Lincomycin (LIN) residue in livestock farming induces antibiotic resistance, which threatens environmental safety and public health, necessitating ultrasensitive detection in complex matrix. Herein, we report a self-calibrating photoelectrochemical (PEC) aptasensor based on SnS2@CdIn2S4 core-shell nanosheets that enables trace LIN detection via the heterojunction-catalyzed polarity-reversal (HCPR) mechanism. The type-II heterojunction enhances light absorption and charge carrier separation, while LIN-aptamer immune-recognition suppresses anodic photocurrent. Auxiliary primers and heme facilitate DNA nanowire/G-quadruplex assembly on photoelectrode, which reverses electron flow to produce dual signals for self-calibration. The aptasensor achieves exceptional analytical performance such as a wide linear range (0.1 pg mL-1-100 ng mL-1) and a low detection limit (0.0296 pg mL-1), whose practical applicability is confirmed using Yangtze River water samples and serum samples (recoveries: 100.29-102.52%). This work provides an effective strategy for ultrasensitive detection of LIN in environmental and biological samples.
Hepatocellular carcinoma therapy is limited by sorafenib (Sor) resistance, hypoxia, and elevated glutathione (GSH). Conventional nanozymes cannot simultaneously address these issues while reprogramming tumor metabolism. We synthesized uniform porous silkworm-like PtFeCoTeMn high-entropy nanorods (HENRs) with peroxidase-, nicotinamide adenine dinucleotide oxidase-, catalase-, and glutathione oxidase-like activities via one-pot co-reduction, coupled by loading them with glucose oxidase (GOx) and Sor. The PtFeCoTeMn HENRs-GOx/Sor generates reactive oxygen species while depleting glucose and GSH, triggering full PANoptosis in MHCC97H cells through apoptosis, pyroptosis, and necroptosis. In vivo studies achieve ∼90% tumor suppression with minimal toxicity, identified by cleaved caspase-3, GSDME-N, p-MLKL biomarkers. The high-entropy nanozyme-driven metabolic-PANoptosis mechanism orchestrates multiple therapeutic pathways beyond single-enzyme systems. This modular approach suggests universal applicability to other solid tumor requiring metabolic-immune reprogramming.
Glycolic acid (GA) synthesis via selective ethylene glycol (EG) electrooxidation offers a sustainable pathway but faces fundamental limitations due to kinetically driven over-oxidation at high current densities, triggering an inescapable activity-stability dilemma. To address these issues, this study introduces a N-AuCu catalyst through low-temperature hydrothermal assembly with pyrazine-mediated coordination on Ni(OH)(2)@NF, achieving atomic-level dispersion of AuCu bimetallic sites at ultralow loading. This design attains unprecedented performance in EG-to-GA conversion, showing 96.83 % GA selectivity and 99.73 % EG conversion at ultrahigh current densities of 2000 mA cm(-2). The integrated electrolyzer produces industrial-grade GA and H-2 at 2.89 kWh & centerdot;m(-3), showing a similar to 32 % energy saving versus benchmarks. Controlled experiments and density functional theory (DFT) studies reveal multi-function orbital coordination catalysis. The pi-conjugated framework of pyrazine tailors local electronic structures and spatially differentiates Au/Cu active sites for reaction intermediates. This configuration strategically weakens *OCCH2OH adsorption on Au, promoting its coupling with adjacent *OH species on Cu to selectively form GA while minimizing unexciting over-oxidation. Simultaneously, pyrazine-mediated electron delocalization across the AuCu conjugation system stabilizes optimal metal valence states under high potentials, ensuring outstanding stability. This work pioneers a pi-electron modulation strategy for highly selective GA electrosynthesis, advancing sustainable electrochemical applications.
The pressing demand to replace noble metal catalysts drives advanced catalyst development, aiming to reduce cost and improve oxygen reduction reaction (ORR) in metal-air batteries. Herein, we prepared a high-efficiency ORR catalyst by integrating Fe/Mn dual-atom sites (DAS) and FeMn nanoclusters (NC) within nitrogen-doped porous carbon (FeMn DAS/FeMn NC) via spatial confinement pyrolysis. The synergistic interactions between Fe/Mn-N-4 DAS and FeMn NC optimize intermediate adsorption and reduce energy barrier of rate-determining step (protonation of O-2 to form *OOH), enhancing overall activity, identified by density functional theory (DFT) calculations. The catalyst demonstrated exceptional ORR performance with an onset potential (E-onset) of 1.05 V, half-wave potential (E-1/2) of 0.88 V, and remarkable stability. When applied as cathode catalyst, the assembled battery showed a high-power density of 114 mW cm(-2), narrow charge-discharge voltage gap of 0.913 V, and outstanding cycling stability (1020 cycles over 340 h). This work provides constructive insights for designing low-cost, high-performance ORR electrocatalysts via dual-atom engineering and alloying strategies. However, future work will focus on simplifying the synthesis process for scalable production.
A novel 2-mercaptobenzothiazole (2-MBT) detection method is introduced based on ultrathin PtRuFeCoRhW high-entropy alloy nanorods (HEANRs) synthesized via a solvothermal-coreduction strategy. These HEANRs contained numerous defects and atomic steps, providing abundant active sites. It exhibited peroxidase (POD)-like activity for its entropy-driven catalytic synergy and modified electronic structure, which was utilized to construct a colorimetric sensing platform. The platform operates via competitive inhibition between 2-MBT and 3,3’,5,5’-tetramethylbenzidine (TMB) oxidation, enabling ultrasensitive 2-MBT detection with a linear range of 1–7 µM (R2 = 0.997) and a detection limit of 0.42 µM (S/N = 3). Notably, the sensor demonstrates reliable performances in practical analysis of rubber wastewater. This work provides an efficient method for detecting 2-MBT. It also demonstrates that entropy-driven structural engineering is a promising strategy for designing advanced high-entropy materials. This research advances high-entropy-initiated catalysis and offers a versatile platform for environmental remediation, addressing a broad range of analytical challenges.
Ascorbic acid (AA) detection is a prior analyte for food safety and clinical diagnostics, yet traditional electrochemiluminescence (ECL) sensors depend on hydrogen peroxide (H₂O₂) coreactant whose instability degrades operational stability. To address this, we built a dissolved-O₂-driven ECL platform based on MoC nanoclusters/Co single-atom sites co-anchored on N-doped porous carbon (MoC NCs/Co SAs). The MoC NCs in the heterostructure activate dissolved O₂ to generate reactive oxygen species (ROS), while the Co SAs oxidize luminol, thus separating the two half-reactions in time. XRD, XPS, and TEM characterizations confirmed the hierarchical porous architecture and the EPR analysis verified singlet oxygen (¹O₂) as the active ROS. The sensor achieved a wide linear range of 568.79 pM to 28.39 mM (R² = 0.999) with a detection limit of 505.3 pM. Spike-recovery tests in fruit juices showed recoveries of 97.94–102.12
Sulfadiazine (SDZ), a widely used sulfonamide antibiotic, is frequently detected in environmental matrices due to its extensive application and high persistence, posing significant threats to ecosystems and public health. To address the limitations of conventional detection methods with inadequate sensitivity, we developed an ultra-sensitive and regenerable photoelectrochemical (PEC) biosensor for SDZ monitoring. The proposed PEC sensor integrates a metal-organic framework (MOF)-derived In2O3/In2S3 S-scheme heterojunction as a high-efficiency photoactive substrate with a pH-responsive DNA hydrogel-based signal amplification strategy. Upon specific recognition of SDZ, glucose oxidase (GOx)-functionalized aptamers are released from double-stranded DNA complexes, catalyzing glucose oxidation and generating protons. The localized proton accumulation triggers cross-linking of the DNA hydrogel, thereby modulating the microenvironment, and suppressing the photocurrent of the In2O3/In2S3 system. The proposed PEC biosensor demonstrated exceptional analytical performance with a broad linear range (0.2-1.0 x103 ng mL-1) and a low detection limit of 0.026 ng mL-1 (S/N = 3). This work offers a novel strategy for designing high-performance PEC sensors and provides valuable insights into photo-active interface engineering and intelligent signal amplification for environmental pollutant detection.
Developing high-efficiency and stable oxygen reduction reaction (ORR) electrocatalysts is critical for practical applications in zinc-air batteries, yet it is still challenging to achieve optimal catalytic activity through structural engineering. Here, CoFeVMnNi high-entropy intermetallic alloy/N-doped carbon nanocages (CoFeVMnNi HEI/CNCs) with abundant carbon nanotubes were fabricated by a one-step pyrolysis method. The structural and electronic properties of the material were characterized by multiple techniques. And its ORR performance was evaluated in details. The CoFeVMnNi HEI/CNCs catalyst achieved an onset potential (E-onset) of 1.106 V and a half-wave potential (E-1/2) of 0.859 V, with minimal E-1/2 degradation after 2000 cycles. In the catalyst assembled zinc-air battery, it delivered a high open-circuit voltage of 1.58 V, the maximum power density of 163.3 mW cm(-2), and a stable discharge for 378 h, outperforming commercial Pt/C-based system. These results underscore the synergistic effects of the high-entropy alloy and N-doped carbon in enhancing ORR kinetics and durability, offering a promising alternative to precious metal catalysts. This study provides a facile and promising strategy for fabricating multi-functional electrocatalysts, advancing sustainable and efficient energy storage technologies.
The hollow PtPdRhRuCoNi high-entropy alloy was synthesized via an oil-bath and subsequent etching. With a specific surface area 1.7 times larger than Pt black, it exhibits superior activity and stability in 1 M KOH electrolytes containing ethanol, ethylene glycol, or glycerol. These improvements originate from the synergistic effect between its unique hollow architecture, which provides abundant accessible active sites, and its multi-element composition, which optimizes the electronic structure and facilitates efficient electron transfer.
Single-atom catalysts maximize atomic utilization efficiency but suffer from limited activity and stability. Bimetallic alternatives overcome these limitations via synergistic interactions between adjacent metal sites. Herein, we synthesized a bimetallic single-atom catalyst with Fe and V uniformly distributed in N-doped porous carbon (Fe/V-N-C) via one-step pyrolysis. Synergistic electron transfer between the binary metals optimized active-site electron density, cooperatively activating H2O2 to boost reactive oxygen species generation and enhance ECL efficiency. The Fe/V-N-C catalyst showed 6.50-fold ECL enhancement, surpassing monometallic Fe-N-C (3.43 times) and V-N-C (2.05 folds). The alternating-current voltammetry (ACV)-ECL coupling and supplementary techniques confirmed that enhanced H2O2 affinity drives the improved catalytic performance, coupled by clarifying the ECL mechanism. The "signal on-off-on" ECL aptasensor was designed for ultra-sensitive aflatoxin B1 detection, achieving a dynamic linear range of 0.05-100 ng mL-1 and a low detection limit of 0.0025 ng mL-1. This work advances single-atom catalyst design for stable ECL sensing platforms.
A novel photoelectrochemical (PEC) aptasensor based on high-entropy sulfide (CdZnMnCrCo)xS for ultrasensitive ampicillin (AMP) detection has been developed. The sulfide, synthesized by a simple one-pot solvothermal method, featured abundant heterointerfaces and rich grain boundaries, which enhanced charge separation/transport, amplifying the PEC signals. Integrated with methylene blue (MB, as a photosensitizer) and exonuclease Exo-1-mediated recycling, the sensor achieved a broad linear range (0.1–1×106 pg mL-1) and a low detection limit (0.09 pg mL-1) with strong anti-interference characteristic. Spike-recovery tests on actual water samples at 10 and 50 pg mL-1 produced excellent recoveries of 97.4–103.8
In this work, we introduce hierarchical heterophosphide interface catalysis (HHIC) for water splitting. 3D self-supported hollow columnar FeP4-Ni5P2-NiMoP2 arrays is synthesized via hydrothermal synthesis, ion exchange, and controlled phosphidation. The hollow columnar architecture integrates three phosphide phases, creating abundant heterogeneous interfaces that enlarge active surface area. In 1.0 M KOH, it requires only 238 mV to achieve a current density of 100 mA cm-2 for the OER, outperforming commercial RuO2. The over-potential for the HER is 145 mV at 100 mA cm-2, surpassing commercial Pt/C. DFT calculations reveal optimal hydrogen binding (0.03 eV) and reduced OER energy barrier (1.81 eV), clarifying the HHIC mechanism. The assembled symmetric electrolyzer operated at a cell voltage of only 1.68 V and maintained 95% activity over 100-h continuous operation at 100 mA cm-2 for water splitting. This work shows an effective strategy to fabricate bifunctional low-cost catalysts for water electrolysis.
Di-2-ethylhexyl phthalate (DEHP) is a pervasive endocrine-disrupting compound that poses significant toxicological risks to both human health and ecosystems, highlighting the urgent need for sensitive and reliable monitoring strategies. Herein, we developed a novel photoelectrochemical (PEC) aptasensor for ultrasensitive DEHP detection, in which MnPP-encapsulated ZIF-8 nanozymes (MnPP@ZIF-8) mediate catalytic precipitation to engineer the interface of ZnCdS/NiCoP heterojunctions. Upon specific DEHP recognition, the aptamer-cDNA duplex unwinds, releasing MnPP@ZIF-8 conjugates from the electrode surface. The reduced surface-confined nanozymes weaken the catalytic precipitation process that otherwise hampers interfacial charge transfer, leading to target concentration-dependent photocurrent recovery. Benefiting from this interface-engineered signal regulation, the PEC aptasensor achieves outstanding analytical performance, including a broad linear range (0.1 pg mL(-1) similar to 100 ng mL(-1)), an ultralow detection limit (0.062 pg mL(-1), S/N = 3), excellent selectivity, and reliable applicability in complex environmental samples. This work not only provides an effective tool for accurate trace-level monitoring of hazardous plasticizers but also establishes a versatile strategy for designing advanced interface-engineered PEC sensing platforms to support environmental risk assessment.
The development of highly active and cost-effective electrocatalysts is essential for advancing the hydrogen evolution reaction (HER) in water splitting. Herein, Ni@PtIrRhCo nanodendrites (NDs) were synthesized through a simple oil bath method. These NDs exhibit a dendritic structure assembled from branched nanocrystals. Benefiting from their multielement composition and structural features, the catalysts demonstrate superior HER activity under both alkaline and acidic conditions. Specifically, in 1.0 M KOH and 0.5 M H2SO4, the overpotentials required to reach 10 mA cm−2 are merely 24 mV and 51 mV, respectively, outperforming those of previously reported electrocatalysts. Moreover, the Ni@PtIrRhCo NDs exhibit outstanding catalytic stability during prolonged operation. This study offers a straightforward yet effective route toward the development of advanced HER electrocatalysts with both high activity and robust stability.
Accurate monitoring of thiol-containing biomolecules is crucial for understanding redox balance in biological systems. However, conventional luminol-based electrochemiluminescence (ECL) systems rely on unstable H2O2 or suffer from low dissolved O₂ solubility and sluggish kinetics, leading to insufficient reactive oxygen species (ROS) generation and competitive side reactions that compromise sensitivity and reproducibility. To overcome these limitations, we synthesized EuTb nanoparticles/N-doped carbon nanosheets (EuTb/NCSs) as a bimetallic valence relay catalysis (BVRC) platform for H2O2-free luminol ECL detection of L-cysteine (L-Cys). By engineering mixed-valence Tb³⁺/Tb⁴⁺ and Eu³⁺ active centers within the carbon framework, the system decouples cathodic oxygen reduction reaction (ORR) from anodic luminol oxidation, maximizing ROS utilization efficiency and avoiding competitive consumption pathways. The thiol groups of L-Cys scavenge the generated ROS, producing a concentration-dependent decrease in ECL intensity. The sensor achieved a broad linear range of 0.01–1000 ng mL⁻¹, a lower detection limit of 4.52 pg mL⁻¹, and reliable quantification of L-Cys in milk samples (97.7–101.9
Early liver cancer diagnosis requires detecting tumor biomarkers at ultralow concentrations. Conventional methods lack sufficient sensitivity for liver cancer biomarker PIVKA-II in early-stage disease. This study addressed this issue by developing an electrochemical immunosensor based on hollow TePtIrFeCo high-entropy alloy (HEA) nanorods (HEANRs), which were synthesized by a coreduction method. The hollow architecture provided abundant active sites for the antibody immobilization and signal amplification. By leveraging the entropy-stabilized redox synergy effect, the biosensor exhibited a wide linear range from 0.1 to 1,000,000 pg mL-1 and an ultralow detection limit (0.02 pg mL-1) for PIVKA-II. Biosample analysis shows good accordance with standard ELISA, validating the reliability. This platform establishes HEA as high-performance material for label-free immunosensing of biomarkers in early cancer diagnosis.
Rapid, sensitive detection of acetylcholinesterase (AChE) and adenosine triphosphate (ATP) is essential for early diagnosis of metabolic disorders and neurological diseases. Herein, we synthesized porous PtFeMoTeV high-entropy nanotrepangs (HENTs) as nanosheet assemblies, whose five-metal configuration generated electronic synergy that accelerated peroxidase (POD)-like catalysis. This high-entropy nanozyme functioned as a robust POD mimic for colorimetric quantification of both targets. The linear ranges were 0.01–2.0 U L−1 for AChE and 2.0–50.0 μM for ATP, with corresponding detection limits of 0.007 U L−1 and 0.51 μM, respectively, coupled by discriminating ATP analogs and common ions with strong anti-interference capability. In diluted serum samples, standard addition experiments confirmed the high reliability and accuracy of the platform, with recoveries of 103.5%–104.8% for AChE and 98.0%–106.5% for ATP. Overall, this PtFeMoTeV HENTs-based platform holds great promise for biomedical analysis and clinical diagnostics, while providing valuable insights for design of multi-component nanozymes through high-entropy engineering in complex biological media.
Rapid and efficient electrochemiluminescence (ECL) biosensors are crucial for low-injury in vitro testing in emergencies. This work introduces a silver needle electrode (Ag NE) as a replacement for a glassy carbon electrode to build an ECL platform. The ECL emitter, 2,6-dimethyl-1,7-sulfonyl-8-(3-carboxyphenyl)4,4'-difluorobor diazodiazepine (BETS) is covalently linked on Ag NE (BETS-Ag NE), coupled with K2S2O8 as a coreactant for enhanced ECL efficiency. Alternating current voltammetry-driven ECL (ACV-ECL) applied to the BETS-Ag NE system shortens response time to 0.5 s, and the mechanism is examined. Afterward, 2,4-dinitroaniline (DTE), linked via sulfonamide bond, quenches the ECL signal but allows 66.3% recovery within 1.0 min when selenocysteine (Sec) exists even at ultralow-volume samples without dilution. The biosensor shows a wide linear range (10.0-160.0 μM) with a low detection limit of 5.1 pM. It also achieves 97.5% accuracy for auxiliary diagnosis of cerebral hemorrhage (ICH) using Sec as a biomarker with low-volume blood samples, enabling early prediction of edema severity and timely intervention. This work advances the construction of in vitro diagnostic ECL setups, providing a reliable approach for ICH edema diagnosis and microenvironment research.