查找使用阿拉丁产品的科研文献

Copper-tailored d-p-π multi-orbital coupling in sulfurized polyaniline enables ultralong cycling aqueous sulfur batteries

Zhiwei Chen,Chaoyi Qiu,Zhichao Wang,Xiang Liu,Zihao Tao,Jiahe Geng,Xikun Zhang,Haoxiang Yu,Lei Yan,Peng Li,Liyuan Zhang,Ting-Feng Yi,Jie Shu,Bao-Lian Su

The practical application of sulfur-based batteries is significantly limited by sluggish reaction kinetics and structural collapse. Herein, a copper-modified sulfurized polyaniline (CuSPANI) cathode with distinctive d-p-π multi-orbital coupling is constructed through Cu heteroatom introduction. This coupling, arising from hybridization between Cu d orbitals and sulfurized polyaniline (SPANI) p/π orbitals, enables triple electronic modulation: reducing energy barriers to enhance kinetics, expanding electron delocalization to improve conductivity, and activating horizontal Cu d orbitals to strengthen structural stability. Consequently, the aqueous CuSPANI battery delivers a high reversible capacity of 834.75 mAh g s −1 at 3 C and exceptional cycling stability (61.2% capacity retention after 60,000 cycles at 15 C). Moreover, the designed flexible quasi-solid-state pouch cell achieves a 1.25 V output and maintains stable power under deformation, highlighting its potential for wearable energy storage. This work provides new insight into designing high-performance sulfurized polymers via orbital hybridization.

Modulating the d-band center of Ni3Fe via cobalt-interface engineering for efficient bifunctional overall water splitting

Siwei Sun,Xinxin Zhang,Haitao Yu,Ying Xie

NiFe alloy is regarded as a promising electrocatalyst for water splitting owing to its superior conductivity, tunable electronic structure, and abundant active sites. Nevertheless, its practical application is hindered by slow water dissociation kinetics and unfavorable adsorption of hydrogen intermediates. Herein, we develop a composite catalyst, denoted as Co/Ni 3 Fe@NC-3 through a coordination-pyrolysis route, where ZIF-67-derived Co nanoparticles are anchored on Ni 3 Fe@NC porous nanosheets. In 1 M KOH, the catalyst exhibits remarkable bifunctional activity, requiring overpotentials of 67 mV for HER and 240 mV for OER at 10 mA cm −2 . Notably, a symmetric electrolyzer based on this catalyst (Co/Ni 3 Fe@NC-3) (+||−) achieves overall water splitting at a low voltage of 1.499 V (10 mA cm −2 ), superior to the commercial Pt/C||RuO 2 benchmark (1.592 V), and sustains stable operation for 100 h at 100 mA cm −2 . In-situ electrochemical impedance spectroscopy (EIS) indicates that Co incorporation optimizes the interfacial electronic structure, leading to faster charge transfer and reduced impedance. Density functional theory (DFT) calculations and experimental results further demonstrate that Co-induced interfacial electron redistribution upshifts the d-band centers ( E d ) of Ni/Fe sites, strengthens the adsorption of H* and H 2 O, and thus synergistically enhances both HER and OER performance. This study highlights the effectiveness of interface engineering and electronic structure modulation, providing a viable strategy for designing advanced NiFe-based water-splitting catalysts.

Assessment of p-Xylene Migration Behaviour in Unsaturated Soil Systems: A 3-D Sand Flow Chamber Study

The influence of soil water content and contaminant injection pressure on the migration behaviour of p-Xylene (one of the organic pollutants in Benzene Toluene Ethylbenzene & Xylene) is investigated in the unsaturated zone using the controlled laboratory sandbox experiments. The results show that, at equivalent migration distances, higher soil water content leads to longer migration durations and reduces transport velocities, whereas greater injection pressure promotes faster contaminant movement. These findings highlight the governing role of water saturation in the water–oil–gas three-phase system, in which increased water content decreases the relative permeability of the oil phase and retards capillary-driven BTEX transport. Unlike many previous studies in which contaminants commonly migrate downward toward the groundwater table, the BTEX in this study did not reach the water table and exhibited partial upward migration. Overall, the results provide experimental-scale insight into key mechanisms governing BTEX transport in unsaturated sandy media and serve as a reference for improving predictions of contaminant fate and migration pathways in field settings.

Shape-Induced d-Band Center Optimization of PdBiNi Nanocubes for Exclusive Oxidation of Glycerol into C3 Products

Zeng Qing,Tamtaji Mohsen,Zhou Rui,Zhou Tao,Guo Zhengxiao,Chen GuanHua,Tse Edmund C. M.

Electrocatalytic oxidation of glycerol toward high-value C3 products on Pd-based catalysts presents a promising strategy for upgrading and converting glycerol. However, C3 intermediates often adsorb too tightly on Pd-based catalyst surfaces during glycerol oxidation, leading to C–C bond cleavage. Herein, cubic-shaped PdBi nanoparticles with tunable Ni doping levels are successfully synthesized through a one-step solvothermal method. Owing to the downshift of d-band center originating from the introduction of Bi and Ni as well as the cubic shape, the PdBiNi ternary nanocubes (NCs) exhibit excellent electrocatalytic performance for the glycerol oxidation reaction (GOR). Specifically, Pd 83 Bi 12 Ni 5 NCs with the lowest d-band center exhibit a specific activity of 61.12 mA cm geo –2 and a mass activity of 5.34 A mg Pd –1 . Notably, the Faradaic efficiency (FE) toward C3 products exceeds 97%. In situ Fourier transform infrared spectroscopy and density functional theory calculations show that key C3 intermediates are easily desorbed from the catalyst surface, thereby suppressing C–C bond cleavage and thus preventing overoxidation into low-value products. In addition, Pd 83 Bi 12 Ni 5 NCs possess long-term durability over the course of 16 cycles (1 h/cycle) with an FE for C3 products between 92.5% and 97.6% upon scale-up deployment in a flow electrolyzer, validating its feasibility in practical operations.

Stable isotope labeling LC–MS for profiling the amine submetabolome in a D-lactate treated cell model

Yue-qiang Chen,Xiao-xia Dong,Li Liu,Xiu-ping Chen,Chen-guo Feng,Li-xing Zhan,Yue Su,Fang Zhang,Yin-long Guo

Background Alterations in the amine submetabolome are closely associated with cellular metabolic status and are important for understanding metabolic regulation under intervention conditions. In this study, a stable isotope labeling derivatization combined with liquid chromatography–mass spectrometry (LC–MS) was employed to characterize alterations in the cellular amine submetabolome. Optimization of chromatographic separation and cellular metabolic quenching procedures improved the separation performance of amine metabolites while enabling more accurate preservation of the metabolic state at the time of sampling. Results The established method was applied to a D-lactate–treated BEAS-2B cell model to evaluate amine submetabolome alterations under different compound intervention conditions. The results demonstrated that selenomethionine (SeMet) and berberine alleviated D-lactate induced abnormalities in the amine submetabolome and showed metabolic regulatory effects consistent with tumor-suppressive trends observed under in vivo experiments. Significance Overall, this analytical strategy enables characterization of the amine submetabolome in complex biological samples and provides a reliable methodological reference for metabolome-based investigations of cellular metabolic alterations.

Preparation of highly efficient bifunctional water electrolysis catalysts by controlling selenide d-band centers via polyatomic doping

WenYu Yan,Hao Yi,ZhongKe Luo,Fei Qi,XinFeng Li,Chao Wang

Constructing MoSe 2 @Ni 3 Se 2 heterostructures optimized active site distribution and charge transport. • Three-dimensional nanostructure achieved high specific surface area and outstanding mechanical stability. • Synergistic Mn/Co/Se regulation optimizes adsorption behavior of reaction intermediates. • Theoretical calculations reveal d-p orbital hybridization as the electronic-scale mechanism for high activity. • Demonstrates highly efficient bifunctional full water splitting activity (1.57 V@10 mA cm −2 ). This paper reports an MCS-MoSe 2 @Ni 3 Se 2 /NF composite electrocatalyst with remarkable performance advantages, achieving breakthroughs in full hydrolysis performance through ingenious structural design and interfacial engineering. The catalyst first constructs MoSe 2 @Ni 3 Se 2 nanosheet arrays on a nickel foam substrate, followed by Mn–Co–Se introduction via electrodeposition for interfacial modification. This forms a unique spherical structure that substantially exposes active sites and optimizes electron transport pathways, significantly enhancing reaction kinetics. Under alkaline conditions, this material exhibits outstanding bifunctional catalytic activity: HER achieves 10 mA cm −2 at just 103 mV overpotential, while OER requires only 263 mV. Notably, when assembled as an integrated water electrolysis cell with simultaneous anode and cathode functions, it drives a current density of 10 mA cm −2 at a low voltage of 1.57 V and operates stably for over 50 h. Density functional theory calculations further reveal that its outstanding performance stems from the precise regulation of the material's d-orbital electronic structure by Mn–Co–Se. This creates a strong, broad d-p orbital hybridization region near the Fermi level, achieving an ideal balance between high conductivity and catalytic activity, thereby optimizing the reaction pathway. This work provides crucial material systems and theoretical insights for designing efficient, stable bifunctional water electrolysis catalysts. The MCS-MoSe 2 @Ni 3 Se 2 /NF structure engineered through interface design enhances water electrolysis performance by optimizing electron transfer pathways and regulating d orbitals. Download: Download high-res image (318KB) Download: Download full-size image

Cu-Mo dual-doped carbon nitride with excellent peroxidase-like activity for portable colorimetric quantifying D-penicillamine

Xianfeng Ma,Huiying Dai,Luyao Zhao,Xiaolan Liang,Xiuquan Xu,Xiaofeng Yu

A low-cost Cu-Mo dual-doped carbon nitride nanozyme was synthesized. • It shows excellent peroxidase-like activity via superoxide radical pathway. • A smartphone-based platform enables portable and visual D-PA detection. D-Penicillamine (D-PA), a sulfur-containing amino acid, is used to treat various diseases such as Wilson's disease, fibrotic lung disease, and cystinuria. However, excessive intake of D-PA can cause adverse effects, necessitating the development of accurate quantitative detection methods. This study aimed to establish a visual colorimetric method for D-PA detection using a synthesized Cu-Mo dual-doped carbon nitride nanomaterial ( Cu - Mo - VC - CN ). The synthesis capitalizes on the simplicity and cost-effectiveness of a one-pot thermal polymerization reaction, utilizing only inexpensive and commercially available precursors, namely copper chloride, ammonium molybdate, urea, and vitamin C. The material exhibited exceptional peroxidase-like activity, catalyzing the oxidation of TMB by H 2 O 2 via a superoxide radical pathway. The optimal reaction conditions were: temperature 30 °C, time 30 min, pH 5.5, TMB concentration 0.2 mM, and H₂O₂ concentration 0.2 mM. Steady-state kinetic analysis revealed that the Cu - Mo - VC - CN nanozyme had Michaelis-Menten constants ( K ₘ) of 0.083 mM for TMB and 0.603 mM for H 2 O 2 . Under optimal conditions, the system enabled highly sensitive D-PA quantification with a linear range of 0.5–100 μM and a detection limit of 0.45 μM. The nanozyme was successfully applied to determine D-PA content in pharmaceutical tablets with satisfactory recovery (from 97.73 to 98.27%). Furthermore, a smartphone-based testing platform was established to provide a portable and practical solution for the real-time monitoring of D-PA. This work provides both an efficient strategy for developing multi-metal-doped nanozymes and a reliable colorimetric platform for D-PA monitoring. Download: Download high-res image (279KB) Download: Download full-size image

Modulating d-p orbital hybridization in V2O3/Fe3Se4@C heterostructure anode for high-performance sodium-ion batteries

Jinghao Zhao,Baoqin Hao,Wei Tan,Jing Chen,Yan Meng,Lin Han,Xinhao Qu,Xin Li

Constructing vanadium oxide/metal selenide heterostructure is a promising strategy to enhance the reaction kinetics and structural stability for high-performance sodium-ion batteries (SIBs) anode. However, achieving a uniform and robust heterointerface remains challenging due to the multivalent state transformation of the V and the thermodynamic stability difference between V O and V Se bonds. Herein, we design and synthesize the V 2 O 3 /Fe 3 Se 4 @C heterostructure via a facile liquid-phase reaction followed by a seleniziation method. The unique coordination environment in a ferric vanadate and the reduction potentials difference between Fe and V cations promote the formation of a well-defined heterointerface. Density functional theory calculations confirm the formation of a built-in electric field at the heterointerface, thereby accelerating the reaction kinetics. The electric field originates from the orbital hybridization, which promotes the formation of a robust Se V O bonding configuration. Meanwhile, the carbon coating maintains structural integrity by suppressing volume expansion during cycling. These synergistic effects effectively enhance the overall structural stability of the material. Thus, the prepared V 2 O 3 /Fe 3 Se 4 @C anode exhibits exceptional electrochemical performance, delivering a high specific capacity of 378.2 mAh g −1 at 0.5 A g −1 and 308.9 mAh g −1 at 8 A g −1 , and retaining a specific capacity of 313.8 mAh g −1 after 2500 cycles at 5 A g −1 . This work establishes a new electron orbital modulation strategy for exploring high-performance vanadium oxide-based anode materials for SIBs.

d-Band Engineering of Layered (Fe1−xNix)3GaTe2 for Enhanced Alkaline Hydrogen Evolution by Ni-Substitutional Doping

Xiaomin Tian,Yuan Cao,Huilin Zhou,Fanjie Tan,Ziqin Zhang,Liying Pei,Yi Ma,Jianzhi Gao,Wenliang Zhu,Minghu Pan

Tuning the d -band electronic structure of non-noble-metal catalysts is a central strategy for an alkaline hydrogen evolution reaction (HER), yet how composition controls the d orbital in multi-Wyckoff-site layered systems remains insufficiently understood. Here, layered (Fe 1- x Ni x ) 3 GaTe 2 single crystals ( x = 0.2–1.0) were synthesized by the self-flux method as a platform to address this question. Single-crystal XRD and EDS confirm that Ni is uniformly incorporated into the parent P6 3 /mmc framework while inducing a composition-dependent lattice evolution. Electrochemical measurements in 1.0 M KOH reveal a clear volcano-shaped composition dependence, peaking at x = 0.6, where the lowest overpotential, the smallest Tafel slope (94 mV dec −1 ), the lowest charge-transfer resistance and the largest double-layer capacitance are simultaneously reached. First-principles calculations show that Ni doping reshapes the Fe-site d orbital strongly composition-dependent rate: the Fe d -band center upshifts rapidly by ~0.5 eV between x = 0.4 and x = 0.6, while the Ni d -band center stays nearly fixed in the same composition range. The maximum of HER activity therefore aligns with a steep upshift of the Fe d -band center rather than with the Ni content itself. Charge-density mapping of (Fe 0.4 Ni 0.6 ) 3 GaTe 2 further demonstrates that the electron-enriched regions are located on the Fe and interlayer Ni3 sublattices that dominate the d states near E F .

Gasdermin D regulates choroidal blood flow and axial elongation in high myopia and therapeutic potential of apigenin

Yujuan Li,Jingyi Yang,Xiaotong Shao,Yunhe Tao,Shihui Ling,Xiaomeng Li,Qifeng Ye,Bin Guo,Hongsheng Bi

Despite advancements in treatments such as atropine, the pathological changes in high myopia still lead to vision loss, highlighting the need to identify novel therapeutic targets. Clinically, axial elongation are closely related to reduced choroidal blood flow. This study revealed that the pyroptosis-associated protein Gasdermin D (GSDMD) may play a key role in high myopia. Experiments showed that chemical inhibition of GSDMD significantly reduced axial elongation and choroidal blood flow reduction. Furthermore, by screening pharmacologically active traditional Chinese medicine compounds, we identified that Artemisia argyi (Aiye) and its active ingredient apigenin act as effective GSDMD inhibitors, capable of replicating the protective effects observed with chemical inhibition. In all, this study suggests that GSDMD is a potential target mediating axial elongation and choroidal blood flow changes in high myopia, and apigenin is a potential therapeutic strategy for intervening in high myopia.

Combining a chitosan-immobilized phospholipase D with a mixed micelle system for highly efficient synthesis of phosphatidylserine

Zhicen Liu,Caiyun Wang,Junjian Wu,Ming Chen,Yue Zhang

This study developed a highly efficient immobilized phospholipase D (PLD) system using a magnetic chitosan-based carrier with the natural crosslinking agent genipin (Fe 3 O 4 @CS-Gnp-PLD). Systematic characterization confirmed successful PLD immobilization, with chitosan's abundant amino and hydroxyl groups providing stable binding sites that enhanced both enzyme loading and stability. In the sodium deoxycholate-based mixed micelle system, the Fe 3 O 4 @CS-Gnp-PLD achieved an 8.05-fold higher phosphatidylserine (PS) conversion rate than free PLD, owing to enhanced substrate solubility and improved enzyme accessibility. The immobilized enzyme demonstrated exceptional operational stability, retaining 80% activity after 6 reuse cycles and 72% activity after 12 days of storage at 4 °C. This integrated platform, combining chitosan-based enzyme immobilization with a mixed micelle system, offers an efficient, stable, and recyclable approach for sustainable PS biomanufacturing.

Electric-dipole resonance in a graphene-coated double-D terahertz metamaterial sensor for trace-level glucose detection

Haoyu Zheng,Zhen Sun,Jianjun Liu,Su-an Xu,Jiadan Xue,Yong Du

A graphene-enhanced double-D metamaterial sensor exhibits electric-dipole scattering. • The maximum refractive index sensitivity of the optimized sensor reaches 204 GHz/RIU. • The graphene-coated sensor responds measurably at the lowest tested level of 1 μM. • The double-D electric-dipole sensor enables trace glucose detection using THz-FDS. Terahertz metamaterial sensors provide an efficient platform for highly sensitive biochemical detection. Herein, a graphene-enhanced terahertz metamaterial sensor was developed and coupled with a terahertz frequency-domain spectroscopy (THz-FDS) system for trace-level detection of glucose. A metamaterial sensor comprising a double-D-shaped split-ring aluminum resonator was fabricated, which exhibited a pronounced resonance at 0.951 THz under transverse-electric (TE)-polarized terahertz incidence. Multipole decomposition, together with electric-field, magnetic-field, and surface-current analyses, showed that the resonance is dominated by the electric dipole (ED). The ED channel accounts for approximately 98.59% of the summed isolated multipolar scattering power, whereas the toroidal dipole (TD) and magnetic quadrupole (MQ) provide only minor contributions. After structural optimization, CST simulations of bulk refractive-index variation yielded a sensitivity of 204 GHz/RIU, characterizing the simulated index-sensing performance of the resonator. To achieve high-precision detection of trace-level glucose, monolayer graphene was transferred onto the metamaterial surface using a wet transfer method. Experimental measurements showed a measurable response at the lowest tested concentration of 1 μM for the graphene-coated sensor, whereas the bare sensor showed a clear concentration-dependent response primarily in the millimolar range. Although the resonance amplitude varied nonmonotonically with concentration, the resonance-frequency shift increased monotonically and yielded a log-concentration calibration with R 2  = 0.932. Controlled paired simulations separated the contributions of graphene Fermi-level modulation and conventional dielectric loading. At an analyte thickness of 40 μm, the graphene-associated shift was +182.609 GHz, whereas dielectric loading produced redshifts of −245.081 GHz at E f  = 0 and −247.997 GHz at E f  = −120 meV. The interaction residual was −2.916 GHz, or 1.60% of the graphene contribution, indicating that the two effects are approximately additive under full loading. This work demonstrates that graphene-enhanced terahertz metamaterials can serve as highly sensitive sensing platforms for trace substance detection and provides both a physical strategy and experimental basis for developing high-performance terahertz biosensors involving interactions with low-dimensional materials. Download: Download high-res image (148KB) Download: Download full-size image