Photoderived Bi nanobridge enabling an S-scheme BiOCO-Bi-TiO heterojunction for efficient photocatalytic water splitting and methanol reforming
Constructing strongly coupled S-scheme heterojunctions without sacrificing redox capability remains a central challenge in photocatalytic water splitting. Herein, we report the in situ photogeneration of metallic Bi (Bi) nanobridges from layered BiOCO (BOC) under UV irradiation, which effectively wire BOC with TiO (P25) to form a ternary BOC-Bi-TiO S-scheme heterojunction. Under ultraviolet-visible light or simulated sunlight, the optimized BOC-0.5P25 catalyst achieves a high H evolution rate of ∼5.8 mmol·g·h, which further increases by ∼24 % (to ∼7.2 mmol·g·h) after light-activated cycling. The apparent quantum efficiency (AQE) reaches 2.45 % at 380 nm. Structural characterizations confirm the light-induced formation of Bi, accompanied by a slight chemical shift in Ti 2p and Bi 4f spectra, consistent with interfacial band bending. Band structure and kinetics analyses elucidate an S-scheme charge transfer mechanism where electrons preferentially flow via Bi into TiO while holes stay on BiOCO, driven by the built-in field. Isotopic labeling experiments via Gas Chromatography-Mass Spectrometry (GC-MS) isotopologues (CHD in DO/MeOH) together with online Differential Electrochemical Mass Spectrometry (DEMS) signals confirm that water contributes to both H production and methanol oxidative reforming (partially to CH). The concept of light-triggered, in-situ mediator activation provides a practical route for photocatalytic water reduction coupled with methanol oxidative reforming under unbiased and noble-metal-free conditions through engineering tightly coupled S-scheme interfaces.
Dual-functional copper nanoplatform potentiates cuproptosis through p53 reactivation and metabolic reprogramming
Cuproptosis, a copper-dependent form of regulated cell death driven by mitochondrial metabolism, holds promise as a therapeutic strategy for cancer. However, its efficacy is hampered by tumor metabolic heterogeneity and mutant p53 (mut-p53)-driven metabolic rewiring that blunts cuproptosis sensitivity. Here, we report the rational design of CuF16@246, an acid-responsive, dual-functional copper-based nanocoordination polymer that integrates Cu and the p53 reactivator eprenetapopt (APR-246) within a single perfluorosebacic acid (PFSEA)-coordinated framework to synergistically induce cuproptosis and reverse tumor metabolic reprogramming. CuF16@246 comprises a PFSEA-coordinated copper framework with good colloidal stability and pH-dependent co-release of Cu and APR-246, enabling controlled Cu release and in situ APR-246 loading. Mechanistically, CuF16@246 triggers hallmarks of cuproptosis, including dihydrolipoamide S-acetyltransferase (DLAT) oligomerization and the depletion of the iron‑sulfur (Fe-S) cluster proteins ferredoxin 1 (FDX1) and lipoic acid synthase (LIAS), while APR-246 converts mut-p53 toward a wild-type-like, DNA-binding-competent state, upregulates metabolic targets such as TP53-induced glycolysis and apoptosis regulator (TIGAR) and glutaminase 2 (GLS2), suppresses glycolysis, and enhances tricarboxylic acid (TCA) cycle flux, thereby sensitizing tumor cells to cuproptosis. In vitro and in vivo studies demonstrate that CuF16@246 exhibits more efficient cellular uptake, more potent cytotoxicity, and more significant tumor growth inhibition than individual treatments, without inducing hemolysis or major organ toxicity. This work establishes a dual-functional strategy that combines metabolic reprogramming with sensitized cuproptosis, providing a promising framework for developing advanced copper-based nanomedicines for the treatment of mut-p53-positive cancers.
Efficient removal of dimethylacetamide through the activation of peroxymonosulfate in a continuous flow-through electrocatalytic membrane reactor utilizing Co-N doped carbon membrane anode
The cobalt-doped conductive carbon membrane (CoCM) with a single-atom Co-N active structure was synthesized from activated carbon and ZIF-67 via compression molding and high-temperature carbonization. The effect of ZIF-67 doping (0-10 wt%) on CoCM's microstructure and performance was systematically studied. The optimal CoCM5 (5 wt% ZIF-67) showed a honeycomb pore structure (37.2 nm average pore diameter, 42.3 % porosity, 462.7 m/g BET surface area) and maintained 5.8 MPa bending strength. Electrochemical tests confirmed CoCM5 had a much lower charge transfer resistance (1.67 Ω) than undoped CoCM0 (8.95 Ω), boosting peroxymonosulfate (PMS) activation. As the anode in a continuous flow-through electrocatalytic membrane reactor (ECMR), CoCM5 achieved 63.8 % degradation of 0.2 g/L dimethylacetamide (DMAc) at 2 V-1.5 times higher than the Fe-N doped carbon membrane system. High-performance liquid chromatography identified N-methylacetamide and acetamide as key intermediates, verifying DMAc's stepwise N-demethylation. Density functional theory (DFT) and experiments revealed the core mechanism: the Co-N structure (dominant active site) reduces PMS activation energy barrier to 0.39 eV (0.39 eV lower than CoCM0) and promotes electron transfer from Co(III) to PMS, generating 2.3 times more sulfate (SO) and hydroxyl (OH) radicals than CoCM0. This study provides a strategy for designing self-supported, stable metal‑nitrogen-doped carbon membranes and highlights ECMR's potential in solving low mass transfer and secondary contamination issues in refractory organic wastewater treatment.
Simultaneously regulating hydrophilicity and adsorption-reduction isosite of carbon cathode to achieve efficient photoelectrocatalytic recovery of uranium from complex wastewater
Organics inevitably present in uranium-containing wastewater pose significant challenges for conventional uranium recovery methods. Here, a N-doped carbon cathode, which is simultaneously modified with cyano (-C ≡ N) groups and zirconia (ZrO), and grown on a carbon felt (ZCN-NC/CF), has been developed for application in a self-powered photoelectrocatalytic (SP-PEC) system for the treatment of complex uranium-organic wastewater. Density functional theory (DFT) calculations indicate that -C ≡ N can serve as a common site for electron aggregation and U(VI) adsorption, thereby shortening the electron migration path and improving the photocatalytic uranium extraction performance. Hydrophilicity tests demonstrate that the introduction of ZrO can significantly enhance the hydrophilicity of the carbon matrix, thereby promoting the interaction between the cathode and uranium in the aqueous environment. Therefore, the SP-PEC system with ZCN-NC/CF as the cathode exhibits outstanding activity in simultaneously reducing U(VI) and degrading organic matter. After 30 min of illumination, the removal rates of uranium and aureomycin (ARM) can reach 99.7 % and 100 %, respectively. This work presents an example of designing highly efficient carbon-based cathode materials in PEC system for the treatment of complex uranium-containing wastewater.
Efficient epimerization of highly concentrated glucose to mannose over electronic structure-modulated Mo/NC catalyst
The catalytic conversion of concentrated glucose to mannose is of considerable interest due to the latter's therapeutic value, yet it is constrained by low catalytic efficiency. Herein, a Mo/NC-300 catalyst was constructed by introducing active Mo species into a nitrogen-doped carbon (NC) matrix via pyrolysis. The resulting catalyst demonstrated outstanding activity in the epimerization of high-concentration glucose (50 wt%) to mannose, achieving a high yield of 33.4 % and selectivity of 94.6 %, alongside an excellent productivity of 123.7 mmol·g·h. Catalyst characterizations and density functional theory calculations revealed that the NC layer modulates the electronic structure of Mo species, shifting the d-band center upwards. This preferentially enhances glucose adsorption and lowers the epimerization energy barrier. Isotope labeling experiments further confirmed the reaction follows an intramolecular 1,2‑carbon shift mechanism. The catalyst also exhibited excellent stability and reusability, primarily attributed to the hydrophobicity imparted by the NC layer. This work not only provides a catalytic system that simultaneously overcomes the challenges of concentration, stability, and efficiency, but also offers insights into the role of electronic metal-support interaction in glucose epimerization.
Synergistic oxygen vacancy and electron donor engineering in Au nanoclusters@NiCo-MOF/BiVO heterojunction for highly efficient photoelectrochemical water oxidation
The development of more efficient strategies for spatial charge separation and transfer represents a promising avenue to enhance photoelectrochemical performance. A vacancy engineering and electron donor-assisted strategy, which entails introducing electron-donor Au nanoclusters (NCs) onto the photoelectrode based on oxygen vacancy (O)-rich metal-organic frameworks (MOFs), is proposed. The Au NCs@NiCo-MOF/BiVO heterostructure exhibited a photocurrent density of 4.86 mA cm at 1.23 V vs. reversible hydrogen electrode (RHE) in 0.5 M NaSO solution, which is 4.9 times higher than that of pristine BiVO. Experimental characterizations and density functional theory (DFT) calculations demonstrate that O with a high concentration in NiCo-MOF function as electron trapping sites, which effectively facilitates spatial charge separation and suppresses electron-hole recombination. Meanwhile, the introduced Au NCs serve as electron donors to increase the charge density of active sites, reduce the adsorption energy barrier of reaction intermediate and provide fast electron transport nanochannels to enhance the charge transfer. This work presents an approach for significantly enhancing charge carrier separation and transport.
Site-selective luminescence in Ca-doped SrYNbO:Eu phosphors for high-color-purity red emission
Narrow-band red phosphors excited by blue light are vital for high-color-rendering lighting and wide-color-gamut displays. Nevertheless, the commonly utilized red phosphors exhibit considerable deficiencies in hydrothermal stability and color purity, thus constraining their practical usage. In this study, by using a developed doping strategy with Ca to regulate a local crystal field and the possible preferential occupation behavior of the SrYNbO:Eu red phosphor with a double perovskite structure, it is found that their luminescence intensity and thermal stability are significantly enhanced. High-resolution scanning transmission electron microscope (STEM) measurements equipped with an aberration corrector revealed that Eu occupied the Sr or Y sites, forming two emission centers. This resulted in significant changes in the emission intensity at 594 nm and 611 nm with changes in the excitation wavelength. Furthermore, the introduction of Ca can increase the proportion of Eu at the Sr site, thereby enhancing the emission of the D → F transition at 611 nm. Meanwhile, we have significantly improved the color purity and thermal stability of the obtained red phosphors. The current findings reveal the site-selective luminescence mechanism in Eu-activated double perovskite structures and propose a cation substitution strategy to optimize excitation and emission simultaneously. This approach may provide an effective pathway for the design of high-performance red phosphors for advanced optoelectronic applications.
Enhancing solar-driven biological hydrogen production through a copper-based MXene-polypyrrole and Escherichia coli-integrated semiartificial photosynthetic system
The biohybrid-mediated semi-artificial photosynthetic system ingeniously combines the superior light-trapping characteristics of photosensitizers with the highly efficient catalytic capabilities of biocatalysts. However, the slow transfer of electrons at the micro-interface between the photosensitizer and biocatalyst is challenging for the performance of semi-artificial photosynthetic systems. Here, we report a semi-artificial photosynthetic biohybrid system comprising the positively charged hybrids of copper quantum dots/Mxenes encapsulated inside conducting polymer polypyrrole (Cu-MXene-PPY) and negatively charged Escherichia coli (E. coli) via electrostatic interaction. This system achieved an ideal state, wherein the photosensitizer possesses strong light absorption capability and a positive surface charge, enabling efficient electron transfer with E. coli. The semi-artificial photosynthetic system delivered a high catalytic performance for hydrogen production, with a yield of 2.37 mmol of hydrogen in 5 h (420-780 nm, 2000 W/m). The mechanistic investigation of the catalysis indicated that the E. coli/Cu-MXenes-PPY biohybrids enabled inhibition of lactate production coupled with acceleration of formic acid production in bacteria under the influence of photoelectrons, which facilitated H reduction and H production. Overall, this approach enables the construction of a robust semi-artificial photosynthetic system for H production.
High-performance polymer binders for silicon-based anodes: Advances in molecular design and applications
Silicon-based anodes represent a pivotal innovation for circumventing the energy density limitations inherent in current lithium-ion batteries (LIBs), chiefly because of silicon's exceptional theoretical specific capacity (4200 mAh/g). Nevertheless, its significant volume expansion (approximately 300 %) during electrochemical cycling presents critical challenges, such as electrode pulverization, continuous rupture and reformation of the solid electrolyte interphase (SEI), and rapid capacity fading, which collectively hinder commercial viability. Contemporary research paradigms to mitigate these issues primarily revolve around intrinsic material modifications-such as nano-structuring, carbon coating, alloying, and polymer binder composites-each yielding considerable advancement. Notably, while nano-structuring and alloying approaches aim to ameliorate volume strain from a crystallographic and mechanical perspective, carbon coating and polymer binder strategies primarily function through extrinsic confinement mechanisms, concurrently enhancing electrical percolation. Among these, polymer binders, albeit used in minimal quantities, fulfill an indispensable role. This review delineates the landscape of mainstream binder categories and their molecular tailoring strategies, presenting a balanced appraisal of their respective merits and drawbacks. It methodically encapsulates advanced tactics including graft modification, crosslinking, and copolymerization, deciphering their operational principles and molecular interaction mechanisms through sophisticated structural design. Moreover, it proves the profound impact of molecular engineering on the electrochemical behavior of silicon-based anodes, thereby furnishing both theoretical underpinnings and pragmatic directives for the advancement of binder technologies.
Amorphous CoO-SnO Nanocubes with dual sites enable efficient Electrocatalytic Ammonia synthesis via pathway switching
Amorphous metal oxides are attracting considerable attention as electrocatalysts due to their higher density of catalytically active sites and unique electronic structure. Traditional tin-based amorphous oxide materials, however, suffer from low intrinsic electronic conductivity and sluggish ion diffusion kinetics, limitations that hinder their application. Herein, we successfully developed the amorphous CoO-SnO nanocube material using co-precipitation and calcination. It has been demonstrated by means of microstructural and surface analysis that the amorphous framework characterized by uniformly distributed CoSn dual sites induces strong electronic interaction, thereby effectively modulating the adsorption of key reaction intermediates. This catalyst achieves exceptional NRR performance with 93 μg h mg NH yield and 59 % Faradaic efficiency (FE) at -0.5 V vs. RHE, outperforming monometallic controls. Mechanistic studies, incorporating in-situ FTIR and DFT calculations, demonstrate that the CoSn electronic structure modulation directs the reaction along an unconventional "alternating-distal" hybrid pathway. In this pathway, the dual-site configuration regulates the adsorption energy of intermediates and reduces the energy barrier of the rate-determining step. This work demonstrates amorphous bimetallic oxide engineering as a paradigm for efficient electrocatalytic ammonia synthesis.
A shikonin/Cu coordination complex-encapsulated hydrogel drug depot alleviates myocardial ischemia-reperfusion injury by disrupting energy metabolism-mediated intercellular crosstalk
In the pathological progression of myocardial ischemia-reperfusion injury (MI/RI), M1 macrophages and hyperactivated cardiac fibroblasts (CFs) synergistically drive tissue damage through metabolic reprogramming-mediated inflammatory storms and fibrotic remodeling. However, addressing the challenge of influencing the interactions between macrophages and CFs through energy metabolism intervention remains a significant therapeutic hurdle. Herein, we developed an innovative hydrogel-based drug depot (pH-SC@ZIF-8) by incorporating hyaluronic acid (HA)-modified zeolitic imidazolate framework-8 (ZIF-8) nanoparticles, which are loaded with shikonin/Cu metal-drug coordination complexes (SC), into a thermosensitive Pluronic F-127 hydrogel. In vitro studies have shown that HA modification enhances the targeting efficiency of nanoparticles toward M1 macrophages and activated CFs, facilitating the accumulation of shikonin and Cu in target cells. This process inhibits glycolysis and activates cuproptosis, leading to a significant reduction in the secretion of inflammatory cytokines (TNF-α, IL-1β) and inducing CF death. In vivo results indicate that the thermos-responsive gelation of the hydrogel facilitates stable and sustained drug release, effectively reducing the inflammatory response at the injury site while exhibiting anti-fibrotic effects. Our study offers a novel therapeutic strategy for cardiovascular diseases by inhibiting energy metabolism to modulate the interactions between immune and tissue cells.
Multi-functional zwitterionic glycerylphosphorylcholine hydrogel for human motion detection and human-machine interaction
Zwitterionic hydrogels have emerged as promising candidates for next-generation epidermal sensors owing to their inherent biocompatibility, ionic conductivity, and environmental responsiveness. However, achieving a single system that simultaneously integrates good anti-freezing capability, high ionic conductivity, and autonomous self-healing ability remains a big challenge. Here, we report a glycerylphosphorylcholine (GPC)-based, multifunctional zwitterionic hydrogel reinforced with cellulose nanofibers (CNFs) featuring a honeycomb-like hierarchically porous structure. GPC endows the hydrogel with good anti-freezing capability by retaining non-freezable water, while enabling rapid ion transport through ion-dipole interactions. CNFs serve as a mechanically robust scaffold and facilitate good stretchability and resilience. The resulting hydrogel exhibits an exceptional stretchability of 5540 % and a high ionic conductivity of 19.7 S m. Moreover, the presence of multiple reversible physical crosslinks imparts strong interfacial adhesion and rapid self-healing. When integrated into wearable electronics as self-adhering strain sensors, the hydrogel enables reliable human motion detection, real-time electrophysiological signal monitoring, and robotic control through human-machine interfaces, even in subzero environments. Additionally, the hydrogel demonstrates inherent antibacterial activity, further expanding its potential in bio-interfacing applications. This work presents a versatile design strategy for engineering next-generation zwitterionic hydrogels toward multifunctional, low-temperature-tolerant, and self-healing wearable systems.
Spontaneous imbibition in cellulose: an absorption-mediated non-Lucas-Washburn phenomenon
The classical Lucas-Washburn (LW) model, which assumes a saturated front progressing uniformly with a height scaling as the square root of time, has long been used to describe liquid seepage in various porous media. However, for hygroscopic cellulose-based materials, a fraction of water can be absorbed in the form of (nanoconfined) bound water into the amorphous regions of cellulose microfibrils thus inducing cellulose swelling. Thus, water imbibition in cellulose fiber networks might not be solely governed by capillary effects but could be significantly impacted by bound water absorption, leading to a coupled two-phase transport behavior.
Modulating dimensional transitions in covalent organic frameworks for seawater-based photocatalytic hydrogen peroxide production
Covalent organic frameworks (COFs) with identical compositions but distinct dimensionalities are exceptionally rare, and the intrinsic relationship between their structure and photocatalytic performance remains poorly understood. Herein, we report the precise synthesis, achieved through meticulous monomer design, enabling a dimensional transition from one-dimensional (1D) chain-like structures (BS-OB-COF and BS-MB-COF) to a two-dimensional (2D) layered framework (BS-PB-COF). Compared to their 1D counterparts, the 2D COF exhibits significantly enhanced photocatalytic HO production via the predominant two-electron oxygen reduction reaction (2e ORR) pathway. This improvement stems from the highly efficient carrier transport channels established through the enhanced in-plane conjugation of the donor-acceptor (D-A) network. Under oxygen atmosphere without sacrificial agents, BS-PB-COF demonstrated 3.2-fold and 1.6-fold higher seawater-based photosynthetic HO production than small-ring 1D COFs and 1D COFs, respectively, while also exhibiting activity under near-infrared irradiation. Furthermore, BS-PB-COF demonstrated excellent stability and notable antibacterial performance. This study unveils the profound impact of dimensionality control on HO photosynthetic performance and provides new insights for the rational design of COFs for HO production.
Novel thermal-induced anisotropic conductivity film and descendable 3D pipe or 2D + 3D architectures
In this study, a brand-new thermal-induced anisotropic conductivity film (TACF) is developed by using VO with magnetism and semiconductor-to-metal phase transition to generate thermal-induced conductivity, and thus a new concept of thermal-induced anisotropic conductivity is advanced. [polymethyl methacrylate (PMMA)]//[VO/PMMA] Janus ribbon used as microscopic fabricating unit is orientationally aligned to create TACF via parallel electrospinning. A well-designed dual strategy of strengthening both conductivity in the conductive direction and insulation in the insulating direction to improve conductive anisotropism of film is realized by using the Janus ribbon with two micro-partitions. Upon heating, TACF exhibits strong conduction along the length direction of Janus ribbons (i.e. conductive direction) owing to VO in metallic state to form conductive networks in VO/PMMA ribbons and intense insulation along the width direction of Janus ribbons (i.e. insulating direction) owing to introduction of insulating PMMA ribbons, achieving high thermal-induced conductive anisotropy. The anisotropic degree and paramagnetism of TACF are adjustable by modulating VO contents and heating temperatures. TACF exhibits strong thermal-induced conductive anisotropic degree of 10 at 80 °C. Meanwhile, the paramagnetism of TACF at 80 °C is four times higher than that at 25 °C. Two-dimensional (2D) TACF is curled into three-dimensional (3D) pipes and 2D plus 3D (2D + 3D) architectures, achieving convenient and cross-dimensional preparation of 3D or 2D + 3D thermal-induced anisotropic conductive materials from TACF. The descendable 3D pipes and 2D + 3D architectures exhibit similar performances as TACF. As applicative demonstrations, TACF, 3D pipes and 2D + 3D architectures display reliable conductive interconnection and anisotropic conduction in microcircuits upon heating.
Beyond the oil-water interface: Cooperative alkali-lipase catalysis induces pH-responsive self-assembly in triolein hydrolysis
Lipase-catalyzed and alkaline hydrolysis of triglycerides generate amphiphilic molecules that reorganize oil-water interfaces and form supramolecular assemblies with defined colloidal properties in oil and water. Here, we present a structural and compositional analysis of a biphasic triolein/buffer system subjected to alkaline treatment or enzymatic hydrolysis by Sus scrofa, Rhizomucor miehei, and Thermomyces lanuginosus lipases across a pH range of 7.0-11.0. Small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) reveal minimal structural changes below pH 9.0. In contrast, at pH 11.0, reaction-driven self-assembly produces water-in-oil emulsions and vesicles in the oil phase. In the aqueous phase, oil-swollen micelles and vesicles form, with size and morphology dependent on the hydrolysis conditions. These nanostructures correlate with variations in product composition and interfacial enrichment, markedly increasing the available interfacial area. While previous studies have examined lipase-catalyzed lipid hydrolysis, the coupled structural evolution of both oil and aqueous under enzymatic and alkaline conditions has, to the best of our knowledge, not been resolved. This study reveals a direct link between hydrolysis, amphiphile generation, and pH-dependent self-assembly beyond the oil-water interfaces. It offers mechanistic insight relevant to lipid digestion, interfacial catalysis, and the design of pH-responsive colloidal materials.
Polymerizable inverse HIPEs-based inks towards 3D printing of highly tailorable polymeric materials
Due to its processing requirements, extrusion 3D printing of plastics is limited to a rather narrow range of thermoplastic polymers. Here we present a strategy to formulate 3D printing polymerizable inks with rheological features compatible with extrusion-based approaches and applicable to hardly processable polymers, surpassing their thermal limitations. To do so, we formulate inverse oil-in-water high internal phase emulsions (i-HIPEs) with dispersed phase consisting of polymeric precursors and reaching 90 % volume fraction. As opposed to their water-in-oil counterparts, inverse-HIPEs polymerization, after 3D deposition, yields dense plastic rather than macroporous structures, mimicking the deposition of a fused thermoplastic filament. To demonstrate the validity of the approach, we formulate highly tailorable inks for room-temperature 3D printing of polystyrene (PS) and polymethyl methacrylate (PMMA), which are notoriously difficult to process via conventional thermal strategies. Despite their potential, inverse-HIPEs are far less characterized than classical ones. Here we provide a comprehensive rheological characterization, showing that these emulsions behave as Herschel-Bulkley fluids, exhibiting controllable yield stress, elasticity, and shear-thinning behavior, which are modulated by droplet packing, phase hydrophobicity, and continuous phase viscosity. The resulting inks display shear recovery and good printing potential. Preliminary curing tests demonstrate that methacrylate-based HIPEs undergo rapid UV polymerization, whereas styrene-based systems are thermally polymerized but require alternative strategies for efficient photopolymerization. This work provides a robust framework for the design of broadly applicable, monomer-in-water inks that unlock new possibilities in additive manufacturing with chemically diverse polymer targets.
Nanobubble nucleation dynamics in reacting microdroplets: Insights from confocal laser scanning microscopy and molecular dynamics simulations
Gas-evolving interfacial reactions in microdroplets underpin processes in catalysis, energy conversion, and microreactor technologies, yet the principles of nanobubble nucleation remain unclear. Here, we integrate confocal laser scanning microscopy with coarse-grained molecular dynamics simulations to elucidate hydrogen nanobubble formation during base-catalyzed reactions of liquid organic hydrogen carrier (LOHC) droplets with aqueous NaOH. We reveal a competition-controlled nucleation mechanism governed by gas production rate, asymmetric solubility in droplet and surrounding phases, and water-gas interfacial tension. Nucleation occurs only when local gas concentrations exceed a critical threshold that is largely independent of production rate but strongly influenced by gas solubility in two phases. High production rates shorten induction times and shift nucleation toward the LOHC-water boundary, whereas increased solubility in LOHC or water suppresses nucleation, raising the critical threshold or extracting gas from the droplet. Reduced interfacial tension lowers the nucleation barrier, accelerates onset, and favors interfacial nucleation. These findings establish principles for controlling gas evolution in reactive emulsions, offering design guidelines for interfacial microreactors and nanobubble-enabled catalytic systems.
Designing high-performance Ni/co single-atom catalysts for ORR/OER through spin-coordination engineering
Oxygen reduction (ORR) and oxygen evolution (OER) reactions are fundamental to the operation of metal-air batteries but are often constrained by sluggish interfacial kinetics. In this work, density functional theory (DFT) calculations were conducted to elucidate how local coordination environments modulate the bifunctional electrocatalytic performance of graphene-supported Ni and Co single-atom catalysts (SACs). TM-N@G-L (TM = Ni, Co) models with heteroatom ligands of varying electronegativity were constructed. Electronic structure and free energy analyses revealed that the type and number of coordinating atoms affect the metal d-band center, electron transfer, and intermediate adsorption. Nitrogen atoms act as electron-bridging centers, accepting electrons from carbon and donating to the metal via a "receive-donate" mechanism. Configurations such as NiNGe, NiNS, and CoNCl exhibited low OER and ORR overpotentials (0.27-0.44 V). Most interestingly, local magnetism was found to critically influence catalytic activity, with moderate values yielding optimal performance. Our study provides atomic-level insight into SACs interfacial behavior.
BP/PdSe heterojunction device for broadband polarization-sensitive synaptic simulation, logic operation, navigation, all-day image processing and recognition
Visual function is one of the most critical abilities of organisms to perceive the outside world, playing an indispensable role in the interaction between them. Especially, the polarization-sensitive visual function can process the polarized visual information in nature. However, this capability is a huge challenge for semiconductor devices. Here, an anisotropic BP/PdSe van der Waals (vdW) heterojunction device is proposed, which can realize wide-band photoelectric response from visible to short-wave infrared. The device shows a high responsivity of 0.459 A/W and an anisotropy ratio of 1.41 under 638 nm laser irradiation, which also exhibits good optical response to 405, 520, 980 and 1550 nm. Image edge processing and logical operations are realized by taking advantage of the polarization performance of the BP/PdSe device. In addition, the device also successfully achieves synaptic simulation. Interestingly, based on this, we have constructed artificial neural networks for image recognition. It realizes color recognition and shape recognition at day time, and still perform shape recognition at night for night vision, thus completing all-day image recognition. Besides, the device realizes polarization-sensitive synaptic simulation, mimicking the navigation behavior of bees by recognizing polarized light, and providing ideas for the research of artificial compound eyes. This work realizes multi-function application based on a single BP/PdSe vdW heterojunction device, which offers a potential technique for the development of intelligent optoelectronic systems.
Structure and morphology of vesicular dispersions based on novel glycophospholipids with various monosaccharide head groups
Glycophospholipids combine the structural versatility of phospholipids and carbohydrates, but their potential as excipients and performance in other related applications remains largely unexplored due to their low natural abundance. We have synthesized four novel phosphatidyl saccharide conjugates with different carbohydrate head groups; glucose, galactose, fructose and xylose by using a Phospholipase D catalysed transphosphatidylation reaction. The combination of Small Angle X-ray Scattering (SAXS) and Cryogenic Transmission Electron Microscopy (cryo-TEM) data allowed us to characterize the dispersed glycophospholipid vesicles in excess water and under physiologically relevant solution conditions in terms of their morphology and structure. The different carbohydrate head group generated a large variability of the vesicle structures. Lipids conjugated with glucose and fructose self-assembled into unilamellar vesicles whereas galactose and xylose conjugated lipids formed multilamellar structures. Phosphatidylgalactose conjugated lipids formed a high number of stacked bilayers, while the phosphatidylxylose equivalent assembled into aggregates with only a few bilayers. These results highlight how carbohydrate hydroxyl spatial arrangements strongly influence lipid packing and self-assembly. The versatility of this glycophospholipid platform offers opportunities to generate biocompatible and biodegradable phospholipid excipients with properties that can be tailored for specific applications.
