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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

A novel electrochemical sensor based on Cu(Ⅱ) metal organic framework for the determination of metformin

Yuting Hao,Hao Zhang,Xizhuang Yue,Zhen Zhao,Shuang Zhao

Herein, a novel, simple prepared and robust electrochemical sensor based on the copper-containing metal organic framework (CuBTC) has been developed for the determination of metformin (MET), a first-line drug for type 2 diabetes mellitus. CuBTC was synthesized by hydrothermal method. The morphology and structure of CuBTC were characterized by scanning electron microscopy, X-ray powder diffraction and infrared spectroscopy. The electrochemical behavior of MET at the glassy carbon electrode modified with CuBTC/Nafion mixture was deeply explored by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The electrochemical studies showed that CuBTC had excellent electrocatalytic ability towards the redox reaction of MET. Under the optimal conditions, the linear range of MET on the modified electrode was 0.5–280 μmol/L, and the detection limit was 0.19 μmol/L. Additionally, the proposed sensor exhibited good long-time stability, reproducibility and selectivity, which was successfully applied to detect MET in tablets, serum and urine samples.

CAS / MDL: 1115-70-4
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Ratiometric Fluorescent Detection of Ultrasound-Regulated ATP Release: An Ultrasound-Resistant Cu,N-Doped Carbon Nanosphere

Zhezhu Nan,Hengyu Liu,Linrong Shi,Hongrui Zhu,Junjie Chen,Tali Ilovitsh,Daocheng Wu,Mingxi Wan,Yi Feng

Focused ultrasound, as a protocol of cancer therapy, might induce extracellular adenosine triphosphate (ATP) release, which could enhance cancer immunotherapy and be monitored as a therapeutic marker. To achieve an ATP-detecting probe resistant to ultrasound irradiation, we constructed a Cu/N-doped carbon nanosphere (CNS), which has two fluorescence (FL) emissions at 438 and 578 nm to detect ultrasound-regulated ATP release. The addition of ATP to Cu/N-doped CNS was conducted to recover the FL intensity at 438 nm, where ATP enhanced the FL intensity probably via intramolecular charge transfer (ICT) primarily and hydrogen-bond-induced emission (HBIE) secondarily. The ratiometric probe was sensitive to detect micro ATP (0.2–0.6 μM) with the limit of detection (LOD) of 0.068 μM. The detection of ultrasound-regulated ATP release by Cu,N-CNS/RhB showed that ATP release was enhanced by the long-pulsed ultrasound irradiation at 1.1 MHz (+37%, p < 0.01) and reduced by the short-pulsed ultrasound irradiation at 5 MHz (−78%, p < 0.001). Moreover, no significant difference in ATP release was detected between the control group and the dual-frequency ultrasound irradiation group (+4%). It is consistent with the results of ATP detection by the ATP-kit. Besides, all-ATP detection was developed to prove that the CNS had ultrasound-resistant properties, which means it could bear the irradiation of focused ultrasound in different patterns and detect all-ATP in real time. In the study, the ultrasound-resistant probe has the advantages of simple preparation, high specificity, low limit of detection, good biocompatibility, and cell imaging ability. It has great potential to act as a multifunctional ultrasound theranostic agent for simultaneous ultrasound therapy, ATP detection, and monitoring.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Synergistic contribution of metal–acid sites in selective hydrodeoxygenation of biomass derivatives over Cu/CoOx catalysts

Xiaofeng Wang,Zuyi Zhang,Ziyi Yan,Qingbo Li,Chengcheng Zhang,Xinhua Liang

The efficient hydrodeoxygenation (HDO) of biomass derivatives to yield specific products is a significant yet challenging task. In the present study, a Cu/CoO x catalyst was synthesized using a facile co-precipitation method, and subsequently used for the HDO of biomass derivatives. Under optimal reaction conditions, the conversion of 5-hydroxymethylfurfural reached 100% with a selectivity of ∼99% to 2,5-diformylfuran. In combination with the experimental results, systematic characterizations revealed that CoO x , as the acid site, tended to adsorb C O bonds, and the metal sites of Cu + were inclined to adsorb C O bonds and enhance C O bond hydrogenation. Meanwhile, Cu 0 was the main active site for 2-propanol dehydrogenation . The excellent catalytic performance could be attributed to the synergistic effects of Cu and CoO x . Further, by optimizing the ratio of Cu to CoO x , the Cu/CoO x catalysts exhibited notable performance in HDO of acetophenone, levulinic acid, and furfural, which verified the universality of the catalysts in the HDO of biomass derivatives.

CAS / MDL: 67-47-0
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Acta Biomaterialia · 2023 · IF 9.7

Cu-GA-coordination polymer nanozymes with triple enzymatic activity for wound disinfection and accelerated wound healing

Haotian Tian,Jianqin Yan,Wei Zhang,Huaixu Li,Shouwei Jiang,Haisheng Qian,Xulin Chen,Xingliang Dai,Xianwen Wang

During the past few years, bacterial infection and oxidative stress have become important issues for wound healing. However, the emergence of numerous drug-resistant superbugs has had a serious impact on the treatment of infected wounds. Presently, the development of new nanomaterials has become one of the most important approaches to the treatment of drug-resistant bacterial infections. Herein, coordination polymer copper-gallic acid (Cu-GA) nanorods with multi-enzyme activity is successfully prepared for efficient wound treatment of bacterial infection, which can effectively promote wound healing. Cu-GA can be efficiently prepared by a simple solution method and had good physiological stability. Interestingly, Cu-GA shows enhanced multienzyme activity (peroxidase, glutathione peroxidase , and superoxide dismutase), which can produce a large number of reactive oxygen species (ROS) under acidic conditions while scavenging ROS under neutral conditions. In acidic environment, Cu-GA possesses POD (peroxidase)-like and glutathione peroxidase (GSH-Px)-like catalytic activities that is capable of killing bacteria ; but in neutral environment, Cu-GA exhibits superoxide dismutase (SOD)-like catalytic activity that can scavenge ROS and promote wound healing. In vivo studies show that Cu-GA can promote wound infection healing and have good biosafety. Cu-GA contributes to the healing of infected wounds by inhibiting bacterial growth, scavenging reactive oxygen species, and promoting angiogenesis . Statement of significance Cu-GA-coordinated polymer nanozymes with multienzyme activity were successfully prepared for efficient wound treatment of bacterial infection, which could effectively promote wound healing. Interestingly, Cu-GA exhibited enhanced multienzyme activity (peroxidase, glutathione peroxidase, and superoxide dismutase), which could produce a large number of reactive oxygen species (ROS) under acidic conditions and scavenge ROS under neutral conditions. In vitro and in vivo studies demonstrated that Cu-GA was capable of killing bacteria, controlling inflammation, and promoting angiogenesis.

CAS / MDL: 7447-39-4 70-18-8
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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

Engineering of An Aptamer-Functionalized Fluorescent DNA Sensor for Cu(II) Responding in Living Tumor Cells

Yue Mou,Peng Yin,Meiyun Chen,Chonghui Wei,Yanfei Zhang,Jiaheng Zhang,Yujie Zhao,Xingyu Luo,Yilin Wang

Copper ions play vital roles in regulating life processes and being closely involved in several diseases such as cancer. Although detection methods based on fluorescent sensors or other strategies have been developed, it still remains a challenge to simultaneously realize the convenience, specificity, and accuracy in intracellular copper ion analysis. Herein, we propose an aptamer-functionalized DNA fluorescent sensor (AFDS) for accurate and specific detection of Cu(II) both in vitro and in cells by engineering the linkage of two DNA aptamers, namely, Lettuce aptamer and AS1411 aptamer, to achieve the manner of recognition response. Taking advantage of the functions of each aptamer, the tumor cell recognition capability and the high-contrast detection performance are simultaneously equipped in the AFDS. Furthermore, the AFDS shows high specificity and selectivity in Cu(II) response to avoid interference from common metal ions, chelators, and reactants by being associated with the irreversible interaction between nucleobases and Cu(II), which can destroy the topological structures and switch off the fluorescence of the AFDS. It also enables a sensitive in vitro detection of Cu(II) with a detection limit as lower as 0.1 μM and a wide detection linear range from 0.1 to 300 μM. The feasibility and superiority of the AFDS provide an opportunity to reveal both concentration-dependent and time-dependent intracellular Cu(II) responses in living cells. Therefore, the AFDS has achieved the novel detection performance of Cu(II) to exhibit great potential in exploring copper-related biological and pathological research.

CAS / MDL: 70-18-8
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CARBON · 2023 · IF 10.9

Interfacial Cu2O enables the unanticipated boosting activity of arc-converted graphitic chain mail encapsulated Cu nanocatalysts

Yonghui Zhao,Xiaoli Yang,Xiang Meng,Rui Hu,Xiaoliu Duan,Zhengya Gan,Jianjun Ding,Yi Gong,Xingyou Tian

Encapsulation of Cu nanoparticles by carbon chain mail is a promising approach to extend the service endurance. However, the diffusion of oxygen across the surfaces and interfaces of Cu nanoparticles (NPs) may induce obvious changes to their surface compositions, thereby dramatically altering catalytic properties . Here we reported an unanticipated boosting catalytic activity of graphitic chain mail-encapsulated Cu nanocatalysts (1.3- to 6.8-fold enhancement from initial 1.6–13.4 s −1 g −1 to stable 6.6–21.5 s −1 g −1 ) for the reduction of 4-nitrophenol by simply immersing these NPs in water for 10 days without any further treatment. The graphitic shells were arc-converted from sixteen types of biomass residuals and polymeric wastes. The rising catalytic activity was attributed to the temporal formation of Cu 2 O at the interface of Cu core and graphite shell, which was derived from the diffusion of dissolved oxygen across the defective graphitic chain mail. The increment of catalytic activity was linearly related with the rising content of Cu 2 O. The monotonous relations of initial and enhanced activities with shell thickness and interfacial composition of NPs were also well established. This work provides a new insight into the interfacial manipulation of core/shell nanocatalysts, and paves a versatile path for the high value-added utilization of carbon wastes.

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ACS Applied Nano Materials · 2023 · IF 5.9

Construction of Cu/ZIF-67/Prussian Blue Nanostructures with Photothermal-Enhanced Multizyme Activity for Cancer Therapy

Le He,Gang Ding,Sasha You,Si Lu,Xianfeng Huang,Ling Li,Xiaolan Yu

Nanozymes that mimic the catalytic reaction of natural enzymes show great prospects for tumor catalytic therapy because they possess the properties of nanomaterials and natural enzymes. However, the therapeutic effect of nanozymes is restricted by the low catalytic efficiency and specific oxidation–reduction systems in the tumor microenvironment (TME), such as overexpressed glutathione (GSH) level. In order to improve the catalytic efficiency, a multifunctional nanozyme, Cu/zeolitic imidazolate framework-67 (ZIF-67)/Prussian blue (PB), was designed through the modification of Prussian blue (PB) on the surface of the copper-doped zeolitic imidazolate framework, which can be used for imaging-guided synergistic therapy with photothermal-enhanced multienzyme-like catalytic therapy and chemotherapy. The doping of Cu2+ provided better glutathione oxidase-like (GPx-like) activity and peroxidase-like (POD-like) activity to deplete GSH and increase the generation of •OH in TME. The modification of PB provided better catalase-like activity (CAT-like) to promote the production of O2 and enhance the multienzyme-like catalytic therapy. In vivo experiments showed a satisfactory anticancer effect. This work thus provided a strategy for designing a type of multifunctional nanozyme for imaging-guided combination therapy.

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ENERGY & FUELS · 2023 · IF 5.3

Cu–Ni Alloy Nanoparticles Anchored on Nitrogen-Doped Carbon Nanotubes for Efficient CO2 Electroreduction to CO

Yi Ren,Yujia Bai,Genxiang Wang,Yijian Liu,Chuancheng Mou,Jiayu Chen,Baohuan Wei,Hui Wang,Yuhan Sun

Efficient conversion of CO2 to value-added fuels or chemicals using electricity from renewable sources is an appealing approach to realize carbon neutrality. Under this background, it is crucial to design efficient and low-cost catalysts for CO2 electroreduction. Herein, we fabricated an electrocatalyst with the structure of Cu–Ni alloy nanoparticles grown on nitrogen-doped carbon nanotubes (CuxNi/NCNT, x = 2.4, 1, and 0.36) for electrochemical CO2 reduction reaction (CO2RR) via a hydrothermal method followed by pyrolysis. The optimized CuNi/NCNT demonstrates a favorable CO2RR performance with a CO Faradaic efficiency (FECO) of 94.8% and a current density of 26.6 mA cm–2 at −0.9 V versus the reversible hydrogen electrode (vs RHE) in the H-cell, far superior to those of single metal counterparts. Density functional theory (DFT) calculations unravel that the Cu–Ni alloys possess much lower free energy changes for the formation of the key COOH* intermediate than those of the Cu metal, thereby facilitating CO2 reduction into CO. Additionally, the CO2RR performance of CuNi/NCNT was further evaluated in the gas diffusion electrode (GDE) involved in the flow cell to examine the practical application of the prepared catalyst, which can deliver a current density of 124.6 mA cm–2 with a FECO of 92.8% at −1.1 V vs RHE. This work enriches electrocatalysts for highly efficient CO2 electroreduction to CO.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Efficient photocatalytic degradation of sulfamethazine by Cu-CuxO/TiO2 composites: Performance, photocatalytic mechanism and degradation pathways

Shuang Shu,Hongjun Wang,Xinyan Guo,Yan Wang,Xiaolan Zeng

In this study, a novel Cu-Cu x O/TiO 2 composite photocatalyst was synthesized using combined sol–gel and impregnation methods. Several technologies were employed to characterize the morphology, crystalline structure, optical properties, and surface composition of the as-synthesized photocatalysts . The successful preparation of the Cu-Cu x O/TiO 2 composite was confirmed with superior properties compared to pure TiO 2 and Cu-Cu x O composite. The results for the degradation experiment employing sulfamethazine (SMZ) as the target pollutant indicated that the CT9 (the theoretical molar ratio of Cu(CH 3 COO) 2 to TiO 2 was 9:1) composite exhibits the best photocatalytic performance, and the degradation rate of SMZ reaches 98.2% after 60 min of irradiation. The good repeatability of CT9 was proved by five-cycle experiments. Radicals trapping experiments indicated that superoxide radicals and holes were primary oxidative species in photocatalytic degradation of SMZ. Eleven intermediates for SMZ degradation were identified employing LC-MS technology and the possible degradation pathways were proposed. ECOSAR models were used to predict the biotoxicity of the degradation intermediates. The present research exhibits a new opportunity for the construction of Cu-Cu x O-based photocatalysts to remove contaminants from antibiotic wastewater.

CAS / MDL: 6381-92-6 75-65-0
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2023 ·Vol. 25 ·期 18 ·12754-12766 · IF 3.3

Enhanced plasmonic photocatalytic performance of C3N4/Cu by the introduction of a reduced graphene oxide interlayer

Qixiao Gai,Shoutian Ren,Xiaochun Zheng,Wenjun Liu

Cu nanoparticles (NPs) are low-cost surface plasmonic resonance (SPR) metal nanostructures, and their SPR properties can be used to enhance the photocatalytic hydrogen evolution performance of carbon nitride (C3N4). But their actual performance is usually limited, and one key factor is their poor interfacial quality. In this work, a highly conductive reduced graphene oxide (RGO) interlayer is introduced between protonated C3N4 (PCN) nanosheets and Cu NPs, which can act as an efficient sink for photogenerated electrons from C3N4 and hot electrons from Cu NPs, and simultaneously serve as reaction sites for the hydrogen evolution reaction, and accelerate the charge transport by the formed C–O–C and C–O–Cu bonds. The optimal hydrogen evolution rate of the optimized PCN/RGO/Cu is 1.30 mmol g−1 h−1, which is 6.76, 2.47 and 2.41 times that of PCN, PCN/RGO and PCN/Cu, respectively, and it can further reach up to 13.22 mmol g−1 h−1 by loading moderate Pt NPs. Meanwhile, the introduced RGO can effectively anchor Cu NPs to enhance the stability of the photocatalyst. In addition, due to the broad SPR response of Cu NPs, a near-infrared photocatalytic performance is realized for PCN/RGO/Cu with an apparent quantum efficiency of 0.46% at 765 nm.

CAS / MDL: 1910-42-5 57-13-6
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ACS Applied Nano Materials · 2023 · IF 5.9

Single-Phase Cu,Mn-Codoped ZnGaS/ZnS Quantum Dots for Full-Spectrum White-Light-Emitting Diodes

Hanxu Lu,Zhe Hu,Hong Liu,Zizhao Fu,Hanqing Dai,Wanlu Zhang,Ruiqian Guo

Transition-metal-ion-doped quantum dots (QDs) are promising candidates to fabricate full-spectrum white-light-emitting diodes (WLEDs). In this work, a series of efficient white-light-emitting Cu,Mn-codoped ZnGaS/ZnS (Cu,Mn:ZnGaS/ZnS) QDs were synthesized by controlling the Zn/Ga molar ratio and the amounts of Mn dopants. After ZnS shelling, the photoluminescence quantum yield reached 58% and the spectrum almost covered the whole visible spectrum. Further, the stepwise doping process was investigated, which had considerable reference value to subsequent research. The Cu,Mn:ZnGaS/ZnS QDs were employed to fabricate WLEDs displaying a color rendering index of 94 and CIE coordinates of (0.34, 0.35).

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2023 · IF 4.2

Oxidative Desulfurization of Benzothiophene by Persulfate and Cu-Loaded g-C3 N4 via the Polymerization Pathway

Shao-Qi Zhi,Jun-Yuan Zhang,Song-Hai Wu,Wen-Shuang Zhu,Yu-Dong Shan,Yong Liu,Xu Han

Turning aromatic sulfur impurities to value-added polymers is a promising technology for fuel desulfurization. In this study, Cu(I,II)@g-C3N4 plates prepared via facile calcination show high reactivity in catalytic oxidation of benzothiophene (BT) by persulfate in a mixture of MeCN/H2O (v/v = 50/50). Quenching experiments rule out the primary contributions of SO4•–, •OH, and O2•– to BT oxidation and confirm the presence of carbon-centered radicals during the desulfurization process. XPS and Raman analyses reveal that Cu(I) and graphitic-N are reactive sites for persulfate activation, accompanied with moderate activation of the peroxo group in persulfate via the nonradical pathway. Solid characterizations indicate the formation of polybenzothiophene S,S-dioxide during the oxidation process, which further reveals that the moderately activated persulfate abstracts H from BT to form a BT radical cation, followed by subsequent polymerization of BT radical cations to a BT tetramer, and then the BT tetramer is further oxidized to a BT S,S-dioxide tetramer. The high electrochemical stability and pseudo-capacitive properties of the obtained polymers also imply their high potential to be used for capacitors. This work provides new insight on turning aromatic sulfur impurities in fuels to “treasures”.

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