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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

GAA/(Au–Au/IrO2)@Cu(PABA) reactor with cascade catalytic activity for α-glucosidase inhibitor screening

Yingying Zhong,Qing Wang,Zi-Jian Chen,Hongwu Wang,Suqing Zhao

Background In vitro screening strategies based on the inhibition of α-glucosidase (GAA) activity have been widely used for the discovery of potential antidiabetic drugs, but they still face some challenges, such as poor enzyme stability, non-reusability and narrow range of applicability. To overcome these limitations, an in vitro screening method based on GAA@GOx@Cu-MOF reactor was developed in our previous study. However, the method was still not satisfactory enough in terms of construction cost, pH stability, organic solvent resistance and reusability. Thence, there is still a great need for the development of in vitro screening methods with lower cost and wider applicability. Results A colorimetric sensing strategy based on GAA/(Au–Au/IrO 2 )@Cu(PABA) cascade catalytic reactor, which constructed through simultaneous encapsulating Au–Au/IrO 2 nanozyme with glucose oxidase-mimicking and peroxidase-mimicking activities and GAA in Cu(PABA) carrier with peroxidase-mimicking activity, was innovatively developed for in vitro screening of GAA inhibitors in this work. It was found that the reactor not only exhibited excellent thermal stability, pH stability, organic solvent resistance, room temperature storage stability, and reusability, but also possessed cascade catalytic performance, with approximately 12.36-fold increased catalytic activity compared to the free system (GAA + Au–Au/IrO 2 ). Moreover, the in vitro GAA inhibitors screening method based on this reactor demonstrated considerable anti-interference performance and detection sensitivity, with a detection limit of 4.79 nM for acarbose. Meanwhile, the method owned good reliability and accuracy, and has been successfully applied to the in vitro screening of oleanolic acid derivatives as potential GAA inhibitors. Significance This method not only more effectively solved the shortcomings of poor stability, narrow scope of application, and non-reusability of natural enzymes in the classical method compared with our previous work, but also broaden the application scope of Au–Au/IrO 2 nanozyme with glucose oxidase and peroxidase mimicking activities, and Cu(PABA) carrier with peroxidase mimicking activity, which was expected to be a new generation candidate method for GAA inhibitor screening.

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JOM · 2024 · IF 2.1

Galvanic Couple-Induced Depression Effect with Clean and Efficient Regulation Regime of Cu-Mo Separative Flotation

Lei Shan,Wu Jiaxing,Miao Yu,Guo Bao

It is difficult to depress secondary copper sulfide minerals in the separative flotation of copper–molybdenum coexisting ores with a huge NaHS consumption, and causing serious safety and environmental problems. Galvanic interaction between active metallic granular (low consumption depressant; LCD) and secondary copper sulfide mineral particles can induce surface passivation, thereby depressing its floatability and achieving clean and efficient regulation of copper molybdenum separation. The use of 10% LCD was applied at the first stage and 5 kg/t NaHS at the second stage can recover 89.71% of Cu, while only 52.89% of Cu can be recovered for single stage flotation where 20 kg/t NaHS was used without any presence of LCD. To avoid the negative effect of Mg(OH) 2 colloids at higher pH at the second stage, sodium hexametaphosphate (SHMP) was added as a dispersant and Mo recovery could be pulled up to 89.63%.

CAS / MDL: 10124-56-8 7757-82-6
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

In-situ surface modified water-soluble Cu nanoparticles as lubrication additives in water-based cutting fluids

Keying Hua,Yongjia Shi,Miaomiao Tang,Xiangyu Zuo,Jun Gao,Xia Zhang

Water-based lubricants are essential in the field of tribology , and the application of nanoparticles as additives in water-based lubricants shows promise and significant practical importance. In this study, water-soluble Cu nanoparticles modified with methoxypolyethyleneglycol xanthate long-chain polymers were fabricated by a in-situ surface modification method. The tribological behavior of the Cu nanoparticles synthesized as additives in a water-PEG system was evaluated using a universal micro-tribotester. It was found that the synthesized nanoparticles could be stably dispersed in the water-PEG system and could enhance the tribological properties and load-carrying capacity of the system significantly. For example, the coefficient of friction could be reduced to 0.052, and the P B value increased to 588 N when the Cu nanoparticles were added at a mass fraction of 1.5 %. This was mainly attributed to the formation of a boundary lubrication film consisting of Cu, Fe 2 O 3 , Fe 2 (SO 4 ) 3 , and FeS throughout the entire friction process. The boundary film effectively prevents direct contact between the friction surfaces, thereby improving the tribological properties. The incorporation of Cu nanoparticles as additives into commercial cutting fluids resulted in a lower coefficient of friction and significantly enhanced the extreme pressure performance of the cutting fluids, demonstrating promising application prospects.

CAS / MDL: 9004-74-4
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ACS Catalysis · 2024 · IF 11.3

Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO2 Reduction

Yuheng Ma,Yu Zhang,Guanshun Xie,Zhaohui Huang,Linfen Peng,Changqiang Yu,Xiuqiang Xie,Shuanglin Qu,Nan Zhang

Doping engineering has enabled the construction of homogeneous and abundant atomic-level catalytic sites for photocatalytic CO2 reduction with improved selectivity for the target product. However, little is known about the effect of the spatial position of the heteroatoms on the photocatalytic activity of the semiconductors toward CO2 reduction. Herein, uniform Cu doping into the bulk phase of hollow CdS cubes (HCC) and Cu doping onto the surface of HCC, denoted as Cu/HCC and HCC@Cu, respectively, are prepared by tuning the introduction order of Cu sources. Experimental analysis shows that the introduction of Cu by both methods can promote the separation and migration of photoinduced charge carriers in CdS. Notably, Cu doping onto the surface of CdS in HCC@Cu leads to much better proton reduction to H2 production performance but lower CO2 reduction efficiency as compared to bare CdS. In sharp contrast, Cu doping into the bulk phase of CdS enhances the CO2-to-CO conversion while mitigating H2 evolution. This should be ascribed to the smaller overpotential of Cu/HCC in the CO2 saturated system than that in the Ar system. In addition, doping Cu atoms into the bulk phase of CdS shifts the d band center of Cu/HCC upward to near the Fermi energy level, which promotes the adsorption and activation of CO2 on CdS. These results indicate that the photoelectrons with a prolonged lifetime in Cu/HCC preferably reduce CO2 molecules rather than protons. The density functional theory (DFT) calculation results show that the introduction of Cu heteroatoms can promote the desorption of CO*, and the adaptable sulfur vacancies (Vs) produced by in situ doping techniques can stimulate the formation of CO* intermediates, resulting in the high performance of photocatalytic CO2 reduction to CO. This work reveals the effect of different heteroatom doping locations on the catalytic activity and will provide a reference for the design of efficient photocatalysts with atomic-level fine structure.

CAS / MDL: 13778-31-9
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Journal of Environmental Sciences · 2024 · IF 5.9

Insight into catalytic performance and reaction mechanism for toluene total oxidation over Cu-Ce supported catalyst

Xuan Liang,Jin Zhang,Juntai Tian,Zenghua Xie,Yue Liu,Peng Liu,Daiqi Ye

Herein, three supported catalysts, CuO/Al 2 O 3 , CeO 2 /Al 2 O 3 , and CuO-CeO 2 /Al 2 O 3 , were synthesized by the convenient impregnation method to reveal the effect of CeO 2 addition on catalytic performance and reaction mechanism for toluene oxidation. Compared with CuO/Al 2 O 3 , the T 50 and T 90 (the temperatures at 50% and 90% toluene conversion, respectively) of CuO-CeO 2 /Al 2 O 3 were reduced by 33 and 39 °C, respectively. N 2 adsorption-desorption experiment, XRD, SEM, EDS mapping, Raman, EPR, H 2 -TPR, O 2 -TPD, XPS, NH 3 -TPD, Toluene-TPD, and in-situ DRIFTS were conducted to characterize these catalysts. The excellent catalytic performance of CuO-CeO 2 /Al 2 O 3 could be attributed to its strong copper-cerium interaction and high oxygen vacancies concentration. Moreover, in-situ DRIFTS proved that CuO-CeO 2 /Al 2 O 3 promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene. This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.

CAS / MDL: 10294-41-4 10031-43-3
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JOURNAL OF MOLECULAR LIQUIDS · 2025 · IF 5.2

In situ self-assembled Ti-MOF@Cu with enzyme activity for colorimetric sensing of sulfur ions

Xiupei Yang,Hanyu Yang,Die Deng,Yujie Kang,Yuxiu Fan,Ya Wang

Copper (Cu) nanoparticles have been widely used as catalysts for colorimetric assays. The challenge in developing Cu nanoparticles is to design nanomaterials with high catalytic activity and stability. Herein, a series of NH 2 -MIL-125(Ti)@Cu (Ti-MOF@Cu) composites with enzyme activity were obtained by in situ growth of different proportions of copper on titanium-based metal organic frameworks (Ti-MOFs), among which [email protected] showed the highest enzyme activity. Electron transfer at the interface of Ti-MOF and Cu promoted the decomposition of hydrogen peroxide (H 2 O 2 ) to generate active species under near-neutral conditions, thereby oxidizing colorless TMB to blue oxidized TMB (ox-TMB). On this basis, a sulfide ion (S 2− ) detection method based on a [email protected] colorimetric sensor was constructed, in which the limit of detection (LOD) was 0.16 μM in the linear range of 0.5–30 μM. Furthermore, [email protected] was successfully used for detecting S 2− in water samples. The successful synthesis of Ti-MOF@Cu provides new insights for further study of the enzyme-like activity of copper-based materials, and the constructed facile and sensitive sensor system has broad application prospects.

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Journal of Energy Chemistry · 2024 · IF 14

In-situ electrochemical interface of Cu@Ag/C towards the ethylene electrosynthesis with adequate *CO supply

Haotian Duan,Wenyang Li,Lixiu Ran,Fulong Zhu,Tianxiang Li,Ming Miao,Wen-jin Yin,Xin Wang,Yongzhu Fu

The conversion of carbon dioxide to ethylene by electrochemical reduction (CO 2 RR) provides a new strategy for achieving carbon dioxide conversion. However, copper-based catalysts have the disadvantages of unsatisfactory selectivity and low current density, which limit the potential CO 2 RR industrial expansion. Researches have verified that the real reaction sites at the catalyst surface often undergo reconstruction during the reaction, therefore, understanding and utilizing this phenomenon is crucial for improving catalytic performance. In this work, we introduced additional Ag component into Cu@Ag/C tandem catalyst by in-situ electrochemical reconstruction of Cu 2 CO 3 (OH) 2 /AgCl/C precursor. This electro-reduced catalyst exhibits a C 2 H 4 Faradaic efficiency of 50.41% in H-cell, and 58.03% in the flow cell, surpassing the counterparts of pure Cu and Ag, as well as the Cu-Ag homolog with separated interface. Moreover, it also provides a long-term stability of 21 h with the ethylene Faraday efficiency (FE) over 50%. The appropriate amount of Ag dopant into the Cu catalyst changes the electronic structure of Cu surface by the electron transfer from Cu to Ag, which distinctly enhances the binding energy of CO 2 on the catalyst. Meanwhile, in-situ Raman results and theoretical calculation reveal that the introduction of silver increases the number of active sites and improves the coverage of *CO intermediate, thereby accelerating the kinetics of C–C coupling and reducing its energy barrier. The combination of cascade catalytic strategy and in-situ electroreduction interface provides potential applications for future artificial carbon balance.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Low-temperature CO preferential oxidation in H2-rich stream over Indium modified Pd-Cu/Al2O3 catalyst

Lijun Yue,Wanjun Zhao,Jinfang Li,Ruifang Wu,Yongzhao Wang,Hongxi Zhang,Yongxiang Zhao

The impact of Indium (In) doping upon the catalytic performance of Pd-Cu/Al 2 O 3 for carbon monoxide preferential oxidation (CO-PROX) in hydrogen (H 2 ) rich atmosphere at low temperature has been studied. A series of catalysts with extremely low palladium (Pd) loading (0.06 wt%) are synthesized by the facile co-impregnation method. When the In/copper (Cu) atomic ratio equals 0.25, Pd-Cu-In 0.25 /Al 2 O 3 can keep 40% CO conversion and 100% carbon dioxide (CO 2 ) selectivity at least 120 min at 30 °C, which is significantly superior to the catalytic performance of Pd-Cu/Al 2 O 3 . The elaborate characterization findings reveal that the added In species to Pd-Cu/Al 2 O 3 causes Indium oxide (In 2 O 3 ) to generate, which produces the interaction of In 2 O 3 with Pd-Cu/Al 2 O 3 , further promoting the dispersion of copper chloride hydroxide (Cu 2 Cl(OH) 3 ). Moreover, the modification of In facilitates the re-oxidation of Pd 0 to Pd + through reducing the formation of palladium hydride (PdH x ) during the CO-PROX reaction. Meanwhile, the addition of In leads to the decrease of Cu + electron cloud density, making it easier to be oxidized to Cu 2+ . Collectively, the easy re-oxidation of Pd 0 and Cu + is favorable to fulfill the Wacker cycle between Pd and Cu species, thus improving the catalytic performance for CO-PROX.

CAS / MDL: 10125-13-0
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Cu–Tremella fuciformis polysaccharide–based tumor microenvironment–responsive injectable gels for cuproptosis-based synergistic osteosarcoma therapy

Chao Xie,Qili Sun,Jingle Chen,Bingsheng Yang,Huiwen Lu,Zhanpeng Liu,Yucong Li,Kai Li,Bin Tang,Lijun Lin

Cuproptosis affects osteosarcoma locally, and the exploitation of cuproptosis-related biomaterials for osteosarcoma treatment is still in its infancy. We designed and synthesized a novel injectable gel of Cu ion–coordinated Tremella fuciformis polysaccharide (TFP–Cu) for antiosteosarcoma therapy. This material has antitumor effects, the ability to stimulate immunity and promote bone formation, and a controlled Cu 2+ release profile in smart response to tumor microenvironment stimulation. TFP–Cu can selectively inhibit the proliferation of K7M2 tumor cells by arresting the cell cycle and promoting cell apoptosis and cuproptosis. TFP–Cu also promoted the M1 polarization of RAW264.7 cells and regulated the immune microenvironment. These effects increased osteogenic gene and protein expression in MC3T3-E1 cells. TFP–Cu could significantly limit tumor growth in tumor-bearing mice by inducing tumor cell apoptosis and improving the activation of anti-CD8 T cell-mediated immune responses. Therefore, TFP–Cu could be a potential candidate for treating osteosarcoma and bioactive drug carrier for further cancer-related applications.

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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Cu single atoms mediated multiple active site reconfiguration to trigger Dual-pathway nonradical peroxymonosulfate activation process

Deyu Qin,Chen Zhang,Fanzhi Qin,Yin Zhou,Danlian Huang,Hou Wang,Hanzhuo Luo,Qi Wang,Lin Tang,Wenwei Li

Developing atomically dispersed metal sites is vital to enhance the activation of peroxymonosulfate (PMS). However, for catalyst systems where single atoms and nanoclusters coexist, how to identify the independent and synergistic effects of atomic sites and investigate the possible coexistence of multiple activation mechanisms still remains a great challenge. Herein, Cu SA /CoO x -CeO 2 catalysts with Cu single atoms and CoO x nanoclusters were fabricated for PMS activation. The introduction of Cu single atoms led to the reconstruction and diversification of catalytic active sites of CoO x -CeO 2 . The synergy between CoO x nanoclusters and neighboring Cu single atoms in Cu SA /CoO x -CeO 2 catalyst led to the 1 O 2 pathway of PMS activation, while the isolated Cu atom induced the Cu(III) oxidation pathway. The introducing of adjacent Cu single atoms caused the redistribution of the site charges in CoO x nanoclusters, which enhanced the charge transfer and promoted the adsorption and activation behavior of PMS molecules. During the evolution of 1 O 2 , the synergistic effect of Cu single atoms and CoO x nanoclusters increased the stability of the reaction intermediate state (*OO*SO 3 ), reducing the total Gibbs free energy change (ΔG) required for 1 O 2 formation. Compared with the cooperative site, the isolated Cu-O4 sites exhibited stronger charge transfer capacity to PMS molecules and were more conducive to the activation of the local substrate electronic structure, facilitating the formation and stabilization of Cu(III)–OH metastable intermediates. Overall, this study demonstrated the importance about the construction of multi-site induced multipath coexisting PMS activation system and the accurate identification of active sites.

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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

An origami microfluidic paper device based on core-shell Cu@Cu2S@N-doped carbon hollow nanocubes

Yuanyuan Li,Huinan Chen,Rong Huang,Dongmei Deng,Xiaoxia Yan,Liqiang Luo

Backgroud The global prevalence of diabetes mellitus, a serious chronic disease with fatal consequences for millions annually, is of utmost concern. The development of efficient and simple devices for monitoring glucose levels is of utmost significance in managing diabetes. The advancement of nanotechnology has resulted in the indispensable utilization of advanced nanomaterials in high-performance glucose sensors. Modulating the morphology and intricate composition of transition metals represents a viable approach to exploit their structure/function correlation, thereby achieving optimal electrocatalytic performance of the synthesized catalysts. Results Herein, a sensitive and rapid Cu-encapsulated Cu 2 S@nitrogen-doped carbon (Cu@Cu 2 S@N–C) hollow nanocubes-functionalized microfluidic paper-based analytical device (μ-PAD) was fabricated. Through a delicate sacrificial template/interface technique and thermal decomposition, inter-connected hollow networks were formed to boost the active sites, and the carbon shell was coated to protect Cu from being oxidation . For application, the constructed μ-PAD is used for glucose sensing utilizing an origami automated sample pretreatment system enabled by a simple application of strong alkaline solution on wax paper. Under optimal circumstances, the Cu@Cu 2 S@N–C electrochemical biosensor exhibits broad detection range of 2–7500 μM (R 2  = 0.996) with low detection limit of 0.16 μM (S/N = 3) and high sensitivity of 1996 μA mM −1  cm −2 . Additionally, the constructed μ-PAD also exhibited excellent selectivity, stability, and reproducibility. Significance By rationally designing the double-shell hollow nanostructure and introducing Cu-encapsulated inner layer, the synthesized Cu@Cu 2 S@N–C hollow nanocubes show large specific surface area , short diffusion channels, and high stability. The proposed origami μ-PAD has been successfully applied to serum samples without any additional sample preparation steps for glucose determination, offering a new perspective for early nonenzymatic glucose diagnosis.

CAS / MDL: 62-31-7 1313-82-2
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ANGEWANDTE CHEMIE-INTERNATIONAL EDITION · 2025 ·Vol. 64 ·期 27 ·e202425601 · IF 16.9

Natural Sunlight-Driven Activation of Inert Aryl Halides Using Plasmonic Cu@CdS with Polysulfide Active Sites

Yuemei Li,Shi-Yu Guo,Hongfei Gu,Bingyu Wang,Peiwu Su,Xiuming Zhang,Haoqing Zhang,Shuping Zhang,Fanzhi Yang,Jia Liu,Qing-An Chen,Jiatao Zhang

Visible light photoredox catalysis has become a rapidly emerging area owing to its potential of using sunlight to tame previously hard-to-harness radicals for organic synthesis. At present, such a blueprint faces a significant challenge, namely how to accomplish thermodynamically demanding reactions with sunlight encompassing a wide range of low-energy photons. Here, we report a new reaction framework to overcome this bottleneck through decoupling the thermodynamic limits of photoreduction from photoexcitation. This is fulfilled based on the construction of a heterogeneous photocatalyst Cu@CdS possessing in situ-formed surficial polysulfide species (including S 3 •− and S 4 2− ), which can efficiently harvest solar energy via plasmonic absorption of Cu while manifest sufficient redox potential for activating inert aryl bromides/chlorides enacted by excited polysulfides. We demonstrate that this designed material composes a potent photoredox catalyst for efficient aryl cross-coupling, borylation, hydrogenation, as well as Birch-type dearomatization reactions, with good recyclability and stability. In particular, when exclusively using natural sunlight as an energy source, the product yield can still reach up to 90%. Our findings introduce a straightforward yet viable way to progress toward the century-long dream of leveraging natural sunlight to produce structurally complex organic molecules, just like plants on Earth. Graphical Chemists have long aspired to construct complex organic compounds the way that plants do by harnessing natural sunlight as an energy source. This study presents an advancement toward this goal via synergistic exploitation of the plasmonic absorption of Cu and the unique redox potentials of excited polysulfide species (S 3 •− and S 4 2− ) on semiconductor surfaces to decouple the thermodynamic limits of photoreduction from photoexcitation.

CAS / MDL: 2459-24-7
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