International Journal of Electrochemical Science
·
2024
·
IF 1.3
Bin Li,Pingxia Wang
Dexamethasone, a potent synthetic glucocorticoid, is widely used for its anti-inflammatory and immunosuppressive properties. However, its misuse as a performance-enhancing drug in sports has raised concerns among regulatory authorities. To address this issue, an electrochemical sensor based on Fe 3 O 4 /polyaniline (PANI)-Cu(II) microspheres and hematite nanoparticles was developed for the sensitive and selective detection of dexamethasone. The sensor exhibited excellent electrocatalytic activity towards the oxidation of dexamethasone due to the synergistic effect of the high conductivity and large surface area of the Fe 3 O 4 /PANI composite microspheres, the electrocatalytic properties of the loaded copper(II) ions, and the enhanced electron transfer of the hematite nanoparticles. Under optimized conditions, the sensor showed a wide linear range of 0.05–50 μM, with a detection limit of 0.015 μM. The sensor also demonstrated good selectivity, reproducibility (RSD = 3.2 %, n = 5), and long-term stability (92 % retention after 4 weeks). Furthermore, the sensor was successfully applied for the determination of dexamethasone in spiked human serum and urine samples, with recoveries ranging from 97.5 % to 103.5 % and RSDs less than 3.5 %.
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ACS Nano
·
2025
·
IF 16
Yipeng Zang,Haitao Li,Yan Sun,Lei Tang,Kangli Xu,Dunfeng Gao
Electrochemical CO2 reduction reaction on Cu catalysts can generate high-value multicarbon (C2+) products, making it a significant research area of growing commercial interest. However, the production rate of ethanol remains low owing to the trade-off between the activity and selectivity of Cu catalysts. Here, we develop a defect-rich Cu catalyst with abundant high-index step sites by chemically etching commercially available Cu nanoparticles. This catalyst exhibits a high Faradaic efficiency of ∼50% and a partial current density of ∼416 mA cm–2 for ethanol production. Furthermore, it shows good stability at a high total current density of ∼800 mA cm–2, without obvious decay in ethanol selectivity. Control experiments indicate that the impressive ethanol selectivity is closely associated with the high density of high-index steps present on the defect-rich Cu catalyst. In situ Raman spectroscopy and density functional theory calculations further verify that the optimal high-index step sites enable balanced adsorption of *CO, *OH, and *H, and facilitate the hydrogenation of *CHCOH to *CHCHOH, thereby improving ethanol selectivity. This work underscores the importance of step density control for steering the reaction pathway and selectivity toward ethanol.
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ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Yonghou Xiao,Qiang Guo,Shuohan Yang,Qidong Zhao,Gaohong He
The cuprous-ion-based zeolites constructed by introducing Cu(I) adsorption active sites into zeolite Linde Type A have proved to be efficient in carbon monoxide (CO) adsorption with high selectivity and capacity. However, how to directly fabricate zeolite 4A containing copper species and effectively overcome cuprous ion aggregation during the preparation process is still a challenge. Here, we propose an efficient fabrication method to synthesize highly dispersed Cu(I)-modified octahedral zeolite 4A adsorbents using a molecular complex formed by a hydrogel with a silicon/aluminum molar ratio of 1:1, copper ions, and tetramethylammonium hydroxide (TMAOH) as the template. Zeolite 4A containing copper ions was directly obtained by incorporating the precursor of cuprous ions into the confined space between zeolite 4A channel walls and TMAOH. The target zeolite Cu(I)/4A adsorbent with highly dispersed Cu(I) was constructed after introducing VCl3 as the reducing agent via the solid-state dispersion method during the process of removing the template. In comparison with pristine zeolite 4A, a bimodal microporous pore size distribution was observed in as-synthesized Cu(I)/4A. Cu(I)/4A exhibited an enhanced static (1.15 mmol/g) and dynamic (0.0016 mmol g−1) CO adsorption capacity, respectively, at 25 °C and 1 bar. Moreover, Cu(I)/4A displayed a lower H2 adsorption capacity under identical conditions. Through calculation using the ideal adsorption solution theoretical (IAST) equation, the CO selectivity from the CO/H2 mixture on Cu(I)/4A attained ca. 16.95. Therefore, Cu(I)/4A with highly dispersed Cu(I) was successfully fabricated, and its excellent CO adsorption selectivity and capacity enable it to be potentially applied for the actual deep separation of CO/H2.
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Journal of Environmental Sciences
·
2024
·
IF 5.9
Kaini Ma,Kai Li,Ping Ning,Jiayu Feng,Jiacheng Bao,Lei Shi,Xiangyu Wang,Xin Sun
This study employed a wet impregnation method to synthesize five types of Cu/HZSM-5 adsorbents with Si/Al ratios of 25, 50, 85, 200, and 300, used for the removal of H 2 S in low-temperature, low-oxygen environments. The impact of different Si/Al ratios on the adsorption oxidative performance of Cu 30 /HZSM-5–85 adsorbents was investigated. According to the performance test results, Cu 30 /HZSM-5–85 exhibited the highest breakthrough capacity, reaching 231.75 mg H 2 S/g sorbent . Cu/HZSM-5 sorbent maintains a strong ability to remove H 2 S even under humid conditions and shows excellent water resistance. XRD , BET, and XPS results revealed that CuO is the primary active species, with Cu 30 /HZSM-5–85 having the largest surface area and highest CuO content, providing more active sites for H 2 S adsorption. H 2 -TPR and O 2 -TPD results confirmed that Cu 30 /HZSM-5–85 sorbent exhibits outstanding redox properties and oxygen storage capacity, contributing to excellent oxygen transferability in the molecular sieve adsorption-oxidation process. With notable characteristics such as a large surface area, high desulfurization efficiency, and water resistance, Cu 30 /HZSM-5–85 sorbents hold significant importance for industrial applications.
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Energy & Environmental Materials
·
2024
·Vol. 7
·期 5
·e12717
·
IF 13
Dongliang Liu,Hang Shang,Chuan Zhou,Jie Miao,Daxiang Xue,Zeping Chen,Meijuan Fei,Fengli Liang,Qiang Niu,Ran Ran,Wei Zhou,Zongping Shao
Solid oxide electrolysis cells (SOECs), displaying high current density and energy efficiency, have been proven to be an effective technique to electrochemically reduce CO 2 into CO. However, the insufficiency of cathode activity and stability is a tricky problem to be addressed for SOECs. Hence, it is urgent to develop suitable cathode materials with excellent catalytic activity and stability for further practical application of SOECs. Herein, a reduced perovskite oxide, Pr 0.35 Sr 0.6 Fe 0.7 Cu 0.2 Mo 0.1 O 3-δ (PSFCM0.35), is developed as SOECs cathode to electrolyze CO 2 . After reduction in 10% H 2 /Ar, Cu and Fe nanoparticles are exsolved from the PSFCM0.35 lattice, resulting in a phase transformation from cubic perovskite to Ruddlesden–Popper (RP) perovskite with more oxygen vacancies. The exsolved metal nanoparticles are tightly attached to the perovskite substrate and afford more active sites to accelerate CO 2 adsorption and dissociation on the cathode surface. The significantly strengthened CO 2 adsorption capacity obtained after reduction is demonstrated by in situ Fourier transform-infrared (FT-IR) spectra. Symmetric cells with the reduced PSFCM0.35 (R-PSFCM0.35) electrode exhibit a low polarization resistance of 0.43 Ω cm 2 at 850 °C. Single electrolysis cells with the R-PSFCM0.35 cathode display an outstanding current density of 2947 mA cm −2 at 850 °C and 1.6 V. In addition, the catalytic stability of the R-PSFCM0.35 cathode is also proved by operating at 800 °C with an applied constant current density of 600 mA cm −2 for 100 h.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Guanghui An,Heming Zheng,Lianshan Guo,Jingmei Huang,Congling Yang,Zhihao Bai,Nannan Wang,Wenhui Yang,Yanqiu Zhu
Tumors produce a hypoxic environment that greatly influences cancer treatment, and conventional chemotherapeutic drugs cannot selectively accumulate in the tumor region because of the lack of a tumor targeting mechanism, causing increased systemic toxicities and side effects. Hence, designing and developing new nanoplatforms that combine multimodal therapeutic regimens is essential to improve tumor therapeutic efficacy. Herein, we report the synthesis of ultrafine Cu nanoparticles loaded with a drug combination of cisplatin (Pt) and 1-methyl- d -tryptophan (1-MT) and externally coated with 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) photosensitizer, polydopamine (PDA) and CaO 2 of MIL-101(Fe) as a new nanoplatform (Cu@MIL-101@PMTPC). The nanoplatform synergistically combined chemodynamic therapy (CDT), photodynamic therapy (PDT), and immunochemotherapy. The Fe 3+ in MIL-101(Fe) and the surface Cu nanoparticles exhibited strong ability to consume intracellular glutathione (GSH), thereby generating a Fenton-like response in the tumor microenvironment (TME) with substantial peroxidase (POD)-like and superoxide dismutase (SOD)-like activities. In this design, we used the indoleamine 2,3-dioxygenase (IDO) inhibitor 1-MT to overcome chemotherapy-induced immune escape phenomena including enhanced CD8 + and CD4 + T cell expression, interferon-gamma (IFN-γ) and tumor necrosis factor-alpha (TNF-α) production, and accelerated immunogenic cell death. The targeted release of cisplatin loaded into Cu@MIL-101@PMTPC also reduced toxic side effects of chemotherapy. TCPP generated a large amount of singlet oxygen ( 1 O 2 ) upon specific laser irradiation to effectively kill tumor cells. CaO 2 on the outer layer generated oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) to ameliorate hypoxia in the tumor microenvironment, enhance the PDT effect, and provide a continuous supply of H 2 O 2 for the Fenton-like reaction. Thus, this nanocarrier platform exhibited a powerful chemodynamic, photodynamic, and immunochemotherapeutic cascade, providing a new strategy for cancer treatment.
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JOURNAL OF INORGANIC BIOCHEMISTRY
·
2024
·
IF 3.8
Kehua Wang,Ling Wang,Zhuye Shang,Xingzhi Yang,Hongmei Li,Xiaochun Wang,Mingchang Zhu,Qingtao Meng
Copper(II) complexes are very promising candidates for platinum-based anticancer agents. Herein, three Cu (II) complexes ( 1 – 3 ) containing 1,8-naphthalimide ligands were synthesized and characterized by FT-IR, elemental analysis, ESI-MS and single crystal X-ray diffraction (complex 3 ). In addition, a control compound (complex 4 ) without 1,8-naphthalimide ligand was synthesized and characterized. The in vitro anticancer activity of the synthesized complexes against five cancer cell lines and one normal cell line was evaluated by MTS assay. The results displayed the antitumor activity of complexes 1 – 3 was controlled by the aliphatic chain length of ligands, their cytotoxicity was in the order 3 > 2 > 1 , giving the IC 50 values ranging from 2.874 ± 0.155 μM to 31.47 ± 0.29 μM against five cancer cell lines. Complex 4 showed less activity in comparison with complex 1 – 3 . Notably, complexes 1 – 3 displayed much higher selectivity (SI = 2.65 to 10.16) compared to complex 4 (SI = 1.0), indicated that the introduction of 1,8-naphthalimide group not only increased the activity of this series of compounds but also enhanced their specific selectivity to cancer cells. Compound 3 induced apoptosis in cancer cells and blocked the S-phase and G2/M of cancer cells. The interaction with DNA of complexes 3 and 4 was studied by UV/Vis spectroscopic titrations, competitive DNA-binding experiment, viscometry and CD spectra. The results showed that complex 3 interacted with DNA in an intercalating mode, but the interaction mode of compound 4 with DNA was electrostatic interaction.
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WATER RESEARCH
·
2024
·
IF 11.4
Yao Li,Wenhong Fan,Xiaolong Yang,Shu Liu,Ying Wang,Wen-Xiong Wang
Cosmetics and personal care products containing titanium dioxide nanoparticles (TiO 2 NPs) may enter aquatic environments, where the surface coatings of TiO 2 NPs may change with aging due to environmental factors such as light, and potentially affect their bioaccumulation and toxicity. This study examined how aging impacted the physicochemical properties of three commercially available TiO 2 NPs and subsequent influence on the bioaccumulation and toxicity of copper (Cu) in Daphnia magna ( D. magna ). We demonstrated that aging significantly affected the hydrophobicity of TiO 2 NPs, which affected their binding to water molecules and adsorption of Cu. Changes of bioaccumulation of TiO 2 NPs and Cu in D. magna ultimately affected the activities of intracellular antioxidant enzymes such as SOD, CAT, GSH-Px, and the transmembrane protein Na + /K + –ATPase. Molecular docking calculations demonstrated that changes of activities of these biological enzymes were due to the interaction between TiO 2 NPs, Cu, and amino acid residues near the sites with the lowest binding energy and active center of the enzyme. Such effect was closely related to the hydrophobicity of TiO 2 NPs. Our study demonstrated the close relationship between surface properties of TiO 2 NPs and their biological effects, providing important evidence for understanding the behavior of nanomaterials in aquatic environments.
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JOURNAL OF FOOD COMPOSITION AND ANALYSIS
·
2024
·
IF 4
Kai Zhang,Dan Hou,Dongping Wu,Yanxia Li,Xuemei He,Tingting Sun,Jianhua Xiong,Xiaoning Liao
Accurate detection of benzimidazole pesticide thiophanate-methyl (TM) is of vital importance due to its harm to environmental safety and human health. Herein, for the first time, we developed a sensitive nonenzymatic electrochemical sensor for TM detection based on multiwall carbon nanotubes (MWCNTs) functionalized bimetallic iron−copper organic frameworks (Fe/Cu MOF). The synthesized nanocomposites showed excellent electro-oxidation ability to TM owing to the synergistic effect between MWCNTs and Fe/Cu MOF. Fe/Cu MOF enhanced the specific surface area for MWCNTs and MWCNTs improved the conductivity for Fe/Cu MOF, which resulted in a nanocomposite with abundant catalytical active sites and superior conductivity, greatly amplifying the detection signal for TM. Under optimized conditions, the proposed sensor based on the composite presented a wide linearity from 0.3 nM to 200 nM which is wider than that of currently reported methods and a very low detection limit (LOD) of 0.1 nM far lower than the maximum residue levels (MRLs) enacted worldwide. Furthermore, the sensor showed good reproducibility, long-term stability and high anti-interference. Moreover, the sensor can be successfully employed for the determination of TM in apple and cucumber with good recoveries (80.96 %–105. 5 %), highlighting its excellent potential as an alternative to traditional techniques.
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MICROCHIMICA ACTA
·
2025
·Vol. 192
·期 2
·1-11
·
IF 5.3
Zhang Xiaoyu,Sun Ruimeng,Zheng Haoran,Qi Yanfei
A spherical nucleic acid (SNA, AuNPs-aptamer) into CRISPR/Cas12a system combined with poly T-template copper nanoparticles as fluorescence reporter was fabricated to establish an amplification-free sensitive method for Staphylococcus aureus ( S. aureus ) detection. This method, named PTCas12a, utilizes the concept that the bifunction of SNA recognizes the S. aureus and triggers the Cas12a cleavage activity. Then, the Cas12a enzyme cleaves the Poly T40 to generate a signal change in Poly T-Cu fluorescence, indicating the presence or absence of the target bacteria. The PTCas12a platform demonstrated a detection limit as low as 3.0 CFU/mL (3 N/S) in a wide response range of 1.0 × 10 1 –1.0 × 10 6 CFU/mL for S. aureus detection, which holds significant potential in ensuring food safety and preventing the spread of diseases. Graphical abstract
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JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY
·
2024
·
IF 2.3
Xu Peng,Wang Shasha,Dai Wei,Shi Weishan,Xing Gang,Wang Zhaogui,Li Qun,You Chaoqun,Hao Dejun
Abstract Pesticides play a crucial role in modern agriculture, yet their widespread use poses a threat to the ecosystem by causing significant environmental damage. In an effort to address this issue, a novel nanopesticide delivery system was developed, utilizing a tannic acid (TA)-Cu combination deposited onto the surface of dendritic mesoporous silica nanoparticles (DMSNs). This innovative approach aims to enhance the efficiency of pesticide utilization. The process involved incorporating Tebuconazole (Teb) into DMSNs using the one-pot sol-gel method. Subsequently, a coating was applied through the sequential addition of TA and CuCl 2 to an aqueous dispersion of Teb@DMSNs. The resulting nanopesticide, named TA@Teb@DMSNs, exhibited a spherical shape and achieved an impressive Teb loading rate of nearly 26.6%. Kinetic studies on Teb release revealed that TA@Teb@DMSNs demonstrated characteristics conducive to controlled and sustained release. The adhesion quality of TA@Teb@DMSNs on Aesculus chinensis Bunge leaves was confirmed through a comparative study with Teb@DMSNs. Additionally, when compared to Teb suspension, TA@Teb@DMSNs exhibited superior antifungal activity against Fusarium esculenta wilt over an extended period. Consequently, the TA@Teb@DMSNs constructed in this research might be used as an efficient nanopesticide formulation for advancing the sustainable development of agriculture. Graphical Abstract A novel nanopesticide delivery system is prepared by depositing of tannic acid-Cu complex on dendritic mesoporous silica nanoparticles, which effectively improves the adhesion and effective time of pesticide on the leaf.
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JOURNAL OF HAZARDOUS MATERIALS
·
2024
·
IF 12.2
Jiabai Cai,Huan Li,Wenjia Huang,Shuting He,Kai Feng,Masaki Takaoka
Biogas slurry, an inevitable outcome of anaerobic digestion (AD), is a treatment burden for urban environmental management. In this study, two kinds of biogas slurry (slurry J and slurry C), collected from the AD plants in Japan and China, were treated using novel TiZrO 4 @Cu and TiZrO 4 @Cu@SiO 2 multilayered hollow spheres containing Cu sub-nanoclusters as the catalyst. The results showed that the chemical oxygen demand (COD) was removed by 63 % for slurry J and 44 % for slurry C after 5 h. The Cu sub-nanoclusters acted as co-catalysts and active centers, facilitating rapid electron transfer to oxygen molecules and forming highly reactive •O 2 − and •OH species (Use slurry J as the based solution). These free radicals cleaved the interconnecting bonds between benzene rings, disintegrated the ring structure, formed intermediate compounds such as n-hexylic acid, and ultimately mineralized organic pollutants in biogas slurry into CO 2 and H 2 O. At the same time, TiZrO 4 @Cu@SiO 2 had excellent stability due to the protection of the SiO 2 shell and reduced threefold Cu leaching than TiZrO 4 @Cu. The COD removal rate was always 60 % in six cycles in the slurry J. The new catalyst ensured the high performance of catalytic air oxidation at low temperatures, which has significant potential as an environmentally friendly and energy-saving method for organic wastewater treatment.
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