization and DFT calculations reveal that the Cl enables the Ti sites within the Ti─Cl─Ag configuration act as active center for CO 2 activation and C–C coupling, thereby increasing the *CO intermediate concentration and lowering the C–C coupling energy barrier. Concurrently, Ag sites preferentially catalyze H 2 O dissociation, providing active hydrogen for the subsequent protonation of *OCCO intermediates, thus increasing the overall C 2 H 4 formation rate. The optimized Ti─Cl─Ag catalysts achieve high C 2 H 4 production rate of 244 µmol·g −1 ·h −1 with 64.3% selectivity, outperforming O‐bridged Ti–Ag catalysts which mainly favor *CO deep hydrogenation. This work establishes spatially separated Ti–Ag dual sites that orchestrates site‐specific C–C coupling and active hydrogen feeding, providing a rational design concept of photocatalysts for selective reduction of CO 2 to C 2 H 4 .
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Hybridized Host Functions in Polyaromatic Tube‐in‐Capsule Composites
Abstract Noncovalent hybridization of two types of host compounds has emerged as a promising strategy to develop unique functions, unattainable by either of the hosts. Here we report unusual spectroscopic features observed within a new hybrid host, formed by the combination of a polyaromatic tube and capsule, with rigid and flexible frameworks, respectively, in water. The resultant tube‐in‐capsule host selectively encapsulates rod‐like aromatic dyes (e.g., BODIPY and coumarin derivatives), yielding ternary host–guest composites bearing a dye‐in‐tube structure. The ternary composites exhibit strong emission (up to Φ F = ∼60%) from the bound dyes in water, with up to 45‐fold enhancement compared to the corresponding dye‐in‐capsule composites, due to the spatial isolation of the dyes in the tubular cavities. Detailed host–guest studies using dye derivatives and partial tube structures clearly indicate the importance of the rod‐like dye shape and tubular cavity for the present photofunctions. Furthermore, unusual remote chiroptical induction of encapsulated achiral dyes is readily demonstrated within a related hybrid host, where the achiral capsule is replaced with a chiral polyaromatic capsule. The dye‐based, pronounced circularly polarized emission (| g lum | = ∼3 × 10 −3 ) is observed only in this hybridized host–guest system.
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Scaleup Sodium‐Ion Capacitor Ah‐Level Pouch Cells Enable 100 C Ultrafast Charging Capabilities
Abstract Traditional hybrid ion capacitors face the low capacity of electric double‐layer (EDL) storage in narrow potential windows and the requirement of prelithiation (or presodiation) for practical device fabrication. Herein, we demonstrate that the activated carbon negative electrode (AC NE) maintains EDL capacitive behavior without the influence of solid electrolyte interphase (SEI) layers in a wide potential window of 3–0.05 V vs. Na + /Na. Remarkably, the AC NE displays an ultrahigh EDL capacitive storage capacity of 145 mAh g −1 (177 F g −1 ), a high initial coulombic efficiency of 95.6%, capacitor‐level ultrahigh rate capabilities and excellent cycling stability. Importantly, we assemble a 1.6 Ah (1694 F) SIC pouch cell, which delivers a high energy density of 42 Wh kg cell −1 (based on the total mass of the device), a high state of charge (SoC) of 57% at an ultrafast charging rate of 100 C, stable 10000 electrochemical cycles and high safety (passing nailing penetration and thermal runaway tests). Additionally, the high‐performance SIC is assembled without any presodiation treatment, which largely reduces manufacturing complexities and costs. Our work provides a significant milestone for the ultimate goal of electrochemical capacitors, which is increasing the energy density accompanied by capacitor‐level high power density, long‐term cyclability, and easy assembly.
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Solvation Entropy as a Lever for Steering the Macroscopic Properties of a Functional Supramolecular Helical Polymer
Abstract Solvent‐solute interactions are utterly important in supramolecular polymers (SPs), yet the high responsivity of SPs to solvent polarity makes it challenging to play on other solvation effects to tune their macroscopic properties in a rational manner. Herein, we report the characterization at various scales of the assembly properties of a C 2 ‐symmetric benzene‐1,3,5‐tricarboxamide monomer with two (1 S )‐methylheptyl moieties and one diphenylphosphino group as lateral chains. Our investigation reveals a highly cooperative structural transition between two SP states, which can exquisitely be tuned by solvents of similar polarities, leading to variation of the transition temperature (T*) over a range of 85 K. The structural transition was detected in 4 pure solvents and 13 toluene/cosolvent mixtures; a fair relationship is determined between T* and the solvent molar volume. The transition is only weakly favored by enthalpy (by ca. 2 kJ.mol −1 at 286 K). However, minimization of the entropic cost leads to a notable increase in the T*. This allows a fine tuning of the thermothickening and catalytic properties of the resulting SPs auguring that solvation, and notably solvation entropy, may constitute an important lever for steering SPs structure and properties.
Orientation‐Engineered Anderson‐Type Polyoxometalate Sub‐1 nm Nanosheets for High‐Performance Lithium‐Ion Battery Anodes
Abstract The unique atomic‐scale active site exposure of two‐dimensional sub‐1 nm nanosheets (2D SNSs) effectively shorten the electron/ion diffusion distance, significantly enhancing the rapid charge–discharge performance of lithium‐ion batteries (LIBs). However, it is still challenging to precisely regulate the exposed sites of the building blocks. Herein, Zn‐ZnMo 6 sub‐1 nm nanosheets (Zn‐ZnMo 6 SNSs) were successfully synthesized through the cluster self‐assembly strategy. Molecular dynamics (MD) simulations confirmed two stable configurations (Zn‐ZnMo 6 ‐1 and Zn‐ZnMo 6 ‐0.05) with distinct active sites exposure. Notably, Zn‐ZnMo 6 ‐1 exhibited excellent performance as lithium‐ion battery (LIB) anodes, with a reversible capacity of 1361.9 mAh g −1 for 1500 cycles at 1 A g −1 , significantly outperforming Zn‐ZnMo 6 ‐0.05 (258.5 mAh g −1 ). Electrochemical mechanism and density functional theory (DFT) calculations revealed that the terminal‐oxygen (O t ) sites exposed in Zn‐ZnMo 6 ‐1 enabled optimal lithium‐ions adsorption ( E ads = −6.54 eV), which facilitated rapid lithium storage behavior and exhibited exceptional redox reversibility. This study would provide a promising novel approach for the design and synthesis of 2D SNSs at molecule level.
Perfectly Linear α,ω‐Hydroxy‐Terminated Polyethylene with Near‐Ideal Crystallinity
Abstract A novel 1,5‐(bis‐borinane)pentane (1,5‐BBP) has been developed for polyhomologation (C1 polymerization), enabling the synthesis of well‐defined α,ω‐hydroxy polymethylene (PM) with controlled molar masses and narrow polydispersity at elevated temperatures. The structural integrity and complete difunctionality of the PM were confirmed by 1 H NMR, 1 1 B NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS), and SEC analyses. Achieving perfectly linear polyethylene (PE), an analog to PM, without branching remains a longstanding synthetic challenge, as even trace defects disrupt lamellar packing and reduce crystallinity. We address this limitation through the introduction of a monomer purification strategy for dimethyl sulfoxonium methylide in C1 polymerization that, for the first time, reduces residual branching to <0.04%, as confirmed by quantitative 1 3 C NMR. The resulting nascent PM exhibits exceptional properties, including enthalpies of fusion up to 290 J·g −1 , melting temperatures of 138 °C–143.15 °C, and crystallinity values of 93.8%–99.1% (DSC) and 92.0%–95.9% (WAXS). Solid‐state 2D 1 H‐ 1 3 C cross‐polarization magic angle spinningwide‐line separation (CP–MAS WISE) NMR spectra further confirm predominantly crystalline domains with minimal amorphous content. This study demonstrates that precise control over initiator design, monomer purity, and reaction conditions enables α,ω‐hydroxy‐terminated PM with crystallinity approaching the theoretical limits.
Local Electric Field‐Driven Reaction Pathway Regulation via Ru Single Atoms on Highly Curved Carbon Sphere for Stable Li–O <sub>2</sub> Batteries
Abstract Single‐atom catalysts (SACs) are extensively employed in Li–O 2 batteries owing to their exceptional atomic utilization efficiency and precise active‐site control, which collectively enhance battery performance. However, weak metal‐support interactions impede effective anchoring and electronic state modulation, leading to suboptimal catalytic activity, selectivity, and stability. Herein, we report a Ru single‐atom/onion‐like carbon sphere (Ru SACs/OCS) catalyst designed to accelerate oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics. This enhancement stems from the interplay of the local electric field induced by the tip effect, facilitating rapid mass transport of reactive species. Density functional theory (DFT) calculations and experimental results demonstrate that precise modulation of substrate nanostructure curvature significantly amplifies the local electric field intensity surrounding SACs on the support surface. This augmentation elevates surface charge density and active‐site concentration of the catalyst, thereby promoting the preferential disproportionation of reaction intermediates at the catalyst surface. The proposed strategy offers a streamlined and effective approach to engineer SACs with highly curved heterostructures, enabling enhanced catalytic reactions in metal−air battery technologies.
Metal‐Organic Framework/Organocatalyst Combinations as Powerful Multicatalytic Systems for Aerobic Oxidations
Abstract Aerobic oxidation using molecular oxygen as terminal oxidant represents a sustainable route to access valuable organic compounds. However, achieving high selectivity in such transformations remains challenging. Here, an easily tunable biomimetic multicatalytic system combining robust Metal‐Organic Frameworks and simple, commercially available, (hydro)quinone‐type molecules as co‐catalysts, which mimics the cooperative action of enzyme/coenzyme pairs in a confined environment is reported. A Zr‐MOF‐808/1,8‐dihydroxynaphthalene semiheterogeneous system enables the aerobic oxidation of anilines to azoxybenzenes, products that are typically elusive under aerobic conditions, with excellent yields and selectivity. Electron transfer triggers the formation of active oxidation sites in the MOF/(hydro)quinone interface, able to generate reactive oxygen species from O 2 under mild conditions without the need for light or other external stimuli. The generality of this novel multicatalytic approach is demonstrated by expanding it to different reactions and catalytic systems. In particular, the aerobic oxidation of thiols to disulfides is achieved by changing the organic co‐catalyst, whereas benzylamines are aerobically oxidized to their corresponding coupled products by employing a Ti‐based MOF (Ti‐MIL‐125) together with another co‐catalyst. Overall, this work highlights the untapped potential of MOF/organocatalyst combinations to drive challenging reactions under environmentally benign conditions.