ACS Publications最新文献

Motivated by the emerging control of Berry-curvature textures in altermagnets, we explore a two-terminal configuration where a topological-insulator film is interfaced with two altermagnetic electrodes whose crystalline phases can be rotated independently. The proximity coupling imprints each altermagnet's momentum-dependent spin texture onto the Dirac surface states, giving rise to an angular mass whose sign follows the lattice orientation. Adjusting the phase of one electrode redefines this mass pattern, thereby tuning the number and spatial distribution of chiral edge channels. This results in discrete conductance steps and a reversible inversion of the thermoelectric Hall coefficient─achieved without external magnetic fields or net magnetization. A compact Dirac model captures both the quantized switching and its resilience to moderate disorder. Overall, this symmetry-driven mechanism provides a practical and low-dissipation route to programmable topological transport via lattice rotation.

Ammonia (NH₃) is essential for fertilizer production and is increasingly recognized as a promising carbon-free energy carrier. Given the abundant energy input from solar illumination and the widespread availability of relatively inexpensive atmospheric nitrogen (N₂) gas, photocatalytic N₂ fixation has attracted an increasing amount of interest. Here, we report a bismuth-rich design strategy within the Bi-O-Br system to enhance the photocatalytic N₂ fixation. A series of bismuth oxybromides with tunable Bi/Br ratios (BiOBr (1:1) to Bi₄O₅Br₂ (2:1), Bi₂₄O₃₁Br₁₀ (2.4:1), and Bi₃O₄Br (3:1)) were synthesized by a facile solvothermal route and evaluated for N₂ reduction in pure water under visible light without cocatalysts or sacrificial agents. Among them, Bi₃O₄Br achieved the highest NH₃ yield (790 μmol/g/h) and exhibited good structural stability, retaining more than 95% of its activity over three repeated cycles. The efficient activity is attributed to its stronger light absorption, more negative conduction band, efficient charge separation, and longer carrier lifetime. Spectroelectrochemical analysis confirmed its high reduction ability, while oxygen vacancies facilitated enhanced N₂ adsorption and bond cleavage. Selectivity is evidenced by NH₃ being the only detected nitrogen-containing reduction product in the postreaction solution, and concurrent water oxidation is evidenced by H₂O₂ formation. These results establish a clear composition-activity relationship, highlighting bismuth-rich Bi₃O₄Br as a practical and effective photocatalyst for the fixation of aqueous N₂ into NH₃.

Developing peroxidase-like nanomaterials of high activity, low cost, and eco-friendliness remains a key challenge for effective and efficient antibacterial applications. Herein, of the reducibility and molecular simplicity, cysteine (Cys) was introduced into a zinc-iron-layered double hydroxide (ZnFe-LDH) to build the valence-regulated nanozyme (Cys-ZnFe-LDH). Via the reduction and intercalation, Cys-ZnFe-LDH was facile and mildly acquired with valence regulation and interlayer space enlargement, promoting the mass transfer rate and redox cycle, so as to enhance the catalytic performance. Significantly, intercalated with cysteine, the Fe²⁺/Fe³⁺ ratio increased from 1.42 to 3.27 in Cys-ZnFe-LDH, and also the specific surface areas enlarged from 48.989 to 79.445 m²/g. Notably, Cys-ZnFe-LDH remarkably enhanced H₂O₂ decomposition into hydroxyl radicals, with the maximum reaction velocity of 25.80 × 10^-8 M·s^-1, as well as an extremely high affinity, favoring efficient •OH generation. However, leveraging such superior enzyme-mimicking activity, Cys-ZnFe-LDH possessed the potential broad-spectrum antibacterial performance, respectively, achieving 99% elimination of Escherichia coli (0.5 mM H₂O₂, 50 μg·mL^-1) and Staphylococcus aureus (0.1 mM H₂O₂, 100 μg·mL^-1), as well as a remarkable hemolysis rate and cell survival rate. Prospectively, Cys-ZnFe-LDH was a synergistic antibacterial "nanoknife" of the enhanced interfacial enrichment, Fe valence-state regulation, and •OH-driven oxidative damage.

Electron transport across interfaces governs a broad range of fundamental phenomena. Although orbital overlap is recognized as a key determinant, its experimental quantification remains elusive. Here, we establish the interfacial hopping integral (t_eld-mol), quantifying orbital overlap between contacting atoms, as a predictive descriptor of single-molecule conductance in a benchmark domain of saturated α,ω-functionalized alkane junctions. Using scanning tunneling microscopy and molecular-junction mapping technique, we correlate conductance with molecular tilt (tilt_mol) across π- and σ-type headgroups to extract t_eld-mol. We start with single-atom-thick bismuth and lead adlayers on gold, with dominant p-character simpler than gold's d-orbitals. A tight-binding model incorporating Newns-Anderson-Grimley theory yields conductance heatmaps that qualitatively match experiment results and generalize to diverse molecular junctions. Applying this model to the seminal case of alkanedithiols rationalizes literature findings of one to three conductance sets by linking them to tilt_mol and corresponding t_eld-mol variations.

The precise modulation of nanoparticles represents a critical step toward programmable nanodevice architectures and functional material systems. Here, we demonstrate an artificial CeO₂ nanoparticle modulation platform, enabling area-selective manipulation and programmable tunability of the CeO₂ nanoparticle tunneling behavior. Utilizing atomic force microscopy lithography, CeO₂ nanoparticles were attached, detached, and repositioned with nanoscale precision on both insulating and metallic substrates, forming ordered architectures. Sequential strain engineering induces deterministic narrowing of the local density of states, deriving the electronic switching at the single-particle level. Furthermore, vertical 3D stacking of CeO₂ nanoparticle tunneling junctions exhibits designable resonant tunneling and negative differential resistance characteristics, with the threshold strain systematically decreasing with the stacking tier. In conclusion, we envision that our artificial modulation platform provides a systematic foundation for nanoelectronic systems and functional tunneling devices within artificial nanoparticle assemblies.

Despite the growing interest in organic thermoelectrics, n-type polymers generally exhibit lower performance than their p-type counterparts, limiting the development of efficient thermoelectric generators. Herein, we report two new n-type polymers based on cyanothiophene-flanked diketopyrrolopyrrole (CDPP) copolymerized with either diketopyrrolopyrrole (PCDPP-DPP) or dialkoxybithiazole (PCDPP-BTzOR) to investigate the critical yet scarcely explored role of orbital interaction between counits in governing thermoelectric performance. Although PCDPP-BTzOR exhibits a more conformationally locked backbone, higher molecular weight, comparable film crystallinity, and nearly identical LUMO level to PCDPP-DPP, the latter displays markedly superior charge transport and doping response. PCDPP-DPP achieves higher field-effect electron mobility (0.191 vs 0.013 cm² V^-1 s^-1) and carrier concentration after n-doping (1.4 vs 1.0 × 10²⁰ spins cm^-3), yielding over an order of magnitude higher electrical conductivity (25.71 vs 1.97 S cm^-1). These improvements arise from the deliberate tuning of interunit orbital interactions in PCDPP-DPP, which promotes electronic delocalization and mitigates trapping associated with polarized charge-transfer states. Consequently, PCDPP-DPP attains a high power factor of 23.52 μW m^-1 K^-2 and a promising room-temperature figure of merit of ZT = 0.07. Overall, this work establishes orbital interaction engineering as an effective strategy for designing high-performance n-type thermoelectric polymers.

An interconnected loop of messages and counter-messages determine the outcome of host-pathogen interactions. Multihost pathogenicity across plants and animals, particularly nematode, is a major source of new infectious diseases. Fusarium oxysporum, a multihost pathogen, causes vascular wilt in chickpea and fusariosis in worm and humans. To comprehend Fusarium-responsive multihost pathogenicity, we temporally profiled cross-kingdom species, chickpea and worm using SWATH-mass spectrometry. Morphological analyses revealed that increased wilting and intestinal disintegration elicits a disease response in chickpea and worm. Peptide-spectrum library consisted of 5629 and 3138 proteins from Fusarium infected chickpea and worm, respectively. SWATH analysis identified 1573 and 2249 disease-responsive chickpea (CaDRPs) and worm proteins (CeDRPs) linked to diverse organs, organelles, and functionality. Pairwise comparisons; over-representation analysis between time, treatment, and organism; wilt, and fusariosis diseasome revealed common and unique modules. CaDRPs involved in preformed defense, biomolecule synthesis, phytohormone regulation, ser/thr kinase, and ATP signaling have perturbed interactions and functions, majorly in chloroplast. CeDRPs linked to the cuticular support, muscle organization, neuronal information, intestinal metabolism, G-protein, and notch signaling showed a deregulated function, especially in the cytoplasm. Common biological processes, included primary metabolism, ribosome biogenesis, calcium signaling, and proteostasis. Our data provide first evidence of translational plasticity in the Fusarium diseasome providing novel insights into multihost pathogenesis.

Bi₂O₂Se is an emerging n-type semiconductor, but conventional growth methods often rely on high temperatures or complex multisource systems that introduce defects and limit device integration. Herein, we report a simplified and modified physical vapor deposition (PVD) strategy enabling the growth of single-crystal Bi₂O₂Se nanosheets at a lower temperature of 500 °C. The self-powered photoelectric detector with an asymmetric structure was fabricated using a Bi₂O₂Se nanosheet as channel material, exhibiting an ultralow dark current of ∼10 fA, weak-light detection capability (50 nW/cm²), and detectivity up to 1.06 × 10¹³ Jones. The devices also show fast response time and excellent long-term stability with <10% degradation after 12 months in the atmospheric environment. Furthermore, single-pixel imaging demonstrates high contrast and fidelity. This work establishes a practical route for low-temperature growth of high-quality Bi₂O₂Se nanosheets and highlights its strong potential for weak-light detection, broadband sensing, and chip-scale photonic systems.

Regulating gene expression with precision is essential for cellular engineering and biosensing applications, where rapid, programmable, and sensitive control is desired. Current approaches to regulatory circuit design often rely on control at a single regulatory level, primarily the transcriptional level, thereby limiting the capability of fine-tuning the regulatory dynamics in response to complex stimuli. To address this challenge, we developed four novel RNA-protein hybrid type-1 incoherent feed-forward loop (I1-FFL) circuits in Escherichia coli that integrate transcriptional and translational regulators to achieve multilevel control of gene expression. These hybrid circuits leverage the modularity and rapid dynamics of RNA-based activators alongside the versatile inhibition capabilities of the protein-based repressors to endow tunable pulse dynamics through engineered delays that act as transient repressor decoys. By repurposing synthetic RNA regulators at multiple regulatory levels together with aptamers and RNA-binding proteins, we demonstrate previously unexplored circuits with tunable dynamics. Complementary simulation results highlighted the importance of the engineered delays in achieving tunable pulse dynamics in these circuits. Integrating modeling insights with experimental validation, we demonstrated the flexibility of designing the RNA-protein hybrid I1-FFL circuits, as well as the tunability of their dynamics, highlighting their suitability for applications in environmental monitoring, metabolic engineering, and other engineered biological systems where precise temporal control and adaptable gene regulation are desired.

Enzyme-encapsulated nanogels serve as promising platforms for constructing enzyme nanoreactors in which mass transport plays a crucial role in the enzymatic performance. However, it remains a challenge to investigate the relationship between the permeability of nanoreactors and their catalytic efficiency owing to their small dimensions. The molecular permeability behavior and enzyme activity of two types of nanogels with different hydrophobicities are compared using 8-anilinonaphthalene-1-sulfonic acid (ANS) fluorescence assays. Partitioning experiments with different fluorescent dyes demonstrate that hydrophobic and electrostatic interactions govern the molecular distributions within the nanogels. Total internal reflection microscopy (TIRF) further demonstrates that a less hydrophobic microenvironment facilitates the faster mass transport of hydrophobic resorufin molecules. This contributes to the higher catalytic activity and greater reaction heterogeneity observed in the single-particle assays. These results underscore the importance of hydrogel molecular permeability in modulating enzyme kinetics and offer valuable insights into the rational design of efficient enzyme nanoreactors.