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JOURNAL OF MATERIALS SCIENCE · 2020 ·Vol. 55 ·期 28 ·13980-13994 · IF 3.553

A sandwich-type electrochemical immunosensor for ultrasensitive detection of CEA based on core–shell Cu2O@Cu-MOF@Au NPs nanostructure attached with HRP for triple signal amplification

Li Wenjun,Yang Yue,Ma Chaoyun,Song Yiju,Hong Chenglin,Qiao Xiuwen

A novel sandwich-type electrochemical immunosensor based on cuprous oxide (Cu 2 O)@copper-metal organic framework (Cu-MOF)@gold nanoparticles (Au NPs) core–shell structure was proposed. Cu 2 O@Cu-MOF@Au attached with horseradish peroxidase (HRP) triple-catalyzed hydrogen peroxide (H 2 O 2 ) for detecting CEA antigen. In this work, 50 nm Cu 2 O nanospheres were prepared. Using Cu 2 O nanospheres as the core, Cu-MOF was coated on the surface of Cu 2 O nanospheres by reaction of Cu 2 O and ligands. Subsequently, chloroauric acid was reduced to Au NPs without adding any reducing agent and Au NPs dispersed on the surface of Cu-MOF. Finally, the Cu 2 O@Cu-MOF@Au-HRP-Ab 2 nanoprobe was successfully prepared. Immunosensors had good performance due to the following reasons. Firstly, Cu 2 O, Cu-MOF and HRP have excellent catalytic properties for hydrogen peroxide. In addition, the synergistic effect of Cu 2 O, Cu-MOF and HRP promoted the reduction of hydrogen peroxide and tripled amplification of electrical signals. Here, the successfully prepared immunosensor detected carcinoembryonic antigen (CEA) sensitively, the detection range was 50 fg/mL–80 ng/mL, and the detection limit was 17 fg/mL. Besides, the proposed immunosensor had good stability, selectivity and specificity. Detection in human serum samples had good results without matrix effect. This provided a new idea for the clinical detection of tumor markers: "metal oxide—metal organic framework—precious metal nanoparticles" (MMP). Graphic abstract

研究领域: 生物医学工程 · 分析化学
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FOOD CHEMISTRY · 2022 · IF 9.231

Covalent molecularly imprinted electrochemical sensor modulated by borate ester bonds for hygromycin B detection based on the synergistic signal amplification of Cu-MOF and MXene

Haiyang Wang,Lin Cai,Yuwei Wang,Chang Liu,Guozhen Fang,Shuo Wang

A molecularly imprinted electrochemical sensor (MIES) modified with Cu-MOF and Ti 3 C 2 Tx was successfully prepared for the detection of hygromycin B in food. According to the pH sensitive property of reversible borate ester bonds, a molecularly imprinted polymers (MIP) were constructed on the modified gold electrode (GE) surface by electropolymerization to realize the controllable elution and adsorption of template molecules. Cu-MOF with large specific surface area and Ti 3 C 2 Tx with excellent electrical conductivity cooperate to improve the overall analytical performance of MIES. The morphology and electrochemical performance of the sensor were evaluated. Under the optimal experimental conditions, the method showed superior selectivity to hygromycin B with a linear range of 5 × 10 −9 –5 × 10 −6 M and a detection limit of 1.92 × 10 −9 M (S/N = 3). The detection results of this method are in good agreement with HPLC-MS/MS, which proves that the method has reliable practicability and accuracy.

研究领域: 食品科学 · 分析化学 · 生物传感技术
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2020 · IF 7.489

Cu-MOF chemodynamic nanoplatform via modulating glutathione and H2O2 in tumor microenvironment for amplified cancer therapy

Hailong Tian,Mengzhu Zhang,Guoxia Jin,Yue Jiang,Yuxia Luan

Chemodynamic therapy (CDT) utilizes Fenton catalysts to convert intracellular hydrogen peroxide (H 2 O 2 ) into cytotoxic hydroxyl radical (OH∙) for tumor therapy, but endogenous H 2 O 2 is usually insufficient to achieve satisfactory tumor therapy effect. Engineering an efficient CDT nanoplatform for satisfactory cancer therapy remains a challenge. Herein, we rationally designed a Cu-based metal-organic framework-199 (MOF-199) nanoplatform integrating vitamin k3 (Vk3) for amplified CDT-mediated cancer therapy, which could accumulate efficiently in tumor tissues through enhanced permeability and retention (EPR) effect. The MOF-199 nanoparticles (MOF-199 NPs) were dissociated by glutathione (GSH) into MOF-199 fragments, which triggered Fenton-like reaction for CDT. On the one hand, Vk3 was catalyzed by NAD(P)H quinone oxidoreductase-1 (NQO1) to produce sufficient H 2 O 2 to activate Fenton-like reaction. On the other hand, GSH was largely consumed in the tumor microenvironment. Thus, this nanoplatform enabled sufficient cytotoxic reactive oxygen species (ROS) for amplified CDT effect, demonstrating effective tumor growth inhibition with minimal side-effect in vivo. Our work provides an innovative strategy to modulate GSH and H 2 O 2 levels for amplified CDT.

研究领域: 癌症治疗 · 纳米技术 · 生物化学 · 药学
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ANALYST · 2021 ·Vol. 146 ·期 19 ·5951-5961 · IF 4.616

Cu–MOF/hemin: a bionic enzyme with excellent dispersity for the determination of hydrogen peroxide released from living cells

Hong Cui,Shuaishuai Cui,Siyuan Zhang,Qiuju Tian,Yunfeng Liu,Ping Zhang,Mingxiu Wang,Jialing Zhang,Xiangjun Li

The stability, repeatability and sensitivity of an electrochemical biosensor material are closely connected with the dispersibility of metal organic frameworks (MOFs) in aqueous media. Herein, a nanocomposite based on Cu–MOF/hemin, which is not only highly water-soluble but also simple and efficient in synthesis, was used for the construction of a non-enzymatic sensor to detect hydrogen peroxide (H2O2). The Cu–MOF/hemin was characterized via scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS)-mapping, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA), which indicate that hemin and the Cu–MOF were successfully combined. As a H2O2 electrochemical biomimetic enzyme, the Cu–MOF/hemin exhibited excellent electrocatalytic performance, which was confirmed by the electrochemical experiments and chromogenic reactions, and the possible mechanism of the reactions has been deduced. The electrochemical sensor based on the biomimetic enzyme exhibited an extended linear detection range from 0.01–5.0 mM (R = 0.998), low detection limit of 4.14 μM, and high selectivity and stability under the optimized conditions. More importantly, the practical application ability of the sensor was verified by the test of H2O2 in human serum samples and it could be used for the real-time detection of H2O2 released from living cells with satisfactory results. Therefore, this novel nanocomposite has certain potential in preparing electrochemical sensing platforms for nonenzymatic biosensing and provides a new method for clinical diagnosis and real-time monitoring.

研究领域: 分析化学 · 材料科学 · 生物化学 · 生物医学工程
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Journal of Materials Chemistry B · 2023 ·Vol. 11 ·期 19 ·4211-4226 · IF 7

A carbon dot-doped Cu-MOF-based smart nanoplatform for enhanced immune checkpoint blockade therapy and synergistic multimodal cancer therapy

Zhongping Su,Haiying Xu,Ying Zhang,Huanli Zhang,Hui Zhang,Yujun Bao,Xiaodan Wu,Rui Yan,Guanghui Tan,Zhiqiang Wang,Yingxue Jin

Immune checkpoint blockade (ICB) is a kind of promising anti-tumor immunotherapy that can block the negative immune regulatory pathways using a particular antibody. Weak immunogenicity in most patients is a key obstacle to ICB therapy. Photodynamic therapy (PDT) is a non-invasive treatment that can enhance the immunogenicity of the host and realize systemic anti-tumor immunotherapy; yet tumor microenvironment hypoxia and glutathione overexpression severely restrict the PDT effect. To overcome the above issues, we design a combination therapy based on PDT and ICB. We prepared red carbon dot (RCD)-doped Cu-metal–organic framework nanoparticles (Cu-MOF@RCD) as smart nano-reactors because their tumor microenvironment and near-infrared light responsive property can decompose tumor endogenous H2O2 through Fenton-like reactions. Cu-MOF@RCD also shows clear near-infrared photothermal therapy (PTT) effect and has an ability to deplete glutathione (DG), which together enhances decomposition of cellular H2O2 and amplifies reactive oxygen species (ROS) levels in cells, thus leading to enhanced PDT and chemodynamic therapy (CDT) effect. Moreover, programmed cell death-ligand 1 antibody (anti-PD-L1) is used together to enable combination therapy, as Cu-MOF@RCD can significantly enhance host immunogenicity. In summary, the combination of Cu-MOF@RCD with anti-PD-L1 antibody exerts a synergistic PDT/PTT/CDT/DG/ICB therapy and can be used to eradicate the primary tumors and inhibit the growth of untreated distant tumors and tumor metastasis.

研究领域: 纳米技术 · 癌症治疗 · 免疫治疗 · 光疗
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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

Construction of a portable enzyme-free electrochemical glucose detection system based on the synergistic interaction of Cu-MOF and PtNPs

Xin Chen,Xiao-Zhen Feng,Tao Zhan,Yu-Ting Xue,Hai-Xiang Li,Guo-Cheng Han,Zhencheng Chen,Heinz-Bernhard Kraatz

Three enzyme-free electrochemical glucose (GLU) sensors with bimetallic structures were constructed by electrodeposition of gold and copper nanoparticles (AuNPs/CuNPs), nickel and copper nanoparticles (NiNPs/CuNPs), and a copper-based metal-organic framework (Cu-MOF) combined with PtNPs , respectively. Amongst, the Cu-MOF/PtNPs on a gold electrode (GE) exhibited the best catalytic performance for GLU oxidation due to the synergistic amplification. The relevant electrochemical behaviour of GLU showed that two OH - and two electrons were involved in the process. The differential pulse voltammetry (DPV) enables the establishment of linearity in the concentration of 0.40–25.00 mM, with a detection limit (LOD) of 0.06 mM and a sensitivity of 158.41 µA·mM −1 cm −2 . In addition, the Cu-MOF/PtNPs/GE sensor was used to detect GLU in oral liquid as well as human serum samples with a recovery rate of 97.00–103.98% and RSD less than 3.59%. Finally, a portable electrochemical detection system based on the STM32F103C8T6 microcontroller , obtained a GLU concentration 5.24 mM while detecting in a diluted injection where the value 5.40 mM was recorded by a commercial meter to show the system has very broad application prospects in the point-of-care setting.

研究领域: 电化学 · 生物传感器 · 材料科学 · 分析化学 · 即时检测
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Promotion and monitor wound healing by anthocyanin enhanced light curing ε-poly-l-lysine hydrogel encapsulated Cu-MOF

Xiawei Zhao,Rui Liu,Tiantian Tang,Zihao Liu,Xiaozhi Liu,Kai Yu,Ye Zhang,Hao Wang

Drug-resistant bacterial infections and biofilm formation have long posed significant challenges to public health, particularly in the context of chronic wound healing. In this study, the CuHspMOF were derived from copper and hesperitin (Hsp). The photocurable Epsilon-poly-l-lysine (EPLMA) and blueberry anthocyanin (BA) were synthesized through free radical polymerization. The multifunctional EB@CuHsp hydrogel exhibits excellent photothermal effect. One of the key features of the EB@CuHsp hydrogel is its ability to monitor the healing environment through color changes in response to variations in pH. This property allows for real-time assessment of the wound’s pH levels, reflecting the body fluid’s pH range during the healing process (pH 5–9). The hydrogel components work synergistically to facilitate wound healing. The EPLMA, with its positively charged, could captures bacteria and enable copper ions to eradicate bacteria at lower concentrations. This dual action leads to the creation of an optimal healing environment conducive to wound healing. During the inflammatory phase, BA and Hsp could collaborate to combat inflammation, which transited from the inflammatory stage to the proliferative phase soon. Continuous release of BA and Cu 2+ , coupled with thermotherapy, significantly enhances epithelial and blood vessel regeneration, thereby expediting the healing of chronic wounds. Overall, this multifunctional composite hydrogel holds great promise for promoting the regeneration of infected wound tissue, making it a potential candidate for chronic wound dressings.

研究领域: 生物医学工程 · 材料科学 · 药剂学 · 伤口护理 · 纳米技术 · 生物材料
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BIOSENSORS & BIOELECTRONICS · 2024 · IF 10.7

LTP-assisted fabrication of laccase-like Cu-MOF nanozyme-encoded array sensor for identification and intelligent sensing of bioactive components in food

Chao Liu,Qing Huang

Nanozymes are potential candidates for constructing sensors due to their adjustable activity, high stability, and high cost-effectiveness. However, due to the lack of reasonable means, designing and preparing efficient nanozymes remains challenging. Herein, inspired by the property of natural laccase, we applied the novel and facile low-temperature plasma (LTP) technology to fabricate a series of different base-ligand Cu metal organic framework (MOF) nanozymes (namely, A-Cu, G-Cu, C-Cu and T-Cu nanozymes) with laccase-like activity successfully. Owing to the different catalytic capacities of four types of base-Cu-MOF nanozymes in the response to five common effective bioactive substances, we constructed the nanozyme-encoded array sensor for the identification of different bioactive compounds. As a result, the four-channel colorimetric sensor array was constructed, in which four laccase-like nanozymes were utilized as the sensing units, achieving high-throughput, high-sensitivity and rapid detection/identification of five common bioactive compounds in the concentration range of 1.5–150 μg mL −1 through different color output patterns. It is worth noting that the as-prepared sensor array can successfully distinguish the natural bioactive compounds in a variety of real samples. Furthermore, with the assistance of smartphones, we also designed a portable smart sensing approach for detecting the bioactive compounds effectively in food. This study has therefore not only provided an effective way for preparation highly effectively nanozymes, but also established a new sensing platform for intelligent sensing of bioactive components in food.

研究领域: 材料科学 · 分析化学 · 生物技术 · 食品科学
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Journal of Materials Chemistry B · 2025 · IF 5.7

Ligand-Dependent Activity Engineering Cu-MOF Based on Biomimetic Strategies for Nanozyme-Decorated Smart Hydrogel for Therapy of Inflammatory Bone Defects

Shaoxiong Feng,Xu Peng,Xu Wei,Yiqing Deng,Xinyun Pu,Xi Gao,Xixun Yu

Reconstructing inflammatory bone defects using stem cell-based therapy faces challenges posed by the oxidative stress microenvironment. Here, inspired by the response mechanism of the intracellular antioxidant defense systems (IADS), we propose MOF nanozymes that mimic the structure of horseshoe crab hemocyanin and find that a ligand engineering strategy can modulate the SOD- and CAT-mimicking activities of MOF-based nanozymes. Through in vitro screening, the most efficient Cu-Imi nanozymes were selected and incorporated into a smart hydrogel (composed of oxidized dextran and dopamine-functionalized gelatin) for inflammatory bone defect treatment. Studies demonstrate that smart hydrogels are able to respond to the acidic microenvironment induced by oxidative stress and early tissue injury by intelligently releasing biomimetic nanozymes, which can effectively eliminate bacteria, alleviate inflammation, and reduce ROS levels. In addition, the smart hydrogel can effectively sustain stem cell viability and osteogenic differentiation in elevated ROS environments, and has the potential to promote angiogenesis and modulate the inflammatory microenvironment during rat bone tissue regeneration. We believe that this smart hydrogel-like material decorated with antioxidant enzymes offers a promising avenue for treat various inflammation-associated disorders, including arthritis, chronic wound and bone fractures.

CAS / MDL: 62-31-7
研究领域: 生物材料 · 纳米医学 · 组织工程 · 生物无机化学 · 再生医学 · 炎症研究
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ANALYST · 2023 ·Vol. 148 ·期 19 ·4869-4876 · IF 4.2

Diazo-reaction based dual-mode colorimetric-electrochemical sensing of nitrite in pickled food

Yixin Pan,Jing Jiang,Xianwen Kan

Development of an effective and convenient sensor for sensitive detection of nitrites is of great concern since excessive amounts of nitrites can be harmful to both human health and the environment. In this work, Cu-MOF modified exfoliated graphite paper (EGP) was employed as a signal reporter to enable the visual and electrochemical dual-mode sensing of nitrites. Cu-MOFs were in situ synthesized on EGP, which exhibited an excellent oxidase enzyme-like activity to oxidize 3,3′,5,5′-tetramethylbenzidine (TMB) into its oxidation product (oxTMB). The multi-layer structure and the superior electrical conductivity of EGP not only facilitated the loading of the Cu-MOF nanozyme for colorimetric sensing but also enabled its use as an underlying backbone to support electroanalysis. Based on the recognition of nitrite through a highly specific diazo reaction between nitrite and oxTMB, the addition of nitrite caused the colorimetric sensing solution to change color from blue to green, which allowed for the colorimetric sensing of nitrite with a limit of detection (LOD) of 8.5 × 10−6 mol L−1. Meanwhile, the Cu-MOF/EGP electrochemical platform was employed for ratiometric detection of nitrite based on the electrochemical oxidation of nitrite and TMB. Compared with the colorimetric mode, the electrochemical mode possessed higher sensitivity with a LOD of 5.4 × 10−7 mol L−1, indicating the high sensitivity and accuracy of the proposed dual-mode sensing strategy. Furthermore, the determination of nitrite in different pickled food samples is demonstrated.

研究领域: 分析化学 · 环境科学 · 食品科学
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Journal of Materials Chemistry C · 2018 ·Vol. 6 ·期 30 ·8105-8114 · IF 5.976

Cu MOF-based catalytic sensing for formaldehyde

Ping Gao,Xiang-Ying Sun,Bin Liu,Hui-Ting Lian,Xin-Qiang Liu,Jiang-Shan Shen

Developing a catalyst with a uniform and well-defined crystal structure is very important to establish a catalytic sensing system with high efficiency. In this work, Cu-BTC metal–organic frameworks (MOFs) without a crystalline CuO or Cu2O phase were successfully synthesized by using a low temperature synthesis method, and the as-prepared Cu-BTC MOFs were found to have outstanding catalytic activity towards the traditional oxidase substrate, o-phenylenediamine (OPD), to generate a colored and fluorescent product. The results of the kinetics analysis revealed that the catalytic behavior of Cu-BTC MOFs towards OPD could well follow the typical Michaelis–Menten equation, indicative of a strong affinity between Cu-BTC MOFs and OPD. On the basis of these findings, taken together the condensation reaction between the –CHO group of formaldehyde and the –NH2 group of OPD to form Schiff base compounds, a novel Cu-BTC MOF-based catalytic sensing system for detecting gaseous formaldehyde could be successfully established.

研究领域: 催化 · 材料科学 · 分析化学
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WATER AIR AND SOIL POLLUTION · 2023 ·Vol. 234 ·期 2 ·1-16 · IF 2.9

Preparation of Chitosan Modified Cu-Metal–Organic Framework Antibacterial Microspheres and Their Application in Adsorption of Cr(VI) from Aqueous Solution

Kang Yongfeng,Yu Yingyuan,Zhang Bingqian,Fu Jianning,Jiang Xixi,Jia Baiyun,Men Xiaoling,Li Li

Metal–organic frameworks (MOFs) are ideal adsorbents for wastewater treatment and excellent antibacterial agents. In this study, Cu-NH 2 -MOF chitosan composite microspheres were prepared by the in situ method, and the synthesized microspheres solved the disadvantages of poor recoverability of powder adsorbent and complex operation process. Cr(VI) was removed by adsorption, and the microspheres had a good bacteriostatic effect. The synthesized MOF chitosan composite microspheres were systematically characterized. The adsorption kinetics, isotherms, and thermodynamic properties were appraised, and influences of adsorption conditions toward Cr(VI) adsorption were studied. The kinetic study demonstrated that the adsorption of Cr(VI) by CS@Cu-MOF-M conformed to the pseudo-second-order model. The adsorption isotherms fit the Sips model, and the maximum adsorption capacity of CS@Cu-MOF-M for Cr(VI) was 159.25 mg/g under optimal conditions. The thermodynamic result showed that the removal of Cr(VI) was a spontaneous endothermic process. The adsorption rate of CS@Cu-MOF-M was still more than 80% of that of the first one after four cycles of regeneration experiments. The antibacterial activity results showed that MOF chitosan composite microspheres had good antibacterial properties with MIC value of 0.2 mg/mL and MBC value of 1 mg/mL. These results demonstrated that the synthesized CS@Cu-MOF-M had a great potential to treat wastewater containing Cr(VI) and bacterial contamination. Graphical Abstract

研究领域: 环境科学 · 材料科学
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