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Uncapped nanobranch-based CuS clews used as an efficient peroxidase mimic enable the visual detection of hydrogen peroxide and glucose with fast response
Nanosized materials acting as substitutes of natural enzymes are currently attracting significant research due to their stable enzyme-like characteristics, but some flaws of these nanozymes , including their limited catalytic rate and efficiency, need to be remedied to enable their wider applications. In this work, we verify for the first time the catalytic behavior of uncapped nanobranch-based CuS clews as a peroxidase mimic. XRD , XPS , SEM, and TEM proofs demonstrate that high-purity CuS clews composed of intertwined wires with abundant nanodendrites outside are successfully produced via a facile one-pot hydrothermal synthesis approach, with thiourea as both the sulfion source and the structure-directing agent. The synthesized CuS can catalytically oxidize 3,3′,5,5′-tetramethylbenzidine (TMB) by H 2 O 2 to trigger a visible color reaction with rapid response (reaching a maximum change within 5 min). The proposed CuS nanozyme exhibits preferable catalytic kinetics over natural horseradish peroxidase (HRP). This outstanding activity primarily results from the large surface area and rich sites exposed by the uncapped unique structure. Under optimized conditions, the fabricated sensing system provides linear absorbance (652 nm) changes in the H 2 O 2 concentration range of 0.2˜130 μM, with a detection limit of as low as 63 nM. When coupled with glucose oxidase (GOD), the system is demonstrated to be capable of monitoring glucose in blood samples with excellent performance.
The cooperative p-n heterojunction and Schottky junction in Au-decorated hierarchical CuS@SnS2 hollow cubes for boosted charge transport and CO2 photoreduction
During the photocatalytic CO 2 reduction process, fast charge transport, abundant active sites, and high visible light utilization in photocatalysts are key to achieving excellent CO 2 conversion efficiency. In this work, we have designed and prepared hierarchical CuS@SnS 2 p-n heterostructure hollow cubes for photocatalytic CO 2 reduction. First, a monolayer of CuS was in situ generated on the pre-prepared Cu 2 O cubes to construct core–shell Cu 2 O@CuS cubes by sulfidation of Cu 2 O cubes. The following etching process led to the formation of CuS hollow cubes. Finally, the hierarchical CuS@SnS 2 p-n heterostructure hollow cubes were obtained by growing SnS 2 nanosheets on the CuS hollow cubes. The prepared CuS@SnS 2 p-n heterostructure hollow cubes showed an improved photocatalytic CO 2 reduction activity compared with the bare CuS and SnS 2 control samples. The p-n heterojunction formed between SnS 2 and CuS as well as its hollow structure enhanced the charge carrier separation efficiency and the light absorption capacity of the hybrid catalyst. Furthermore, after the decoration of Au nanoparticles, the formed Schottky junction further discouraged the charge carrier recombination. Thus, the cooperative p-n heterojunction and Schottky junction greatly facilitated photocatalytic CO 2 reduction, and exhibiting the maximum CO and CH 4 yields of 140.1 and 77.5 μmol g −1 h −1 , respectively. This work presents an efficient design of high-performance catalysts for photocatalytic CO 2 reduction.
Novel zero-valent copper/CuS heterojunction catalyst with sulfur vacancies for efficient removal of 17β-estradiol via on-site H2O2 generation and activation
Zero-valent metal catalysts are capable of generating hydrogen peroxide (H 2 O 2 ) through oxygen activation. However, their sensitivity to pH and tendency toward surface passivation considerably restrict practical applications. In this study, a ZVC/CuS heterojunction catalyst with sulfur vacancies was successfully fabricated via the hydrothermal method. The catalyst leveraged the synergistic effect between sulfur vacancies and lattice sulfur to first mediate oxygen adsorption on its surface, enabling efficient on-site H 2 O 2 generation and activation. Density functional theory (DFT) calculations confirmed that *OOH served as the key intermediate in the H 2 O 2 formation pathway. Under neutral conditions, the ZVC/CuS self-Fenton system enabled complete (100 %) removal of 17β-estradiol (E2). Electrochemical analyses revealed that the current density of ZVC/CuS was 2.1 times higher than that of ZVC, indicating a substantial enhancement in redox activity. DFT, Liquid chromatography-mass spectrometry (LC-MS) analysis combined with toxicity assessments were collectively employed to deduce the degradation pathways of E2, confirmed that the toxicity of the degradation products was significantly reduced compared to the original pollutants. Importantly, comprehensive experiments under various conditions consistently demonstrated high efficiency in removing pollutants, highlighting the practical potential of ZVC/CuS. This study not only provides a novel strategy to overcome the instability of ZVC but also establishes a highly efficient self-Fenton-like catalytic system that does not require exogenous oxidants.
Growth of Hydrophilic CuS Nanowires via DNA-Mediated Self-Assembly Process and Their Use in Fabricating Smart Hybrid Films for Adjustable Chemical Release
Graphical CuS-tom made : Facile growth of CuS nanowires through self-assembly and their application as building blocks for near-infrared light-responsive functional films is demonstrated (see figure). In vitro studies have shown that the hybrid film possessed excellent biocompatibility and the release rate of chemical molecules from the film could be controlled in a highly spatial and temporal precision. Facile growth of CuS nanowires through self-assembly and their application as building blocks for near-infrared light-responsive functional films have been demonstrated. It is found that DNA is a key factor in preparing the CuS material with defined nanostructure. An exclusive oriented self-aggregate growth mechanism is proposed for the growth of the nanowires, which might have important implications for preparing advanced, sophisticated nanostructures based on DNA nanotechnology. By employing the hydrophilic CuS nanowire as an optical absorber and thermosensitive nanogel as guest reservoir inside alginate film, a new platform for the release of functional molecules has been set up. In vitro studies have shown that the hybrid film possesses excellent biocompatibility and the release rate of chemical molecules from the film could be controlled with high spatial and temporal precision. Our novel approach and the resulting outstanding combination of properties may advance both the fields of DNA nanotechnology and light-responsive devices.
Ultrasensitive determination of sulfathiazole using a molecularly imprinted electrochemical sensor with CuS microflowers as an electron transfer probe and Au@COF for signal amplification
In this work, a molecularly imprinted sensor employing copper sulfide (CuS) as a novel signal probe was successfully developed for ultrasensitive and selective determination of sulfathiazole (STZ). The reduction signals of Cu 2+ produced in the process of electron transfer of CuS containing large amounts of Cu 2+ are easy to be captured, which provide high electrochemical signals. Moreover, gold nanoparticles@covalent organic framework with excellent conductivity was introduced on the electrode surface for signal amplification and facilitating electron transfer processes of CuS. Under optimized testing conditions, the proposed sensor offered a linear DPV response to STZ over a very wide concentration range (1.0 × 10 -4 to 1.0 × 10 -11 mol L -1 ), with a limit of detection of 4.3 × 10 -12 mol L -1 . Fodder and mutton samples spiked with STZ were analyzed using this sensor, and the satisfactory recoveries ranging from 83.0% to 107.2% were obtained. In addition, the proposed sensor was used to determine the concentration of STZ in chicken liver and pork liver, with quantification results being near identical to those determined by high-performance liquid chromatography.
Single-nanozyme based sensor array: mesoporous hollow melanin-CuS with dual-enhanced peroxidase-like and specific recognition activities for sensitive discriminative detection of fluoroquinolones
Antibiotic residues threaten ecosystems and human health, but current nanozyme-based colorimetric sensors suffer from weak activity and low interference resistance. Here, we address these challenges with a rationally designed mesoporous hollow polydopamine-copper sulfide (MHPDA-CuS) hybrid nanozyme. The nanozyme exhibits dramatically enhanced catalytic efficiency, with K m values for TMB and H 2 O 2 (0.146 and 0.206 mM, respectively) being 5.29- and 17-fold lower than those of horseradish peroxidase. Attractively, fluoroquinolones (FQs) function as dual-functional cofactors that dramatically boost the activity of the hybrid nanozyme due to the specific interaction of FQ with both PDA and copper ions in the nanozyme. The effect is closely linked to their molecular structure. This finding enables a three-channel colorimetric sensor array that rapidly (<10 min) discriminates multiple FQs with ultrahigh sensitivity (limit of detection, LOD < 1 nM) at a nanozyme dosage 100-fold lower than conventional methods. This dual-regulation strategy provides a powerful, facile tool for environmental and food safety monitoring and advances the structure-function understanding of polymer-metal hybrid nanozymes.
Dopamine-bridged CuS–ZnIn2S4/PAN nanofibrous membrane for purification of viscous emulsified oil pollutants with integrated oil resistance, photocatalytic self-cleaning, and photothermal conversion
The polymeric membrane encounters huge challenge in dealing with high-viscosity oil pollutants and complicated membrane fouling issues. Herein, the multi-functional polymeric composite membrane (ZCP) is fabricated via anchoring bio-adhesive dopamine bridged gear-like CuS–ZnIn 2 S 4 heterostructure onto PAN nanofiber support, which hits three birds with one stone. Firstly, the unique three-dimensional gear-like structure confers the ultra-low oil adhesion and high permeability to membrane by constructing underwater superoleophobicity (UWCA: up to 157.1° ± 1.6°) and providing efficient mass transfer channels, as confirmed by Molecular dynamics simulation and Hermia equation-fitted blocking models. The ZCP membrane demonstrates superior separation flux (3921.44 ± 196.1 L m −2 h −1 ) and separation efficiency (up to 99.53 %) for diverse oil-in-water emulsions. Besides, the ZCP membrane shows remarkable durability in harsh conditions and cyclic separation stability. Secondly, dopamine bridged CuS–ZnIn 2 S 4 heterostructure mitigates charge recombination, strengthens electron transfer, and extends light absorption, which results in favorable photocatalytic self-cleaning via peroxymonosulfate (PMS) activation. Under simulated sunlight and low PMS input, the ZCP membrane exhibits high-efficiency catalytic degradation of organic pollutants within 60 min (97.9 % tetracycline and 100 % dye degradation rates) and effective self-cleaning for membrane regeneration (98.51 ± 2.4 % flux recovery rate). Moreover, the band structure, charge transfer, and mechanism of photocatalytic PMS activation are elucidated. Thirdly, owing to the photothermal conversion function of CuS–ZnIn 2 S 4 heterostructure, the membrane surface temperature reaches 61.7 °C within 15 s, thus efficiently reducing oil viscosity and achieving 102.04 % enhancement in permeation flux during the simulated O/W separation application. This work opens a new avenue for treatment of complex emulsified oily wastewater and membrane fouling control.
The effect and mechanism of the MW/CuS/H2O2 process in removing refractory organic matter from the effluent of biological treatment of landfill leachate
Although copper-based Fenton-like processes can remove refractory organics from the membrane bioreactor effluent of landfill leachate (referred to as MBR effluent), the kinetic limitations of the Cu 2+ /Cu + cycling lead to oxidant consumption, which further restricts the degradation efficiency. To address this issue, the microwave (MW)/CuS/H 2 O 2 Fenton-like process (pH = 3.0, MW = 160 W, CuS = 96 mg/L, [H 2 O 2 ] = 75 mM, t = 15 min) was used to treat the MBR effluent. The results showed that this process efficiently removed UV 254 (69.26 %) and color number (CN, 94.45 %) and significantly reduced the degree of polymerization, aromaticity, and molecular weight of organics in the MBR effluent. Further reactive species experiments confirmed the presence of hydroxyl radicals ( • OH), singlet oxygen ( 1 O 2 ), and superoxide radicals (O 2 •− ) in the process, with O 2 •− acting as the primary reactive species. On the basis of the changes in the CuS morphology and valence state, it was indicated that the main mechanism of the MW/CuS/H 2 O 2 Fenton-like reaction is a synergy between homogeneous and heterogeneous Fenton-like processes, and the thermal effect of MW accelerated the cycling of the Cu 2+ /Cu + and the generation of reactive species. Finally, after 6 cycles of the CuS catalyst, the removal efficiency of benzoic acid (BA) remained above 70 %. This confirms the structural and chemical stability of CuS. This study provides a reference for overcoming the kinetic limitations of copper-based Fenton-like processes and improving the removal efficiency of refractory organics from the MBR effluent.
Facile and eco-friendly fabrication of biocompatible hydrogel containing CuS@Ser NPs with mechanical flexibility and photothermal antibacterial activity to promote infected wound healing
Bacterial infections can significantly impede wound healing and pose a serious threat to the patient’s life. The excessive use of antibiotics to combat bacterial infections has led to the emergence of multi-drug-resistant bacteria. Therefore, there is a pressing need for alternative approaches, such as photothermal therapy (PTT), to address this issue. In this study, for the first time, CuS NPs with photothermal properties were synthesized using sericin as a biological template, named CuS@Ser NPs. This method is simple, green, and does not produce toxic and harmful by-products. These nanoparticles were incorporated into a mixture (XK) of xanthan gum and konjac glucomannan (KGM) to obtain XK/CuS NPs composite hydrogel, which could overcome the limitations of current wound dressings. The composite hydrogel exhibited excellent mechanical flexibility, photothermal response, and biocompatibility. It also demonstrated potent antibacterial properties against both Gram-positive and negative bacteria via antibacterial experiments and accelerated wound healing in animal models. Additionally, it is proved that the hydrogel promoted tissue regeneration by stimulating collagen deposition, angiogenesis, and reducing inflammation. In summary, the XK/CuS NPs composite hydrogel presents a promising alternative for the clinical management of infected wounds, offering a new approach to promote infected wound healing.
A ternary CdS@Au-g-C3N4 heterojunction-based photoelectrochemical immunosensor for prostate specific antigen detection using graphene oxide-CuS as tags for signal amplification
Photoactive materials with high photo-electron transfer efficiency and stable signal output hold a key role in constructing the photoelectrochemical (PEC) biosensing systems. In this study, the ternary [email protected] 3 N 4 heterojunction was first prepared and characterized, and its application in PEC bioanalysis was explored. The gold nanoparticles sandwiched between CdS and g-C 3 N 4 , acting as both plasmonic photosensitizer and electron relay, significantly boosted the light absorption and accelerated the charge transfer from g-C 3 N 4 to CdS, both of which contributed to the enhancement of photoelectric conversion efficiency. Signal quenching with graphene oxide-CuS efficiently weakened the photocurrent from [email protected] 3 N 4 . The combination of the excellent PEC properties of [email protected] 3 N 4 and the remarkable quenching effects of graphene oxide-CuS enabled construction of a sandwich-type PEC immunosensor for prostate specific antigen (PSA) detection. This immunosensor achieved sensitive PSA analysis by multiple signal amplification mechanisms, with a detection limit of 0.6 pg mL −1 and a wide linear range from 1.0 pg mL −1 to 10 ng mL −1 . This work not only demonstrates the great potential of noble metal sandwiched ternary heterojunctions in the PEC field, but also lays a foundation for developing the general PEC immunoassays .
Critical Role of CUS in the Au/MOF-808(Zr) Catalyst for Reaction of CO2 with Amine/H2 via N-Methylation and N-Formylation
MOF-808(Zr) with the coordinated unsaturated (CUS) Zr4+ centers was synthesized by the thermal reflux method, and a series of Au/MOF-808(Zr) catalysts with different Au loading percentages have been prepared by the impregnation–reduction method. The related X-ray diffraction, Fourier transform infrared spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, N2 adsorption–desorption, Inductively coupled plasma-mass spectrometry, and NH3 temperature-programmed desorption characterizations have been undertaken to understand the structure of catalysts. The catalytic activity in CO2 with aniline/H2 to N-methylation and N-formylation has been studied in a batch reactor. Results show that the MOF-808(Zr) structures in catalysts are of high quality and damage-free. The Au nanoparticles (NPs) are highly dispersed on the surface of the MOF-808(Zr) cage with a mean size of 2–20 nm. Also, the catalysts could catalyze the conversion of CO2 with aniline/H2 to N-methylation and N-formylation products with a high efficiency. With a 3.0 wt % Au/MOF-808(Zr) catalyst, the conversion of aniline is 18.4%, and the selectivity of N-methylaniline is 80.9% and that of N,N-dimethylaniline is 19.1%. The preliminary reaction mechanism and the critical role of CUS were also studied. It is determined that H2 is adsorbed and activated on Au NPs. CO2 is adsorbed on the CUS Zr4+ acidic sites and O2– basic sites. The primary and secondary amines are adsorbed on the CUS Zr4+ acidic sites, where they react with CO2 and H2 to form N-formamide. Subsequently, N-formamide reacts with activated H2 to yield N-methylamine.
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