Organic cathodes possess inherent structural diversity and fast redox kinetics, showing great application prospects in aqueous Zn batteries. Nevertheless, most of the reported organic cathodes display low average working voltage resulting in poor energy density. Herein, diquinoxalino [2,3-a:2',3'-c] phenazine (HATN)@CMK-3 composite is utilized as cathode for aqueous zinc battery, which combines the Zn2+ and H+ co-storage and I-/I0 conversion by introducing I--based active additive into 0.5 M Zn(OTf)2 electrolyte. The in-situ/ex-situ analyses and computational studies disclose that HATN@CMK-3 with C=N groups not only stores Zn2+ and H+ ions at low potential, but also acts as a substrate to promote the conversion reaction of I-/I0 at high potential. Accordingly, the Zn//HATN@CMK-3 cell delivers a high average voltage of 0.75 V, prominent long-life (10000 cycles) and high energy density (198 Wh kg-1). Remarkably, under high mass-loading (10 mg cm-2) or low-temperature conditions, the cell still achieves decent capacity and cycle stability.

Facing energy shortages and hard-to-degrade chemical pollution, especially high ionization potential (IP) organic pollutants, this study developed a novel photoelectrocatalyst, Ni-Mn@OBN, for degrading IP pollutants in seawater and generating hydrogen. Incorporating Ni-Mn dual atoms into an O-doped boron nitride (OBN) framework, Ni-Mn@OBN shows excellent stability and HER performance. Density functional theory (DFT) analysis revealed its low Gibbs free energy change (ΔGH* = 0.03 eV) for the HER, outperforming Pt (111). Achieving an ultra-low overpotential of 43.8 mV at 500 mA cm⁻² under AM 1.5 G simulated light surpasses commercial Pt/C catalysts. High IP pollutants enhance hydrogen evolution rates, indicating a synergistic effect. Theoretical calculations elucidated the interplay between seawater electrolytes and high IP values on the photoelectrocatalytic performance. Ni-Mn@OBN demonstrated excellent stability and a solar-to-hydrogen (STH) efficiency of 3.72%, offering a sustainable solution for marine pollution control and clean energy production.

Developing synthetic biology tools to control cell-to-cell signaling can provide new capabilities to engineer cell-cell communication and program desired cellular behaviors. As cell mimics, abiotic protocells provide an attractive opportunity to modulate the intercellular communication with design-based regulatory features. Despite the chemical communication of protocells that interact with living cells have been demonstrated, the autonomous regulation of intercellular signal transmission in protocell/living cell community remains a critical challenge. Herein, we designed a DNA circuit consisting of a recognition module, activation module, and feedback module that enables protocells to self-regulate the interaction with living cells by sensing and responding to the signal released from living cells. The feedback module with renewable capability is capable of processing the signal transduction on the membrane surface of protocells and controlling intercellular adhesion. Once dissociated from living cells, the disengaged protocells allow the following interaction with multiple target living cells in succession. Overall, this work provides an avenue to control and program dynamic signal propagation in protocell/living cell community. The designed communication with living cells would open new ways to tune cellular behavior and apply them to cell-based therapeutics.

The separation of octafluoropropane (C3F8) from hexafluoropropylene (C3F6) is an industrially important yet challenging process due to their similar physicochemical properties and 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 a unique 'wiggling nanopores' with narrow windows and large cavities. The narrow windows act as diffusion barriers, selectively restricting C3F8 transport, while the large cavities provide strong adsorption sites for C3F6, enabling an equilibrium-kinetic synergistic separation. This dual functionality results in a ~450-fold difference in diffusion rates and exceptional kinetic selectivity for C3F6 over C3F8, 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 ofstructurally similar fluorocarbon mixtures.

Reductive catalytic fractionation (RCF) is a promising technology that can selectively extract lignin in biomass and depolymerize it. Here, we prepared one low Ru loading catalyst (Ru0.8/C) for RCF of biomass to selectively produce different lignin oil (both monomers and oligomers) under different reaction atmospheres. The yield of phenolic monomers reached 46.0wt.% (rich in 4-propylguaiacol and 4-propylsyringol) in the RCF of birch wood under high H2 pressure and using methanol as solvent. But, under N2 atmosphere the dominant monomers shifted to 4-(prop-1-enyl)guaiacol and 4-(prop-1-enyl)syringol (79.6% selectivity) with 35.8wt.% yield of total monomers using the same catalyst. The developed catalyst can also transform native lignin in other biomasses such as pine and corn stover. Mechanistic investigation using different model compounds and deuteration indicates that removal of the Cγ-OH in methanol-extracted lignin fragments occurred before obtaining the monomeric lignin fragment, and the Cα-OH and β-O-4 bonds were then cleaved simultaneously to form 4-(prop-1-enyl) substituted monomers. The results are distinct from the reported mechanism that the precursors of the propyl and prop-1-enyl substituted monomers are monolignols with the removal of Cγ-OH at the monomeric level. Thus, this work provided novel insights into the reaction pathway of (native) lignin depolymerization.

The separation of trace alkyne (C2H2/C3H4) impurities from alkenes (C2H4/C3H6) is a significant but challenging process to produce polymer-grade C2H4 and C3H6. Herein, we reported an optimally designed charge-separated organic framework CPOS-1 with confined polar channels for highly efficient alkyne/alkene separation. CPOS-1 exhibits excellent stability, remarkably high C2H2 (18.4 cm3/g) and C3H4 (20.9 cm3/g) uptakes at 0.01 bar and 298 K, and benchmark C2H2/C2H4 (25.1) and C3H4/C3H6 (43.9) separation selectivities for 1/99 alkyne/alkene mixtures. The practical alkyne/alkene separation performance was completely identified by breakthrough-column experiments under various conditions with excellent cycle stability and high alkene productivities (C2H4: 216.6 L/kg; C3H6: 162.4 L/kg). Theoretical calculations indicated that pore aperture in CPOS-1 acts as a tailored single molecule trap, where alkynes are captured by multiple synergistic electropositive and electronegative sites, thus enhancing the alkyne recognization. Furthermore, the ease of rehealing facilitates its practical application, transcending the limitations of the metal-organic frameworks (MOFs) and covalent organic frameworks (COFs).

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 "Pacman"). Third, we introduce tri(ethylene glycol) monododecylether (C12E3) droplets in the crystalline layer. Whereas the crystalline layer suppresses the motion of the C12E3 droplets, the aldehyde droplets create surface tension gradients upon depletion of surfactants from the air/water interface, thereby driving Marangoni flows that attract the C12E3 droplets as well as the myelin filaments they grow: Causing the C12E3 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.

Cytosine methylation, a key epigenetic modification in the regulation of gene expression, raises intriguing questions about its role in the formation and thermodynamic stability of G-quadruplex (G4) structures. We investigated the impact of the 5-methylcytosine residue (Cm) on the well-characterized bcl2Mid G4 structure that forms in a GC-rich region of the B-cell lymphoma 2 (BCL2) gene promoter, which influences its expression. Using solution-state NMR and biophysical techniques, we discovered an unexpected sequence-specific effect of Cm on the folding kinetics of bcl2Mid G4. Specifically, substituting cytosine at position C6 with C6m slows down G4 folding kinetics and influences the equilibrium between major and minor structures in the presence of K+ ions. Notably, the increased population of the minor structure enabled the characterization of its previously unidentified topology. Additionally, the presence of a single Cm residue induces local structural rearrangements in the major G4 structure and decreases its thermodynamic stability. Furthermore, we found that the zinc finger 3 motif of the Sp1 transcription factor preferentially binds to the minor G4 structure. These results suggest that Cm not only influences G4 polymorphism but may also regulate interactions with transcription factors, potentially affecting the regulation of gene expression.

One-step purification of CF3CF3 from ternary CF3CH2F/CF3CHF2/CF3CF3 mixture is crucial since its vital role in the semiconductor industry. However, efficient separation of chemically inert CF3CF3 remains challenging due to the difficulty in creating specific recognition sites in porous materials. In this work, we report the first example of anion-pillared MOFs to the separation of fluorinated electronic specialty gases, utilizing the unique electrostatic potential matching in the bipolar pores of SIFSIX-1-Cu to realize a benchmark CF3CH2F/CF3CHF2/CF3CF3 separation. SIFSIX-1-Cu exhibits the highest CF3CH2F and CF3CHF2 adsorption capacity at 0.01 bar, as well as the highest CF3CH2F/CF3CF3 and CF3CHF2/CF3CF3 IAST selectivity. Additionally, high-purity (≥ 99.995%) CF3CF3 with record productivity (882.9 L/kg) can be acquired through one-step breakthrough experiment of CF3CH2F/CF3CHF2/CF3CF3 (5/5/90). Theoretical calculations further reveal that the coexistence of electronegative SiF62- and partially electropositive H sites promotes SIFSIX-1-Cu to effectively anchor CF3CH2F and CF3CHF2 through multiple supramolecular interactions.

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 (PMin). By integrating this with the direct anchoring of amphiphilic probes on the outer leaflet (PMout), 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 Mg2+ 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 towards a more localized and nuanced perspective.

While 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 (WO42-) solution spontaneously produces a metal-oxo cluster (W6O192-), 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.

The condensation of prochiral cyclobutanones and diphenylphosphinyl hydroxylamine is achieved under Brønsted acid catalysis. Interestingly, the competing aza-Baeyer Villiger reaction is completely suppressed and the axially chiral oxime esters can be isolated in excellent yield and selectivity (up to 96% yield, up to 97:3 er). Computational analysis highlights the crucial role of the Brønsted acid in facilitating a successful condensation. Building on the inherent reactivity of the corresponding oxime esters, a one-pot protocol towards cyano-cyclopropanes was discovered, which establishes two consecutive stereocenters. This unusual ring contraction is triggered by strong base and permits an axial-to-point chirality transfer with good enantiospecificity (up to 98% es). Fine-tuning the reaction parameters enables stereodivergent access to both diastereomers of the cyanocyclopropanes, and the utility of this method is demonstrated through the formal synthesis of the drug Tasimelteon.

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 d8 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.

Circumacenes with unique electronic structures have garnered significant interest in both fundamental science and nanoelectronics. However, their synthesis and investigations into the structure-property relationships present considerable challenges. In this work, we report the successful synthesis and characterization of a stable circumtetracene derivative in crystalline form. For comparison, a new circumanthracene derivative was also prepared. The electronic properties of both compounds were systematically investigated using both various experimental techniques and DFT calculations. It was found that circumtetracene exhibits a dominant local aromatic nature with small open-shell diradical character, while circumanthracene displays a closed-shell global aromatic character. Both compounds show amphoteric redox behavior with narrow energy gaps. The dication of circumtetracene and the dianions of circumtetracene and circumanthracene can be obtained experimentally through chemical oxidation and reduction, all displaying intense NIR absorptions. Furthermore, the electronic properties of these derivatives were compared with those of previously reported circumacene analogues, revealing a transition in electronic structure from closed-shell global aromatic to singlet open-shell local aromatic configurations upon π-extension. This work provides a comprehensive exploration of the structure-property relationships within the circumacene series, offering valuable insights for the design and synthesis of novel multizigzag-edged nanographenes with tunable electronic properties.

Direct utilization of diluted CO2 enables sustainable CO2 conversion into valuable products, with reduced CeO2 emerging as an attractive candidate due to its exceptional redox flexibility. The catalytic efficacy of CeO2 is intimately tied to the electronic structure of 4f, yet the persistent challenge lies in maintaining a high and stable concentration of Ce3+. In this study, we propose a symmetry-breaking-induced amorphization strategy to achieve an exceptionally high Ce3+ ratio by B doping, which facilitates the reduction of Ce4+ to Ce3+ in amorphous CeO2. 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 CeO2,  facilitating the spontaneous transition to the amorphous phase. Electronic structure analysis confirms that even a modest 7.5% B doping can significantly elevate the Ce3+ ratio to 85.7%. The resulting amorphous B-doped CeO2/GO shows a remarkable CO2-to-CO conversion rate of 249.33 µmol g-1 h-1(under 15% CO2) and 103.4 µmol g-1 h-1(under 1% CO2), with 100% selectivity in both cases. This performance highlights how amorphization stabilizes defect states, making amorphous CeO2/GO with high Ce3+ an effective material for CO2 photoreduction and addressing key challenges in CO2 capture and utilization.

The abiotic synthesis of organic compounds from CO2 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 CO2 to C1‒C6 hydrocarbons and oxygenates driven solely by ultraviolet irradiation of water, mimicking early Earth environments. Using electron paramagnetic resonance (EPR), 17O/13C isotope labelling, and femtosecond transient absorption, we identify ionized water-derived radicals (H2O•+, •OH, e⁻aq, •H) as the key redox mediators. e⁻aq acts as a super-reductant (-2.9 V) to activate CO2 into CO2•⁻, while •H enables sequential hydrogenation. Critically, oxidative radicals (H2O•+ and •OH) recycle recalcitrant oxygenates (formate and oxalate) back into active CO2•⁻, sustaining a dynamic radical network. This process generates a diverse library of organic compounds, including methane, ethylene, and C6 dimethyl succinate, via radical assembly mechanisms spanning hydrogen-atom transfer, self-coupling, and cross-coupling. By integrating experimental validation with prebiotic simulations (formate-mediated redox modulation), we resolve the paradox of inert CO2/H2 activation in primordial environments and establish water not merely as a solvent, but as a reactive matrix directing abiotic organic synthesis.

Addition of tBuOK to orange RuCl2(iPr2PCH2CH2NH2)2 forms the pink, square planar, Ru(II) complex Ru(iPr2PCH2CH2NH)2. This is an active catalyst (ToF 250 s-1) for the dehydropolymerization of H3B·NMeH2 to give high molecular weight polyaminoborane, [H2BNMeH]n (Mn = 138,700 g mol-1) at low loadings (0.03 mol%). An induction period observed is due to the initial formation of a hydroxy-hydride species Ru(iPr2PCH2CH2NH2)2(OH)(H), prior to fast turnover.

Octalenobisterphenylene 1 (also known as terphenylene dimer) was synthesized from 3,3',5,5'-tetraaryl-substituted biaryl by tert-butyllithium-mediated cyclization followed by oxidative coupling. This one-pot two-step protocol facilitated the successive formation of four four-membered and two eight-membered rings. Treatment of 1 with sodium metal, followed by crystallization from THF, yielded the remarkable diradical dianion [(1·-)2]2-, where the two molecular halves are connected by four σ bonds. The cyclodimerization is driven by the pronounced reactivity and strain of the central six-membered ring within the [3]phenylene subunit. The structure and diradical nature of [(Na+)2(1·-)2] were confirmed through X-ray crystallography, DFT computations, and 1H NMR and ESR spectra. These investigations revealed that the two spins, one on each molecular half, exhibit minimal mutual interaction.

The development of donor-acceptor (D-A) covalent organic frameworks (COFs) has emerged as a promising strategy for enhancing photocatalytic performance. While most studies have concentrated on two-dimensional (2D) COFs, research into their three-dimensional (3D) counterparts remains limited. In this study, we rationally designed and synthesized a carbazoyl dicyanobenzene derivative (TBFCC) as an intrinsic D-A building block. By selecting TAPA, TAPB, and TAPT as the donor, acceptor-π, and acceptor donors, respectively, we synthesized three distinct D-A-extended COF materials: D-D-A, A-π-D-A, and A-D-A. Among these, 3D-TAPT-COF, featuring an A-D-A structure, exhibited the highest hydrogen evolution rate of 31.3 mmol g-1 h-1, surpassing most previously reported COF-based photocatalysts. This superior performance is attributed to its A-D-A configuration, which provides multiple charge transfer pathways in three-dimensional space, overcoming the electron transport limitations inherent in 2D COFs. Consequently, this feature facilitates efficient separation of photogenerated charges within the framework and reduces carrier recombination, thereby optimizing photocatalytic efficiency.

Bioisosteric replacement is an important strategy in drug discovery and is commonly practiced in medicinal chemistry, however, the incorporation of bioisosteres typically requires laborious multistep de novo synthesis. The direct conversion of a functional group into its corresponding bioisostere is of particular significance in evaluating structure-property relationships. Herein, we report a functional-group-exchange strategy that enables the direct conversion of aromatic lactones, a prevalent motif in bioactive molecules, into their corresponding cyclic hemiboronic acid bioisosteres. Scope evaluation and product derivatization experiments demonstrate the synthetic value and broad functional-group compatibility of this strategy, while the application of this methodology to the rapid remodeling of chromenone cores in bioactive molecules highlights its utility.

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 mmolH2gcat-1h-1 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.