A Ga3+-Zr4+ co-doping strategy at the B-site is developed to simultaneously enhance oxygen reduction reaction (ORR) activity, structural stability, and CO2 tolerance of La0.6Sr0.4FeO3−δ (LSF64) cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The synergistic charge compensation between lower-valence Ga3+ (ionic compensation) and higher-valence Zr4+ (electronic compensation) significantly increases oxygen vacancy concentration and optimizes the Fe3+/Fe4+ redox equilibrium, thereby accelerating both oxygen surface exchange and bulk diffusion. XPS and EPR analyses confirm substantially enriched oxygen vacancy populations in the co-doped material. Electrical conductivity relaxation measurements further reveal enhanced oxygen surface exchange and bulk diffusion coefficients, indicating accelerated oxygen transport kinetics. As a result, the optimized La0.6Sr0.4Fe0.8Ga0.1Zr0.1O3−δ (LSFGZ) cathode exhibits a low polarization resistance of 0.12 Ω·cm2 at 700 °C, approximately 76
Per- and polyfluoroalkyl carboxylic acids (PFCA) are persistent organic pollutants with complex structures and strong biological toxicity. Single-molecule sensing using Aerolysin (Ael) nanopore and cationic probe enables standard-free quantification of PFCA homologues, but its identification performance is limited by the relatively short analyte dwell time in wild type (WT) Ael. Herein, we engineered the nanopore sensing interface by introducing lysine (K) and arginine (R) at three sites near the trans exit barrier of Ael (T240, E258, and A260) to prolong analyte dwell time and enhance resolution. All-atom molecular dynamics simulation revealed that the electrostatic potentials at trans exit shifted from negative (WT) to strong positive for all mutants. The K-substitutions significantly enhanced the signal difference among analytes, as experimentally validated by two aliphatic isomers. In particular, A260K exhibited the most superior sensing capability: dwell time was increased by 50-fold and the sigma of blockade was reduced by 80
Alkali-metal doping is an effective chemical strategy for tuning the electronic structure of coordination polymers. In this work, single-chain models of alkali-metal doped poly[Ax (Ni-ett)] (A=Li, Na, K; ett=ethene-1,1,2,2-tetrathiolate) were constructed, and their structural stability, electronic structure, and electronic thermoelectric response were investigated using the first-principles density functional theory combined with nonequilibrium Green’s function method. Calculation results show that alkali-metal atoms donate electrons to the Ni-ett backbone and regulate the local coordination environment through structural relaxation and dopant-backbone orbital hybridization. These chemical effects reshape the electronic states near the Fermi level and further regulate the coherent electronic transport channels along the chain. Among the three dopants, K gives more favorable binding with the Ni-ett framework and preserves higher electronic transmission in selected valence-band energy windows than Li and Na. For the x =1/3 K-doped model, the optimized electronic structure leads to a pronounced electronic power factor and a relatively high electronic figure of merit ZTe, with a maximum value of approximately 0.13. This study clarifies the atomic-scale relationship between alkali-metal doping, electronicstructure modulation, and electronic thermoelectric response in poly[Ni-ett] coordination polymer chains, providing theoretical guidance for chemical doping design in low-dimensional coordination-polymer thermoelectric materials.
Herein, we report a water-compatible, reversibly switchable fluorescent assembly engineered from a pyridinium-functionalized triphenylamine (TPA) and a water-soluble pillar[5]arene (WP5). UV-Vis titration confirmed a strong 1:1 host-guest stoichiometry with a high association constant (2.95×106 L/mol). Supramolecular confinement induces significant bathochromic shifts in both absorption (453→472 nm) and emission (607→635 nm), alongside a nearly tenfold fluorescence enhancement. Mechanistically, protonation of the carboxylate rim at low pH reconfigures interfacial electrostatic and hydrophobic interactions, triggering a further redshift to 639 nm and elevating the absolute quantum yield from 1.04
Optical Chemical Structure Recognition (OCSR) is a key technology at the intersection of chemistry and computer science, aiming to convert molecular structure images into machine-readable sequence representations. However, existing OCSR models still fall short in building long-range dependencies within sequences, making it difficult to accurately generate long sequences with complex structures. To address this, we propose a Multi-Scale Memory-Enhanced Transformer (MSMET) model and design two modules: the Layer-wise Hierarchical Fusion (LHF) module and the Cross-Attention Memory Augmentation (CAMA) module. The LHF module employs adaptive feature recalibration across encoder blocks through learnable gating, effectively alleviating feature forgetting phenomena in deep architectures while maintaining multi-scale visual discriminability. The CAMA module equips the decoder with a learnable memory matrix that dynamically enriches cross-modal attention, significantly enhancing the model’s capacity to capture long-distance topological interactions in molecular graph structures. We evaluated the performance of MSMET, and the experimental results demonstrate that the model achieved strong overall state-of-the-art performance.
DNA knots represent critical topological structures arising during DNA replication, recombination, and repair, of which the aberrant accumulation threatens genomic stability. Helicases and topoisomerases act cooperatively to maintain genomic integrity by specifically recognizing DNA knots and progressively unwinding them or relieving topological stress through transient DNA strand cleavage. This study employs solid-state nanopore (SSN) technology to achieve high-resolution detection of λ-DNA knots under optimized conditions. Our work demonstrates that DNA knot translocation generates multistage signals of ionic current blockade, with blockage current amplitude positively correlating with topological complexity. Furthermore, the capture frequency of DNA knots increases significantly with applied bias voltages, while translocation duration decreases with reduced channel length (referring to the thickness of silicon nitride). Notably, topoisomerase II (TOPII) exhibits moderate resolving activity toward DNA knots, manifested by an increased proportion of linear DNA signals and shortened blockade durations. The splitting efficiency of TOPII is influenced by the supercoiling status of DNA and the concentration of enzyme; the underlying molecular mechanism needs further investigation with combined single-molecule fluorescence techniques. This study innovatively applies solid-state nanopore technology to explore DNA topology and DNA-TOPII interaction, providing a new research strategy for related fields.
The pore architecture of zeolite honeycomb monoliths critically governs the balance between mechanical strength and mass transfer performance. However, tailoring pore structure remains challenging because increased porosity often compromises structural integrity. Herein, we develop a composite pore-forming strategy using potato starch, rice starch, and polymethyl methacrylate (PMMA), which provides a graded particle size distribution and complementary morphologies. Hierarchically porous NaY zeolite honeycomb monoliths were fabricated via extrusion, drying, and calcination. Thermal decomposition of the pore-forming agents generated an interconnected micro-mesomacroporous pore network. Increasing the potato starch content progressively promoted the formation of larger interconnected pores and improved pore connectivity. The compressive strength of the porous monoliths (15
Process-directed self-assembly of block copolymers refers to the processes that can reproducibly direct the kinetics of structure formation ensuing from an unstable state, generated by rapidly altering the thermodynamic parameter(s) of system, into a desired, metastable state. Compared with the strategy that focuses on the alleviation of the packing frustration of desired, metastable states by fine-tuning the chain architecture of the block copolymer or blending and therefore makes them thermodynamically stable, it is particularly suitable for the fabrication of desired, metastable states with high packing frustration, which is very hard to release. Moreover, this strategy also provides ample opportunities for the explorations on the symmetry-conserving and symmetry-altering phenomena during the kinetics of structure formation. This review mainly focuses on the theories and particle-based simulations that can be used to explore the process-directed self-assembly of block copolymers. Several representative results, which are obtained by both theories and particle-based simulations using the alchemical transformation and fast, isotropic pressure quench, respectively, to generate the unstable states as the starting points, are reviewed as well to highlight the efficiency of such a strategy as well as the symmetry-conserving and symmetry-altering phenomena during the kinetics of structure formation. The challenges encountered currently are also briefly discussed.
Full-thickness repair of chronic wounds poses significant clinical challenges. Although antioxidant and anti-inflammatory effects accelerate the healing of chronic wounds, achieving complete skin regeneration with appendages remains challenging in clinical practice. Herein, a unique selenium-containing thermo-sensitive hydrogel, poly(ethylene glycol)-block-poly(L-selenomethionine) (EG45SeMet25), is designed to reprogram the wound microenvironments and promote skin appendage regeneration in diabetic chronic wounds. EG45SeMet25 forms an injectable sol at room temperature and undergoes a sol-gel transition at body temperature, enabling complete filling of irregular wound defects. Moreover, EG45SeMet25 enhances cell proliferation and effectively scavenges intracellular reactive oxygen species (ROS), thereby exerting cytoprotective effects. Meanwhile, it modulates macrophage polarization to establish a pro-regenerative immune microenvironment. EG45SeMet25 significantly promotes the healing of full-thickness skin wounds in diabetic mice. After 14 d, the remaining unhealed wound area decreases to 2.53
The increasing demand for strategic mineral resources, together with the need for low-carbon and environmentally responsible extraction technologies, has made the efficient utilization of salt-lake resources an urgent research priority. Salt-lake brines contain abundant Li, Na, K, Cs, B, U, and other valuable elements, but their high salinity and complex multi-ion matrices pose major challenges to selective separation. Covalent organic frameworks (COFs), a class of crystalline porous polymers with designable skeletons, tunable pore environments and modifiable functional sites, offer a promising platform for element extraction from salt lakes. This review summarizes recent advances in the design of COFs for salt-lake resource recovery, with particular emphasis on functional-site engineering, pore regulation, ion-recognition mechanisms and representative applications in the capture and separation of lithium, potassium, cesium, boron, and uranium. Current limitations, including scalable synthesis, long-term stability, and the transition from empirical design to mechanism-guided material development, are also discussed. This review is expected to provide useful guidance for the rational design of high-performance COF materials for sustainable salt-lake resource utilization.
Alkaline-earth metal carbonate, an inorganic mineral resource with abundant reserves and wide distribution on Earth, has historically been used as an ordinary non-metallic mineral to produce cement, building materials, etc. In the conventional usage of carbonate minerals, massive CO2 emission occurs. This review focuses on the remodel of carbonate decomposition reaction from CO2 emission to directed hydrogenation, pioneering a pathway of syngas production from inorganic carbon resource. The state-of-the-art development of hydrogenated decomposition of solid carbonates has been summarized. The carbonate chemical pathway for CO2 capture, as well as the recent progress of integrated carbon capture-conversion (ICCC), is also discussed.
Amorphous nanomaterials, which combine short-range order with long-range disorder, provide defect-rich platforms for tailoring electronic structure. This review surveys the controllable synthesis of two-dimensional amorphous metal oxides (2D AMOs)—spanning top-down, topotactic, template-directed, and wet-chemical paradigms—with an emphasis on regulating the amorphous phase while preserving the 2D morphology. We then examine key structural-modification strategies, including phase engineering, single-atom anchoring, conductive hybridization, and defect manipulation. Building on these foundations, their applications in electrochemical energy storage and conversion are discussed to clarify the underlying structure-property-performance relationships. Finally, the remaining bottlenecks and future perspectives are outlined, charting a roadmap toward practical, scalable use.
Triple-negative breast cancer (TNBC) is an aggressive breast cancer subtype with limited therapeutic targets, highlighting the necessity for serum-based candidate biomarker discovery. In this study, we developed a serum small extracellular vesicle (sEV) proteomic workflow based on functionalized nanobowl enrichment and a simple on-beads lysis and in-tube digestion pretreatment for sEVs. And 107 clinical serum samples were analyzed, each requiring only 50 microliters of serum. A total of 3477 proteins were quantified, and 3152 proteins detected in >50
The molar extinction coefficient (ε) is a fundamental physical parameter for optoelectronic molecules, critically determining the energy conversion efficiencies of corresponding devices. Benefiting from strong intramolecular resonance enabled by donor-acceptor (D-A) structural modulation, merocyanine dyes are capable of delivering large ε at relatively low molecular weights. Such resonance originates from the equilibrium between neutral and zwitterionic resonance forms, whose magnitude can be quantitatively evaluated using the resonance coefficient c2. Specifically, a c2 of 0.5 corresponds to ideal strong resonance and superior photophysical performance. Herein, two D-π-A emitters, namely N-O-2CN and N-S-S, were rationally developed. Both molecules possess prominent two-state resonance characteristics, with calculated c2 values of 0.44 and 0.45, respectively. Consistently, the two compounds display outstanding molar absorptivity: N-O-2CN affords a maximum ε of 6.43×104 L·mol−1·cm−1 at 468 nm. More impressively, N-S-S reaches an exceptionally high ε of 1.23×105 L·mol−1·cm−1 at 509 nm while bearing a low molecular weight of merely 377, which facilitates favorable processing capability. In addition, N-O-2CN and N-S-S exhibit narrowband blue and green luminescence, with full-width-at-half-maximum of 0.26 eV at 491 nm and 0.20 eV at 532 nm, respectively.
Artificial nitrogen photofixation enables green ammonia synthesis under ambient conditions, making it one of the cutting-edge technologies in the fields of energy transition and sustainable development. Rapid growth in nitrogen photofixation has yielded a massive volume of publications, posing new challenges for manual literature screening, mechanism integration, and future trend analyses. Large language models (LLMs), with their robust capabilities in semantic understanding, information extraction, and logical reasoning, can significantly facilitate literature mining in photocatalysis. Taking artificial nitrogen photofixation as a case study, this perspective constructs an LLM-assisted literature analysis system and explores the practical value of intelligent analytical technologies in view of the emerging tendency. Furthermore, we also explore the anticipated contributions and challenges of artificial intelligence in photocatalysis, particularly regarding material design, experimental optimization, and mechanism investigation, with the aim of establishing a forward-looking roadmap for a low-carbon future in photocatalysis.
Phase transitions in strongly correlated system materials have good reproducibility due to the differences before and after the transition, and they have application prospects in fields, such as memory storage and electrochromic materials. Driving protons in ionic liquids into the material lattice using an electric field is an effective way to change the electronic structure of strongly correlated systems and induce their phase transitions. In this study, we used the electrochemical proton injection method to introduce protons into La1−x−yCaxKyMnO3 manganate perovskites with different properties. The combination of protons with O in the lattice hinders the double exchange interaction, preventing effective electron transfer and thereby triggering a phase transition. This work complements the understanding of the effects of proton injection on bulk materials, deepens the understanding of the mechanism of proton injection-induced phase transitions, and provides new ideas for the preparation of novel multifunctional devices.
NaA zeolite membranes are widely utilized in the separation field. However, their large-scale application has been constrained by the requirement of bulky, sealed autoclaves, resulting in high synthesis costs. Herein, we developed a hydroxyl radical-assisted hydrothermal strategy to synthesize NaA membranes. This method enables the synthesis of highly crystalline and continuous NaA membranes within only 8 h at 45 °C in an open system. Notably, we scaled up the synthesis to achieve uniform crystallization on a 10 cm×6 cm substrate, overcoming the scalability limitations inherent to traditional autoclave-based synthesis. The versatility of this approach is further demonstrated by its applicability to diverse substrates, including metal oxides, glass, and polymers. Through a combination of ex-situ characterization techniques [X-ray diffraction (XRD), scanning electron microscopy (SEM)] and spectroscopic analysis [electron paramagnetic resonance (EPR), fluorescence], we confirm the critical role of hydroxyl radicals in accelerating membrane formation. Furthermore, the broad applicability of this method is validated by the successful synthesis of high-quality FAU zeolite membranes. This work establishes a new paradigm for zeolite membrane synthesis, paving the way for their industrial-scale production and broader practical applications.
Stably and controllably doping free carriers, here specifically free electrons, into colloidal quantum dots (QDs) is central to realizing their size-tunable optical and optoelectronic properties. Unlike bulk semiconductors, aliovalent atomic doping in QDs is challenging due to self-purification mechanism. This mini-review focuses on recent advances in one type of unique doping strategies for QDs (i.e., remote electron-doping into their quantum-confined conduction band), including chemical, electrochemical, and photochemical approaches. We discuss optical properties, many-body interactions, and Fermi-level shifts of n-doped QDs. Impacts of n-doping on low-threshold optical gain, infrared intraband emission and detection, and charge-transport layers in devices are discussed.
Cotton textiles (CTs) are in high demand for antimicrobial applications. Traditional approaches often struggle to achieve antibacterial and antifungal efficacy simultaneously. Herein, organosilicon quaternary ammonium salt (QAS/AEM-5700, a contact bactericidal agent) and organosilicon borneol ester (SBA, a stereochemical anti-adhesive agent) are covalently co-grafted onto CT surfaces via siloxane hydrolytic condensation, generating a synergistic antimicrobial coating (CT-A/S) that integrates both offensive and defensive functionalities. The as-prepared CT-A/S exhibits excellent antimicrobial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Aspergillus niger (A. niger), with antimicrobial rates approaching 100
