Neonicotinoid pesticides are a typical category of emerging hazardous micropollutants, and chlorine (Cl2) is a widely used disinfectant that readily induces the chlorination of organic micropollutants. This study systematically investigated the chlorination kinetics and transformation pathways of a representative neonicotinoid pesticide (clothianidin, CLO) and evaluated the cytotoxicity variation via Chinese Hamster Ovary (CHO) cell assays. CLO chlorination followed second-order kinetics, with a first-order dependence on both CLO and Cl2 concentrations, and the apparent rate constant (kapp) value was measured to be 1.758 × 10−4 μM−1 h−1, at a pH of 7.0. The CLO chlorination initially accelerated and then retarded with the increase in pH. The same tendency was involved in the yield of disinfection byproducts (i.e., trihalomethanes and haloacetic acids). Dissolved organic matter was also a crucial factor inhibiting the chlorination of CLO. The reaction of CLO+ with HOCl was more prevalent than between CLO+ with ClO−, wherein HOCl likely exerts electrophilic attack either after 2-nitroguanidine hydrolysis or directly at the nitrogen sites of secondary amines. Cell exposure results revealed that the chronic cytotoxicity of CLO decreased significantly after chlorination. This study helps to the mechanistic understanding of neonicotinoid transformation during water disinfection, and provides a valuable reference for the control of neonicotinoid pesticides in drinking water.
The influence of achiral surfactants on synergistically chiral effect of interfacial nucleation, assembly orientation, and morphological evolution in chiral nanostructural synthesis via a chemical solution method is largely ignored and underexplored. Herein, we report a surfactant-mediated continuous evolution of chiral Cu2-xS (0 < x < 1) from layered nanosheets to twisted nanobowties (TNBs) and uncovered a multiscale chirality amplification mechanism driven by tilted stacking of coordination nanosheets. Surfactant identity, including headgroup and alkyl chain length, controls the potential, adsorption strength, and density, as well as tail packing of interfacial layers formed by Cu2+-cysteine coordination units, thereby directing their assembly pathway. In particular, in sodium dodecyl sulfate, the anionic headgroups electrostatically anchor coordination-derived nanoparticles, while the hydrophobic tails form a dense interfacial soft-template that directs nucleation and anisotropic growth of coordination nanosheets. Under the stereochemical control of chiral cysteine, these nanosheets undergo progressive intersheet tilting and hierarchical stacking, ultimately evolving into micrometer-scale TNBs. Catalytic oxidation of 3,4-dihydroxy-l/d-phenylalanine reveals that higher structural dimensionality and increased chiroptical response of Cu2-xS improve catalytic activity and enantioselectivity. This work demonstrates a surfactant-mediated interfacial soft-template strategy for the rational design of chiral inorganic materials and the translation of molecular asymmetry into continuously tunable micrometer-scale architectures for enantioselective catalysis.
Early cancer screening is pivotal for reducing mortality yet remains constrained by the trade-off between analytical accuracy and operational simplicity. Here, we present a dual-hue recognizable lateral flow immunoassay (DHLFIA) that enables rapid, quantitative, and user-friendly detection of prostate cancer biomarkers. The platform integrates dual-ratiometric fluorescence transitions, establishing two hue recognition pathways (green-to-red and blue-to-red) with distinct sensitivities for the precise quantification of total (t-PSA) and free (f-PSA) prostate-specific antigens. The differentiated color responsiveness of the two ratio system, governed by the inner filter effect, was elucidated both theoretically and experimentally. This dual-hue strategy enables semiquantitative visual discrimination of the clinically significant "gray zone" (t-PSA: 4-10 ng/mL) by the naked eyes, while smartphone-based tonal analysis of the f-PSA/t-PSA ratio (cutoff = 0.16) allows accurate risk stratification within this range. Validated with clinical serum samples, the DHLFIA achieved a diagnostic accuracy of 96.7%, comparable to chemiluminescent assays, yet offered markedly improved speed and ease of operation. By coupling a modular design with dual-ratiometric readout principles, this work establishes a generalizable framework for multiplexed, point-of-care diagnostics of noncommunicable diseases.
Development of ethane-selective porous materials for highly efficient ethane/ethylene (C2H6/C2H4) separation can energy-efficiently produce high-purity C2H4 in one step. Microporous metal-organic frameworks (MOFs) show great promise as ethane-selective materials; however, achieving both high C2H6 capacity and high C2H6/C2H4 selectivity in most reported MOFs remains a significant challenge. Herein, we report, for the first time, the strategy of designing V-shaped pore structure with multiple binding sites in an Al-MOF (CAU-8-ODB) to target both high C2H6 uptake and selectivity for highly efficient C2H6/C2H4 separation. This V-shaped micropore configuration not only enables a large number of inert phenyl rings surrounding the cage to provide stronger interactions with C2H6 over C2H4, but also provides enough pore spaces to take up large amount of C2H6. Gas adsorption studies reveal that CAU-8-ODB exhibits a combination of both large C2H6 adsorption capacity (3.30 mmol & centerdot;g-1 at 0.5 bar) and high C2H6/C2H4 selectivity (2.2) at 296 K and 1 bar, outperforming or comparable to most of top-performing materials reported. Theoretical calculations indicate that the V-shaped cavities with suitable pore spaces can provide stronger multipoint interactions with C2H6 than C2H4, accounting for both high C2H6 uptake and selectivity. The actual separation capacity of CAU-8-ODB was further testified by the breakthrough experiments for 50/50 (v/v) C2H6/C2H4 mixtures, affording a remarkably high C2H4 productivity of 15.1 L & centerdot;kg-1 with high purity of 99.95% under ambient conditions.
Volatile organic compounds (VOCs) are important precursors of ozone and secondary organic particulate matter, with an extensive range of sources and complex composition. Dichloromethane (DCM) and n-hexane, as common and typical VOCs, are extensively applied as solvents, extractants and cleaning agents in the pharmaceutical and chemical industries. The persistence, teratogenicity and carcinogenicity seriously harm the ecological environment and human health. In this study, combining the advantages of microbial electrolytic cell (MEC), the detoxification mechanism between low concentration n-hexane and DCM was analyzed. The results demonstrated that the n-hexane favored the enrichment of key functional genera, including degrading and electroactive microorganisms, which could be attributed to the mild toxicity of n-hexane at low concentrations and sufficient carbon sources. In contrast, DCM significantly inhibited the degradation of n-hexane. Metagenomic annotation results suggested that DCM was converted to formaldehyde via hydrolyzing haloalkane dehalogenase (DhlA) or DCM dehalogenase (DcmA). Formaldehyde was partly oxidized to carbon dioxide (CO2) and partly assimilated into the ribulose monophosphate pathway or the serine pathway. And then converted to acetyl-CoA to enter the TCA cycle, which provided energy and material cycles for microbial metabolism. These results provided a new method for the detoxification of mixed VOCs and offer a new insight into the treatment and disposal of pollutants in practical engineering applications.
Magnetic nanowire arrays derive their magnetic response from the competition among shape anisotropy, magnetocrystalline anisotropy, and interwire magnetostatic interactions. However, the coupling between composition-dependent anisotropy and a continuous axial diameter gradient remains insufficiently understood. In this work, CoxNi1-x gradient-diameter magnetic nanowire arrays spanning pure Ni to pure Co were fabricated, with diameters increasing continuously from approximately 30 to 100 nm along the wire axis. Increasing Co content was accompanied by a gradual evolution from a face-centered cubic (fcc)-dominated Ni-rich structure toward a greater hexagonal close-packed (hcp)-related contribution, thereby strengthening the competition between magnetocrystalline anisotropy and axial shape anisotropy. For all compositions, the coercivity measured with the field parallel to the nanowire axis exceeded that measured in the transverse direction, while both coercivity and remanence ratio varied non-monotonically with Co content. Across the compositional evolution from Ni to Co, the angular magnetic response also changed non-monotonically, revealing a composition-dependent redistribution of the reversal barriers. In particular, an off-axis coercivity maximum emerged at 45° for Co0.47Ni0.53, whereas pure Co exhibited a shallow maximum at 15°. Micromagnetic simulations further revealed spatially differentiated reversal behavior, with the wide end preferentially supporting vortex-mediated nonuniform reversal and the narrow end favoring comparatively coherent switching. Interwire magnetostatic interactions broadened the apparent bias-field distribution and modified the switching sequence within the array. This work provides an experimental foundation for designing nanowire arrays with tunable magnetic properties.
The frequent occurrence of epidemics transmitted via bioaerosols has raised serious biosafety concerns. Photocatalytic technology shows promise for bioaerosol inactivation, yet challenges remain, including poor visible-light utilization, weak bacterial adsorption, and incomplete inactivation. Herein, waste shrimp shell protein was innovatively employed as a sustainable biochar production, and a visible-light-responsive TiO2/C composite photocatalyst was successfully prepared via a solvothermal route. The as-prepared optimal sample, denoted TC-C-0.7, achieved an inactivation efficiency of 99.99% against high-concentration Staphylococcus aureus bioaerosols within only 5 minutes of visible light irradiation. Importantly, this high inactivation performance remained stable even under high flow rate conditions. Such excellent performance arises from multiple synergistic effects. Oxygen-containing functional groups on the biochar surface form hydrogen bonds with amide moieties in bacterial membrane proteins, while hydrophobic domains interact with fatty acid chains of lipopolysaccharides via van der Waals forces, thereby enhancing the adsorption and enrichment of bacteria at the catalyst surface. Under visible light irradiation, the generated reactive oxygen species (ROS) further induce oxidative damage to S. aureus. Specifically, ROS disrupt cell membrane integrity, penetrate into the cytoplasm, attack the deoxyribose backbone of DNA, trigger base modifications and phosphodiester bond cleavage, inactivate the ATP synthesis system, interrupt genetic information transmission, and cause irreversible leakage of intracellular components, ultimately resulting in the death of the bacteria. Additionally, biochar acted as an electron reservoir, facilitating ·OH generation and improving inactivation efficiency. Overall, This work realizes high-value utilization of waste shrimp shells and provides an efficient, reusable, and sustainable strategy for bioaerosol control.
Efficient electromagnetic wave (EMW) absorption requires the synergistic optimization of dielectric loss and impedance matching, which remains challenging for dielectric absorbers. Herein, ZnO-doped carbon hollow nanospheres (ZnO/C) featuring hierarchical porosity and defect-rich architectures are rationally constructed via the pyrolysis of polystyrene-templated ZIF-8. The synergistic effects of sacrificial template removal and controlled framework decomposition give rise to well-defined hollow cavities, multilevel porous carbon shells, uniformly dispersed ZnO nanodomains, and abundant intrinsic defects. The hollow architecture effectively tailors the overall permittivity, thereby optimizing impedance matching, while heterogeneous interfaces, defect-induced dipoles, and interconnected conductive networks collaboratively enhance dielectric loss through interfacial polarization, dipole relaxation, and conduction loss. Benefiting from this integrated structural and defect regulation, ZnO/C-2-800 delivers an effective absorption bandwidth (EAB) of 9.0 GHz at a thickness of 3.1 mm, fully covering the X-Ku band, whereas ZnO/C-5-800 achieves a minimum reflection loss (RLmin) of -41.9 dB at 8.0 GHz. These results highlight hollow MOF-derived architectures with engineered defects as an effective strategy for high-performance EMW absorbers.
Broadband electromagnetic wave (EMW) absorption is fundamentally limited by the intrinsic trade-off between impedance matching and attenuation capability. Herein, a synergistic regulation strategy integrating cross-scale pore structure coupling and in situ confined growth of magnetic nanoparticles is proposed. By combining micro/ mesoporous metal-organic frameworks (MOFs) with macroporous chitosan aerogels, hierarchical porous Fe/ Fe3O4/C composites are constructed via freeze-drying and subsequent pyrolysis. The cross-scale coupling of micro/mesoporous and macroporous structures effectively tailors the dielectric environment, enabling optimized impedance matching. Meanwhile, interfacial interactions between MOFs and biomass induce the in situ confined growth of magnetic nanoparticles, suppressing aggregation and stabilizing magnetic loss behavior. The optimized sample achieves a minimum reflection loss of-39.0 dB at 15.36 GHz with a thickness of 1.5 mm and an effective absorption bandwidth of 4.64 GHz, while full-band coverage (2-18 GHz) is realized through thickness modulation. This work provides a new insight into the structure-performance synergy for designing highperformance broadband EMW absorbers.
The seed-mediated solution growth is largely reported for obtaining chiral noble metal nanostructures, but multistep growth procedures and delicate seed dependence increase its complexity. Herein, we report a seedless, solution-based synthetic strategy for obtaining Ag-Pt hollow nanostructures with chiral nanoarrays on the surface, where enantiomers of 2-deoxy-d-/l-ribose and thymine are utilized as chiral comolecule inducers. By simply changing the feeding sequence, both hollow nanospheres and nanotubes can be synthesized due to the differentiated formation of thymidine as a key intermediate. In situ-formed Ag-rich nanoparticles and nanowires act as sacrificial templates for subsequent Pt growth, leading to hollow nanostructures with Ag-rich inner and Pt-rich chiral surfaces. The growth mechanism can be extended to guide the synthesis of similar chiral Ag-Ir hollow nanostructures. The chiral Ag-Pt hollow nanostructures, especially nanotubes, are fully functional for electrochemical enantioselective detection of tryptophan enantiomers. Our work provides a feasible strategy for fabricating catalytically active noble metals with hierarchical chiral nanostructures.
The integration of chiral catalysts with circularly polarized light (CPL) for enantioselective catalysis is an emerging research direction. Herein, a series of cubic and icosahedral Pd nanoparticles loaded on polyaniline nanohelices with continuously varying helicity were synthesized as chiral catalysts. Under matched CPL, they show chiral structure-dependent photothermal response and enhanced catalytic activity and enantioselectivity, all increasing with the degree of helical twist.
Co-occurring algal blooms and lead (Pb) pollution pose severe threts to freshwater ecosystems. In this study, Aspergillus oryzae (A. oryzae) 3.042 fungal pellets (FPs) were produced to harvest Chlorella pyrenoidosa, creating fungal-algal pellets (FAPs), which were used as heavy-metal capture materials. Under optimized conditions (2 mm diameter, 180 rpm, 3 g·50 mL-1, pH 3-7), FPs achieved 95 %-99 % algae removal efficiency, with these factors significantly influencing removal efficiency. Under complex water conditions, including microalgae concentration, Pb concentration and N:P ratio, FPs achieved satisfactory microalgae removal efficiency, demonstrating its advantages in water body restoration. Multiscale characterization revealed that FAPs formation relies primarily on electrostatic attraction complemented by functional-group interactions. Furthermore, FAPs structure facilitates Pb immobilization via chemisorption (94 mg·g-1), mediated by surface amide, carboxyl, and phosphate groups, forming {FAPs-tyrosine-Pb} complexes. A. oryzae 3.042, utilizing FPs technology, is biosafe, high-efficient, and sustainable solution for microalgae harvesting and Pb remediation in water.
This study compares copper nanoflowers and nanobranches synthesized via constant-current and constantvoltage electrodeposition methods, and proposes an in situ constant-voltage deposition approach for fabricating copper nanoflowers directly on screen-printed electrodes. This strategy enables large-scale, cost-effective production of glucose sensing units. Building upon this copper-based architecture, we introduce a vapor-phasedeposited palladium nanocluster modification technique, which enhances electron transfer kinetics and provides abundant catalytically active sites. The synergistic interaction between Pd and Cu endows the modified electrode with exceptional electrocatalytic performance and long-term stability. The sensor demonstrates a linear detection range of up to 500 mu M, a sensitivity of 0.16 mA & sdot;mM- 1 & sdot;cm- 2, and a low detection limit of 1.6 mu M. Moreover, it retains catalytic activity and anti-interference capability over a 20-day operational period. When integrated with microfluidic modules, this sensing platform shows strong potential for the scalable fabrication of wearable glucose sensors.
Hyperuricemia, marked by elevated blood uric acid levels, poses significant health risks. Current uricase-based treatments have a serious issue of H2O2 and reactive oxygen species (ROS) accumulation. MnO2-based nanozymes have been demonstrated to possess uricase-like catalytic activity, but with the limitations of low catalytic performance and poor H2O2 and ROS removal ability. This study investigates a novel nanostructure of the Au@MnO2 yolk-in-shell for managing hyperuricemia. This unique nanohybrid structure, with an individual Au nanoparticle embedded within the hollow MnO2 shell, reduces the Au loading and shows exceptional uricase-like catalytic performance. Density functional theory calculations reveal the existence of the strong synergistic interactions between the Au and MnO2 interface layer within this structure, and the introduction of Au increases adsorption energies for both oxygen and uric acid on MnO2, facilitating an efficient catalytic process. The Au@MnO2 yolk-in-shell nanostructure exhibits excellent metabolic rates, good biocompatibility, and superior therapeutic effects. (The blood uric acid level is decreased by 71%, and both liver and kidney functions return to normal). These findings underscore the Au@MnO2 yolk-in-shell nanostructure as a promising candidate for hyperuricemia treatment. This approach paves the way for efficient, cost-effective therapies and provides valuable insights into enhancing enzyme activity in various applications.
In this study, a flexible room‐temperature ammonia (NH3) sensor is developed based on MoO3/CuO/Cu2O hybrid nanoclusters (HNCs), specifically designed for the noninvasive diagnosis of nephropathy. The MoO3/CuO/Cu2O HNCs achieve an ultralow detection limit of 0.73 ppm, with high sensitivity (0.163 ppm−1) and rapid response and recovery times (16.4 and 90.6 s). The integration of MoO3 (n‐type) with CuO and Cu2O (p‐type) forms multi‐heterojunctions, enhancing gas‐sensing performance through efficient charge separation and improved NH3 adsorption. Additionally, the sensor demonstrates excellent mechanical flexibility and long‐term stability under dynamic deformation. To address humidity interference in exhaled breath analysis, the sensor with a hydrophobic polytetrafluoroethylene layer is coated via radio frequency sputtering, ensuring effective NH3 detection and differentiation between healthy individuals and kidney disease patients. In this work, the potential of multi‐heterojunction nanostructures in developing high‐performance, flexible gas sensors for practical health‐monitoring applications is highlighted.
The accurate and rapid detection of erythromycin (ERY) is of great significance to environmental protection and human health. Herein, a "turn-on" fluorescent sensor was developed for the quantitative detection of ERY in aqueous solution. The probe Cu-BDC-NH2 exhibits weak blue emission due to the ligand-to-metal charge transfer (LMCT) effect. Upon the addition of ERY, the fluorescence intensity increases by 436%, whereas other similar antibiotics lead to fluorescence quenching. The sensing mechanisms were thoroughly investigated by powder X-ray diffraction, fluorescence lifetime measurements, UV-vis spectroscopy and X-ray photoelectron spectroscopy. Owing to the excellent selectivity and sensitivity, test strips based on the probe were further prepared to evaluate the practical applicability in real samples.
The separation of ethane (C2H6) from ethylene (C2H4) is critical for obtaining polymer-grade C2H4. Adsorptive separation with C2H6-selective MOFs offers a viable alternative to energy-intensive cryogenic distillation, enabling the direct production of high-purity C2H4. In this study, we developed an ultrastable ethane-selective metal-organic framework, UiO-67-(CH3)2, which demonstrates enhanced C2H6 adsorption (4.10 mmol g-1 at 1 bar and 298 K), higher C2H6/C2H4 selectivity of 1.70, and an increased C2H6/C2H4 adsorption ratio of 1.53 compared to unmodified UiO-67. GCMC simulations demonstrate that C2H6 forms more C-H···π interactions with the surrounding benzene rings and more C-H···C interactions with methyl groups compared to C2H4, highlighting the synergistic effects of supramolecular interactions. Furthermore, the hydrophobic pore environment also minimizes water interference, with exceptionally low water uptake (0.019 g g-1 at 60% RH), ensuring robust separation capacity under high humid conditions. The introduction of methyl groups not only significantly enhances C2H6 adsorption performance and C2H6/C2H4 separation selectivity but also improves material's hydrophobicity.