ACS Nano
·
2025
·
IF 16
Hui Wang,Weitao Yang,Yan Xu,Weiwei Zeng,Dinghua Liu,Tianming Cui,Yanjing Yun,Chang Liu,Zhuoyao Wu,Bingbo Zhang
Monovalent copper (Cu(I)) drives cuproptosis and catalytic therapy, yet its rapid oxidation reduces the activity. We developed bioinspired Cu(I)-bovine serum albumin single-atom nanozymes (Cu(I)-BSA SAzymes) via mild biomineralization, achieving stability (>90 days) and dual enzyme-like activities (peroxidase (POD)/catalase (CAT)) to convert tumor H2O2 into cytotoxic reactive oxygen species (ROS) while alleviating hypoxia. These SAzymes deplete glutathione to amplify oxidative stress and release Cu(I), which aggregates dihydrolipoamide S-acetyltransferase (DLAT) to induce cuproptosis─distinct from apoptosis/ferroptosis. Mechanistically, transcriptomics analyses suggest that Cu(I)-BSA SAzymes exerted their effects by regulating the oxidative stress and energy metabolism in 4T1 cells. The tumor microenvironment further mediates SAzymes aggregation and in situ transformation into paramagnetic Cu(II), enabling self-amplified T1-weighted MRI contrast for real-time activation monitoring. In breast (4T1) and colon (CT26) tumors, Cu(I)-BSA SAzymes suppress growth by 68.8% and 80.3% ([Cu] = 4 mg kg–1). This study reports a stable Cu(I) platform for catalytic-plus-cuproptosis theranostics.
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高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2025
·Vol. 39
·期 9
·e70348
·
IF 0
Yongguang Wang,Yi Pei,Siqi Hu,Chunxin Lu,Wei Zhong,Zhiyin Xiao,Junjie Wang,Xiaoming Liu
In this work, the preparation and characterization of a composite of Cu-Cu 2 O with g-C 3 N 4 and its application in the catalysis of aerobic oxidation of benzylic alcohols are reported. The composites Cu-Cu 2 O/g-C 3 N 4 were prepared starting with CuSO 4 under reduction conditions with ball milling, followed by thermal treatment. The introduction of g-C 3 N 4 into the composite can enhance the catalytic oxidation. Band structure analysis based on UPS data reveals that the enhancement can be attributed to the small work function of g-C 3 N 4 , which raises the VBM level of the chief catalyst Cu 2 O through injecting electrons into the oxide at the heterojunction due to Fermi energy alignment. Both VBM ascending and forming an internal electric field (IEF) due to the electron transfer across the interface contribute to the enhancement in the catalysis. Further, the N-rich matrix g-C 3 N 4 promotes proton transfer in the catalysis due to its basicity, which also accelerates the catalysis.
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EUROPEAN POLYMER JOURNAL
·
2024
·
IF 5.8
Lingshan Li,Qian Zhou,Jingyi Zhao,Yuangong Zhang,Zhaolei Jia,Xuan Liu,Hailei Zhang,Xinwu Ba,Libin Bai
Multiblock copolymer macrochain-transfer agents (MBP-CTAs) can be used to synthesize MBPs in one pot via reversible addition-fragmentation chain-transfer (RAFT) polymerization. MBP-CTAs can be efficiently synthesized via a copper-catalyzed azide-alkyne cycloaddition reaction. However, traditional purification methods cannot sufficiently purify MBP-CTAs, resulting in the failure of RAFT. In this study, it was discovered that using a supported catalytic system, namely, Cu@A-HNTs, inhibited the connection between Cu and S. The residual Cu content in the MBP-CTA was successfully reduced to a low level (7.88 µg/mg). Then, hydrophilic and hydrophobic MBPs were synthesized through RAFT polymerization using the MBP-CTAs. Subsequently, multiblock copoly(methyl methacrylate-b-butyl methacrylate-CTA)s (PMMA-b-PBMA-c-CTA)s were successfully prepared. The MBP-CTAs and MBPs were characterized using ultraviolet–visible spectroscopy, 1 H nuclear magnetic resonance, size-exclusion chromatography, matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry, differential scanning calorimetry measurements and uniaxial tensile tests. The results of performance testing of PMMA-b-PBMA-c-CTAs demonstrated that their fracture stress and strain significantly increased comparing with that of PMMA-b-CTAs.
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JOURNAL OF MOLECULAR LIQUIDS
·
2024
·
IF 5.3
Jue Chen,Hexiang Zhong,Shan Zhu
In this study, the selectivity of a hydrophobic deep eutectic solvent (HDES) comprising 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (P507) and L-menthol (Men) was assessed for the extraction and separation of Cu(II), Co(II), and Ni(II) from acidic leaching solutions, aiming to make the HDES system more consummate and provide a novel approach for metal extraction using HDES. The results indicated that under the conditions of a 2:1 M ratio of P507 to Men, an extraction temperature of 40℃, an extraction time of 40 min, an oil-water ratio(O/W, v/v) of 1, and a pH value of 4, the three-stage cross-flow extraction efficiency of the HDES for Cu(II) was over 99 %. Furthermore, successful selective separation of Cu(II), Ni(II), and Co(II) was demonstrated by separation coefficients β Cu/Ni of 2150 and β Cu/Co of 305. Molecular dynamics (MD) simulations and density functional theory (DFT) indicated that the formation of an HDES molecule involved the combination of two molecules of P507 and one molecule of Men through hydrogen bonding interactions. Moreover, compared to other cupric complex configurations, the tetrahedral cupric complex, synthesized using two molecules of P507 and two molecules of menthol with Cu(II), exhibited a lower single-point energy and a higher ΔE(LUMO-HOMO), demonstrating greater stability.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Yuanyuan Zhang,Jingchen Hao,Zhenyu Wang,Jiahao Cui,Yongfang Rao,Wei Yan
This study prepared Cu-doped ZnFe₂O₄ (Cu-ZFO) for peroxymonosulfate (PMS) activation, achieving 94% primidone (PMD) removal in 30 min, much higher than ZnFe₂O₄ (20%) due to the introduction of oxygen vacancies and Cu-enhanced Fe catalytic activity. Kinetic analysis revealed reaction orders of 1.25, 1.2, and 0.22 with respect to Cu-ZFO, PMS, and PMD, respectively. Electron transfer pathway (ETP) and free radical oxidation were believed to be involved in the degradation of various organic contaminants in Cu-ZFO/PMS system under neutral conditions through radicals quenching experiments, EPR measurements, electrochemical measurements, and Density functional theory (DFT) calculations. The dominant oxidation pathway for organic contaminants is dependent on their molecular structure and the solution pH. This study provides new insights into PMS activation mechanisms and signals attention to researchers and engineers about the potential influence of molecular structure and pH on oxidation pathways of organics during wastewater treatment using metal oxide-activated PMS.
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JOURNAL OF FLUORESCENCE
·
2025
·
IF 3.1
Wu Mengying,Huang Xiyang,Li Zhouquan,Gan Xiang,Zheng Yumei,Tang Hui,Xiong Jingwei,Yang Xiaoli,Yang Dongye,Zhang Lizhen,Liang Weiyuan,Li Hongtao
Bio-based fluorescent carbon dots (CDs) have emerged as promising material for advanced sensing applications due to their exceptional sensitivity, stability and biocompatibility. However, it was till constrained by ion selectivity and solution suitability especially in physiological solutions (e.g., PBS). Herein, a novel nitrogen-doped carbon dots (N-CDs) fluorescence quenching sensor derived from Siraitia grosvenorii (named “Luo Han Guo” in China) residue was developed for selective determination of trace Cu(II) ions in different solutions. The N-CDs were synthesized through a one-step hydrothermal process utilizing agricultural waste as carbon precursor and urea as the nitrogen source, demonstrating an eco-friendly synthesis strategy. The developed sensor exhibited remarkable anti-interference capability against acid, base, salt and various metal ions while maintaining excellent photostability and biocompatibility (cell viability > 75% at 1000 ug/mL). With a limit of detection (LOD) of 0.13 µmol/L, the system showed superior sensitivity compared to conventional methods. Furthermore, the sensor demonstrated strong universality across solution types and, more importantly, suitability for trace Cu²⁺ quantification in physiological solutions. Experimental results demonstrated that the fluorescence quenching process resulted from the binding of Cu²⁺ to amino groups on CDs, forming complexes through a non-radiative photoinduced electron transfer (PET) mechanism. This PET effect synergizes with static quenching, underlying the high selectivity and sensitivity of N-CDs for Cu²⁺ detection. The integration of novel phytochemical-based sensing materials with a fluorescence quenching mechanism enables highly selective detection of trace Cu²⁺ for environmental and biomedical applications.
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高影响因子
ChemSusChem
·
2024
·
IF 7.5
Qiuping Zhou,Xinyuan Jiang,Xuecheng Zhang,Dawei Wang,Guang Yang,He Zhou,Yuchao Wu,Fang Guo,Ming Chen,Guowang Diao,Lubin Ni
Graphical A Polyoxomolybdate-based metal-organic framework-derived Cu-embedded molybdenum dioxide hybrid nanoparticles was first applied as sulfur host in aluminum-sulfur batteries to resolve remaining critical challenge of polysulfide shuttle effect. The pouch cell with Cu/MoO 2 @C cathode cycled at 100 mA g −1 exhibits an initial discharge capacity of 150 mAh g −1 and maintains 100 cycles. High-performance rechargeable aluminum-sulfur batteries (RASB) have great potential for various applications owing to their high theoretical capacity, abundant sulfur resources, and good safety. Nevertheless, the practical application of RASB still faces several challenges, including the polysulfide shuttle phenomenon and low sulfur utilization efficiency. Here, we first developed a synergistic copper heterogeneous metal oxide MoO 2 derived from polymolybdate-based metal-organic framework as an efficient catalyst for mitigating polysulfide diffusion. This composite enhances sulfur utilization and electrical conductivity of the cathode. DFT calculations and experimental results reveal the catalyst Cu/MoO 2 @C not only effectively anchors aluminum polysulfides (AlPSs) to mitigate the shuttle effect, but also significantly promotes the catalytic conversion of AlPSs on the sulfur cathode side during charging and discharging. The unique nanostructure contains abundant electrocatalytic active sites of oxide nanoparticles and Cu clusters, resulting in excellent electrochemical performance. Consequently, the established RASB exhibits an initial capacity of 875 mAh g −1 at 500 mA g −1 and maintains a capacity of 967 mAh g −1 even at a high temperature of 50 °C.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Zeyun Yang,Hao Guo,Zhiguo Yu,Mingyue Wang,Xiaoqin Wei,Zongyan Lu,Lei Sun,Henglong Ren,Wu Yang
As a vital biological polypeptide molecule, glutathione (GSH) is involved in the regulation of various life activities. Accurate and sensitive detection of GSH in human body is of great significance for the preliminary diagnosis of related diseases. In this research, Cu(II) modified TADH COF, which has been prepared by Cu 2+ post-synthesis modification of the COF obtained through a condensation reaction of 1,3,5-(4-aminophenyl) benzene (TAPB) and 2,5-dihydroxy-1,4-benzenedicarboxaldehyde (DHTP), and methylene blue (MB) molecules are combined to construct a ratiometric electrochemical sensor for achieving specific and ultra-sensitive detection of GSH. As a stable and active covalent organic framework material, TADH COF possesses the special O(–OH) and N(C N) binding sites, which can load and coordinate with Cu 2+ effectively. The obtained Cu(II)-TADH COF serves as a sensitive electrode material for sensing GSH due to “extrusion effect” caused CuCl solid-state electrochemical signal degeneration by the specific binding of Cu and GSH while MB provides a stable electrical signal in the electrochemical sensing process as an internal reference for eliminating errors and making the detection results more accurate. The constructed electrochemical sensing platform Cu(II)-TADH COF/MB/GCE exhibited an ultrahigh sensitivity with a limit of detection (LOD) of 0.0093 nM (S/N = 3), wide linear range of 0.05 nM–40 μM and high accuracy. For the detection of GSH in real samples including human blood, serum and urine samples, the sensor also showed excellent sensing performance. This is the first research on ratiometric electrochemical sensing platform for the ultra-sensitive detection of glutathione based on covalent organic frameworks, which provides an original and novel strategy for the electrochemical detection of GSH with COF materials.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Yunshuo Zhu,Lili Guan,Xiwen Song,Yarong Huang,Ming Li,Qingxian Zhang,Ruihua Guo
Strict control of carbon emissions is crucial for expediting the achievement of carbon neutrality. However, the current CO 2 RR electrocatalytic exhibits numerous shortcomings that impede the enhancement of catalytic activity. Issues such as lengthy catalyst preparation times, and high levels of precious metal content. Additionally, the aggregation of ultrafine nanoparticles contributes to a rapid deterioration in catalytic performance. Herein, a Joule-heating method is efficiently utilized to synthesize heterostructures nano-catalysts for CO 2 electroreduction on carbon cloth substrates. This method takes advantage of the thermoelectric coupling of the carbon cloth to achieve carbothermal reduction, while also regulating phase composition and introduction of oxygen vacancies. The Cu-CeO 2 /TiO 2 /CC catalyst synthesized in this method showed a current density in CO 2 of −32 mA·cm −2 at −1.0 V (vs. RHE). Notably, this catalyst demonstrated high CO selectivity and Faraday efficiency (FE CO ) of up to 82.5 % at a low potential of −0.3 V (vs. RHE). Optimal electrochemical performance is achieved at a power of 40 W. The ultra-fast temperature change process prevented the agglomeration of catalyst particles and facilitated the construction of a stable heterogeneous interface with a high oxygen vacancy concentration. In conclusion, this study presents a promising approach, particularly for the rapid preparation of low-cost, highly selective non-precious metal electrocatalysts.
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高影响因子
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
·
2024
·Vol. 149
·期 12
·6007-6019
·
IF 3
Li Haijian,Chen Chao,Xu Yi,Qin Zhao,Xie Xiao,Yao Ergang,Xu Siyu,Qu Wengang,Yi Jianhua,Zhao Fengqi
The intense exhaust plumes of the CMDB propellants can be suppressed by the containing potassium salts, but the potassium compounds increased remarkably the combustion pressure exponent of propellants, destroying the combustion plateau effects and resulting in the combustion instability of the rocket motors, so it is critical to reveal the reaction mechanisms of the potassium salts during the combustion process of propellants. In the work, the influence of three potassium hexanitro complexes, K 2 Pb[ M (NO 2 ) 6 ] ( M = Co, Cu, Ni), on the ignition and combustion properties, especially pressure exponent, of solid propellants has been investigated by using the laser ignition apparatus, burning rate instrument, combustion wave temperature, flame morphology, quenched surface, and emission spectrometer. When the hexanitro complexes replaced the β -Pb, the ignition delay time of the propellants was shorter at the low laser flux. The study on the combustion properties showed that the burning rate and pressure exponent of propellant containing K 2 Pb[Cu(NO 2 ) 6 ] was extremely close to the basic propellant ( β -Pb) due to similar temperature gradient until ~ 1942 °C. The flat combustion cross section on the flame morphology of the propellant containing K 2 Pb[Cu(NO 2 ) 6 ] was found to favor the low-pressure exponent. The carbon skeleton, metal agglomerations, and K release identified by using the quenched surface and emission spectra were closely related to the response characteristics of the combustion pressure exponent of the propellants due to the influence of different hexanitro complexes. The relationship between the burning rate of the propellants and the maximum self-heating rate of the mixtures containing the propellant energetic oxides and hexanitro complexes was also revealed, which can predict the relative burning rate for the same propellant system. More importantly, the reasons for the deterioration of the combustion pressure components due to flash suppressors were elucidated clearly from the experimental results and theoretical analysis, which involve three destroying mechanisms: (i) catalytic metals “poison,” (ii) carbon skeleton disappearance, and (iii) high thermal decomposition temperature of potassium compounds. The study also revealed the inhibition mechanism of potassium flash suppressors on the catalytic properties of catalysts during the combustion process of the CMDB propellants. Graphical abstract The influence of three potassium hexanitro complexes on the ignition and combustion properties of solid propellants have been investigated, and the reasons for the deterioration of the combustion pressure components due to flash suppressors were elucidated clearly.
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CERAMICS INTERNATIONAL
·
2025
·
IF 5.6
Yuanzhe Li,Ran Long,Jingmei Tao,Xiaofeng Chen,Yichun Liu,Caiju Li,Zunyan Xu,Jianhong Yi
On the premise of ensuring the structural integrity of reinforcement, optimizing the microstructure of interfaces can be an effective method to improve the comprehensive performance of composites. In this study, carbon nanotubes (CNTs) were pre-coated with ammonium metatungstate, and methane was utilized as carbon source for the creative synthesis of WC nanoparticles on intact CNTs (WC@CNTs) through chemical vapor deposition. The WC@CNTs/Cu composites were prepared by regulating the morphology and distribution of WC on CNTs through powder metallurgy. The results demonstrated a significant enhancement of dispersion uniformity of WC@CNTs within Cu matrix. A specific orientation relationship was observed between WC and CNTs as well as Cu, namely ( 111 ) Cu ∥ ( 001 ) WC and ( 100 ) WC ∥ ( 002 ) CNTs , indicating that the introduction of interfacial WC can achieve robust interfacial bonding. This not only effectively enhanced the load transfer capacity of WC@CNTs by restraining interfacial sliding, but also improved the fracture toughness of the composite through crack deflection and bifurcation. The tensile strength of the WC@CNTs/Cu composite reached 272 MPa, exhibiting a 24.8 % and 18.3 % increase compared to that of pure Cu and CNTs/Cu composite, while maintaining a fracture elongation of 29.4 %. Furthermore, the robust interface bonding can also enhance the electrical and thermal conductivity of the composites by reducing interface scattering. The highest electrical and thermal conductivity of WC@CNTs/Cu composites was 95.9 ± 0.7 %IACS and 390 ± 7 W/mK, respectively, which was 1.9 % and 17.8 % higher than that of CNTs/Cu composite. The method employed in this study can offer valuable insights for interface optimization of nanocarbon reinforced metal matrix composites.
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高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Zhishuncheng Li,Yongheng Yuan,Guangfei Qu,Keyi Xiang,Ping Ning,Wanyuan Du,Keheng Pan,Yingying Cai,Junyan Li
Catalysts for the generation of methane in electrochemical CO 2 reduction reactions (CO 2 RR) must have suitable adsorption energies for the intermediate products. In this study, we used a one-step electrodeposition method to prepare nitrogen(N) and phosphorus(P)-doped copper(Cu)-based catalysts. The introduction of P to the catalyst resulted in a significant change in the CO 2 RR pathway, leading to efficient and highly selective methane production. The Cu-N 2 -P 2 electrocatalyst exhibits a CH 4 Faradaic efficiency (FE) of 73 % at a potential of −1.6 V vs RHE, and it was found to be more effective in promoting the hydrogenation process of *CHO-*CH 2 O-*CH 3 O, which was confirmed by in-situ IR, X-ray absorption techniques and DFT calculations. P serves as the primary electron donation site in the catalyst, thereby influencing the charge distribution properties of the surrounding Cu atoms. This, in turn, facilitates the regulation of intermediate adsorption, representing the primary factor in the notable enhancement of methane selectivity.
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