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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Simultaneous detection of moxifloxacin and gatifloxacin by Cu-TCPP/rGO electrochemical sensor

Xiao-Zhen Feng,Kun-Zhi Wang,Ke-Hang Song,Guo-Cheng Han,Bing-Lun Li,Heinz-Bernhard Kraatz

Moxifloxacin (MOX) and gatifloxacin (GAT) are structurally similar and possess close oxidation peak potentials, making it difficult for simultaneous detection by electrochemical methods. To address this, an electrochemical sensor was constructed with reduced graphene oxide (rGO) and copper porphyrin complex (Cu-TCPP), achieving signal amplification and simultaneous detection of MOX and GAT. The linear relation range from 5.00 to 600.00 μmol·L −1 for MOX (LOD is 1.34 μmol·L −1 ) and 10 to 300 μmol·L −1 for GAT (LOD is 0.59 μmol·L −1 ). When applied to water samples, it achieved recoveries of 100.09–112.02 % with a relative standard deviation (RSD) of less than 6 % for MOX, and 97.27–110.72 % with an RSD of less than 4 % for GAT. Further calculations indicated that the electro-oxidation of GAT involved two protons and two electrons.

CAS / MDL: 50-81-7 51-61-6
研究领域: 分析化学 · 药物分析 · 电化学
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2022 ·Vol. 38 ·期 6 ·1356-1360 · IF 2.726

Synergistic Catalysis of Enzymes and Biomimetic MOFs: Immobilizing Cyt c on Two-dimensional MOFs to Enhance the Performance of Peroxidase

Wang Yitong,Meng Fanchen,Su Ruifa,Sun Changrui,Han Qianqian,Zhang Weina,Zhang Suoying

Metal-organic frameworks(MOFs) have been widely regarded as promising carriers for enzyme immobilization owing to their advantages in improving loading and regulating interaction with enzymes. However, they are still suffering from the problems of slow mass transfer and compromising activity. In this paper, the active two-dimensional(2D) MOF of Cu-TCPP(Fe)[TCPP=tetrakis(4-carboxy-phenyl)porphyrin], which possesses the biomimetic architecture of peroxidase, was adopted to anchor cytochrome(Cyt c) for the enhancement of catalytic activity. The atomic/nanometer thickness and micrometer lateral dimension of 2D MOFs can ensure the full exposure of immobilized enzymes and a shorter diffusion distance for the reactant molecules. Besides, the active carrier can provide synergistic catalysis and activity compensation during the reaction. When tested in the decomposition reaction of H 2 O 2 , Cyt c/Cu-TCPP(Fe) exhibited nearly twice catalytic activity and an accelerated catalytic rate compared to free Cyt c.

研究领域: 生物化学 · 材料科学
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ACS Applied Nano Materials · 2023 · IF 5.9

Ultrathin Cu–TCPP Nanosheet-Based Electrochemical Microsensor for Detecting the Immunosuppressive Drug Mycophenolic Acid

Mingshi Deng,Wei Jin,Wenjuan Yang,Lingling Tian,Xinghua Gao,Xuefeng Wang,Lingyan Feng,Metini Janyasupab,Bingpu Zhou,Yuan Zhang

Mycophenolic acid (MPA), which is a potent immunosuppressant, has been widely used to prevent organ rejection after organ transplantation. In clinical practice, it is essential to monitor the free MPA concentration. Herein, convenient and fast electrochemical microsensing technology is developed for directly detecting the MPA concentration. To implement this method, ultrathin copper-based metal–organic framework (Cu–MOF) nanosheets with a thickness of about 6.6 nm are used to detect MPA. An analysis of electrochemical behavior reveals the direct electrochemical catalytic oxidation mechanism of MPA molecules on a Cu(II) tetrakis(4-carboxyphenyl)porphyrin (Cu–TCPP)-modified electrode. Furthermore, electrochemical testing results show that the ultrathin Cu–TCPP nanosheet-based microsensor exhibits high sensitivity and specificity for MPA in the nano- to micromolar range, with a detection limit of 10 nM. X-ray absorption spectroscopy (XAS) characterization reveals that the unsaturated metal ions in ultrathin nanosheets are the active sites responsible for boosting the catalytic oxidation of MPA molecules. High-performance liquid chromatography–tandem mass spectrometry further shows the catalytic oxidation product of MPA and that the phenolic hydroxyl group in the MPA molecule is the active site where the catalytic reaction occurs. The considerable sensing performance of the Cu–TCPP nanosheet-based microsensor proves that it is possible to develop a fast and convenient method for the direct high-frequency monitoring of immunosuppressive drugs.

研究领域: 分析化学 · 生物医学工程 · 药物分析
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JOURNAL OF MEMBRANE SCIENCE · 2020 · IF 7.183

Photothermal responsive ultrathin Cu-TCPP nanosheets/sulfonated polystyrene nanocomposite photo-switch proton conducting membranes

Shabab Hussain,Zheng Deng,Amin Khan,Peipei Li,Zhuoyi Li,Zhou Fang,Xinyi Wan,Xinsheng Peng

Applying different strategies, nanocomposite membranes formation from functionalized polymer(s) and compatible nanofillers is the most renowned way to make the membrane proton conductive without compromising their mechanical strength . Among different types of nanofillers, incorporating photothermal-responsive metal organic frameworks (MOFs) into the ion exchange polymer is the prominent strategy and has achieved advanced attention in smart protonic solids with versatile potential applications. In this work, ultrathin, highly ordered porous photothermal-responsive copper tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP) nanosheets are incorporated into sulfonated polystyrene (SPS) membranes as novel nanofillers. High loading and well dispersed Cu-TCPP nanosheets incorporated nanocomposite membranes are achieved and demonstrate photo-switchable protonic conductivity due to photothermal response of MOFs nanosheets to visible light. The nanocomposite membrane with highest MOFs content shows a high proton conductivity of 1.42 × 10 −4  S cm −1 at 95 °C at 95% RH. The altered photo-switch proton conductivity of nanocomposite membranes is attributed to the formation and breakage of H-bonding networks with water molecules in the channels of proton transport pathways by the local photothermal heated Cu-TCPP nanosheets. Furthermore, after incorporation of the Cu-TCPP nanosheets into SPS, not only the thermal stability is increased but also almost zero swelling is achieved in water, which reflects the nice durability of nanocomposite membranes. This photo-switchable proton conductivity of polymer proton conducting nanocomposite membranes with nice thermal stability and negligible swelling serves as a new gate for photo-switching proton conductive membranes, photosensors , photoswitches etc .

研究领域: 材料科学 · 化学工程
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MICROCHIMICA ACTA · 2026 ·Vol. 193 ·期 3 ·126 · IF 5.4

FRET-triggered fluorescence switching: a g-CNQDs/Cu-TCPP “turn-on” aptasensor for ultrasensitive GP73 detection

Zhou Yu,Wu Runqiang,Fan Lingling,Qui Pengtao,Deng Xiaohua,Tan Xiaohong,Dong Shuaikang,Li Canru,Chen Jiejing,Liang Jintao,Li Guiyin

Hepatocellular carcinoma (HCC) is one of the most lethal malignancies worldwide, and early diagnosis is crucial. Golgi protein 73 (GP73) has emerged as a promising serum biomarker for HCC. However, current detection methods often fail to meet routine screening requirements due to limitations in sensitivity and operational simplicity. To address these challenges, we have developed a novel fluorescent aptamer-based sensor for highly sensitive GP73 detection based on the fluorescence resonance energy transfer (FRET) mechanism between graphitic carbon nitride quantum dots (g-CNQDs) and a copper-based metal–organic framework (Cu-TCPP). g-CNQDs were covalently conjugated with a GP73-specific aptamer to serve as the fluorescent donor, while two-dimensional Cu-TCPP nanosheets acted as the efficient acceptors. Fluorescence was quenched upon donor–acceptor interaction via FRET. In the presence of GP73, aptamer–target binding disrupted FRET interaction, separating the donor from the acceptor and restoring fluorescence in a concentration-dependent manner. Under optimal conditions, the sensor exhibited excellent linearity over a concentration range 1.0–225.0 ng mL⁻¹, with a detection limit as low as 0.907 ng mL⁻¹. Recoveries for spiked human serum samples ranged from 95.96% to 103.85%, with relative standard deviations (RSDs) of 0.38%–5.48%. The developed aptamer sensor demonstrated excellent sensitivity, selectivity, and stability, providing a powerful tool for early HCC diagnosis and offering strong potential for real-time analytical applications. Graphical A novel fluorescent aptamer sensor for GP73 detection by leveraging the fluorescence resonance energy transfer (FRET) mechanism between graphite-phase carbon nitride quantum dots (g-CNQDs) and a copper-based organic framework (Cu-TCPP). This platform achieved a good linear relationship with GP73 concentration in the range of 1.0–225.0 ng mL -1 for GP73 concentration, and a detection limit of 0.907 ng mL -1 .

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Nanoscale · 2022 ·Vol. 14 ·期 47 ·17670-17680 · IF 8.307

Ultrathin metal–organic framework nanosheets as building blocks of lamellar nanofilms for ultrafast molecular sieving

Guitu Wang,Jingyu Lu,Chuanjie Fang,Wenzhang Fang,Xinsheng Peng,Hongbo Zeng,Liping Zhu

Metal–organic framework (MOF) nanosheets have significant potential applications including separation, catalysis, and sensors. However, the on-demand design with tunable thickness and morphology remains a great challenge, leading to difficulties in modulating their hierarchical assembly for the preparation of macroscopic films. Herein, we report the successful synthesis of smooth and ultrathin MOF (Cu-TCPP (TCPP = 4,4,4,4-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid))) nanosheets used in lamellar nanofilms for the rejection of organic molecules from water. Dopamine hydrochloride (DA-HCl) is used as an adjuvant in the synthesis. Facilitated by a HCl acid environment and DA competitive coordination, the normal and lateral growths of Cu-TCPP nanosheets are modulated to achieve the desired thickness and morphology. DA-HCl can be also easily removed from the nanosheets without affecting their physicochemical properties. The as-synthesized nanosheets are utilized as nanofilm building blocks in which they are stacked into ordered bricks. The obtained membrane displays an ultrahigh water permeance of 2540 L m−2 h−1 bar−1, which is two orders of magnitude higher than the currently reported polymer membranes, while it does not sacrifice the solute rejection as completely determined by the intrinsic pore size of the nanosheets (i.e., 98.8% for molecules larger than 1.3 nm). This work provides a novel and facile strategy to tailor the morphology of the MOF nanosheets for maximizing their functionalities and structure superiority in many engineering applications.

研究领域: 材料科学 · 化学工程 · 纳米技术
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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 12.5

Defect-engineered Cu-TCPP/ZIF-L nanosheet-modified PVDF membrane with enhanced water purification and dye removal performance

Yiming Zhao,Jingyuan Zhang,Junmei Liu,Jiatong Han,Dan Xu,Jing Wang,Fengzhi Lyu,Lin Qin,Donghui Xu,Ge Chen,Guangyang Liu

Defect-engineered Cu–TCPP/ZIF-L nanosheet membrane: tannic acid coordinates with Cu 2+ to create defect sites, while ZIF-L serves as an interlayer spacer to suppress π–π stacking and restore transport. • The optimized membrane achieves 691.20 L·m -2 ·h -1 ·bar -1 , a 75.5× increase over pristine Cu–TCPP. • Efficient dye removal under static conditions: 97.77% (CV) and 97.87% (MG), suitable for agricultural water purification. • Adsorption–degradation self-cleaning via single-layer chemisorption/ion exchange and catalytic oxidation by O₂· - / 1 O₂; cucumber seedling tests confirm irrigation safety. Dye-laden wastewater from aquaculture and agricultural runoff poses serious environmental challenges, calling for membranes that can deliver both high water flux and efficient dye removal. However, MOF-based composite membranes often still face trade-offs between permeance and separation efficiency, and their practical performance is limited by fouling and insufficient self-regeneration. We hypothesize that defect engineering of Cu–TCPP via tannic-acid-mediated metal–phenolic network (MPN) disruption, together with ZIF-L nanosheet interlayer modulation, can create favorable transport pathways and strengthen adsorption/ion-exchange interactions while enabling ROS-driven self-cleaning. A defect-engineered Cu–TCPP/ZIF-L nanosheet-modified PVDF membrane was prepared using an MPN strategy with tannic acid, and its dye removal performance toward malachite green and crystal violet, together with the underlying mechanisms, was systematically investigated. The optimized membrane achieves a 75.5-fold increase in water permeance to 691.20 L/(m 2 ·h·bar) while maintaining high removal efficiencies of 97.87% for malachite green and 97.77% for crystal violet, and it exhibits self-cleaning behavior enabled by superoxide radicals and singlet oxygen. This work demonstrates an integrated Cu-TCPP–TA/ZIF-L/PVDF membrane design that combines MPN-mediated defect regulation with ZIF-L-assisted lamellar structure modulation for adsorption–degradation-based dye removal in agricultural water-related scenarios. Download: Download high-res image (170KB) Download: Download full-size image

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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2020 ·Vol. 27 ·期 31 ·39186-39197 · IF 3.056

Microwave-assisted hydrothermal assembly of 2D copper-porphyrin metal-organic frameworks for the removal of dyes and antibiotics from water

Zhao Shiyin,Li Shun,Zhao Zhicheng,Su Yiping,Long Yangke,Zheng Zuquan,Cui Daling,Liu Yong,Wang Chunfei,Zhang Xuanjun,Zhang Zuotai

Adsorption and photocatalysis are promising strategies to remove pollutants of dyes and antibiotics from wastewater. In this study, we demonstrate a rapid microwave-assisted hydrothermal route for the assembly of 2D copper-porphyrin Metal-Organic Frameworks (Cu-TCPP MOFs) within 1 h. The resulting 2D Cu-TCPP nanosheets with excellent crystallinity and a large surface area (342.72 m 2 /g) exhibited outstanding adsorption performance for typical dyes with adsorption capacities of about 185 mg/g for rhodamine B, 625 mg/g for methylene blue, and 290 mg/g for Congo red, respectively, as well as for representative antibiotics with adsorption capacities of about 130 mg/g for oxytocin, 150 mg/g for tetracycline, and 50 mg/g for norfloxacin, respectively. Meanwhile, the as-prepared 2D Cu-TCPP showed good photocatalytic degradation activity of pollutants after adsorption under irradiation by visible light, reaching removal efficiencies of 81.2 and 86.3% toward rhodamine B and norfloxacin, respectively. These results demonstrate the promising potential of 2D Cu-TCPP for use in the removal of contaminants from wastewater.

研究领域: 环境科学 · 材料科学 · 化学工程 · 纳米技术
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APPLIED SURFACE SCIENCE · 2025 · IF 6.9

Microfluidic continuous flow production of Pt nanoparticles stabilized on Cu-TCPP@ MOFs for efficient photocatalytic degradation: mechanism and degradation pathways

Li Ma,Xiong Zhao,Zijuan Luo,Zhenzhen Chen,Jinjia Wei,Nanjing Hao

Porphyrin-based metal–organic frameworks are widely utilized in the photocatalytic field owing to their unique photosensitive properties. Whereas controllable substrate morphology and uniform distribution of the noble metal nanoparticles still remain challenging in traditional synthesis. Herein, Cu-TCPP@MOFs and PtNPs/Cu-TCPP@MOFs with flower-like architecture were produced via continuous flow strategy and double spiral microreactor efficiently and controllably. The results revealed that 5.2 wt% Pt nanoparticles with 2.68 nm were embedded evenly on the Cu-TCPP@MOFs within 5 min. Compared to the Cu-TCPP@MOFs, the PtNPs/Cu-TCPP@MOFs exhibited much superior catalytic performance for rhodamine B (RhB) degradation under visible-light-driven, the reaction rate constant and catalytic activity parameter increased from 0.010 to 0.027 min −1 , and 0.03 to 11.25 s·g −1 , respectively. The free radical capture experiments revealed that h + , ·OH, and ·O 2 − played a synergistic role in the RhB degradation, whereas ·OH plays the most prominent effect. The reasonable degradation pathways of RhB were proposed by combining the density functional theory (DFT) with liquid chromatography mass spectrometry (LC-MS) investigation. This work not only provided insights into the design and controllable preparation of high-performance photocatalysts but also provided an effective strategy for degrading organic pollutants in the water environment, which poses significant environmental and economic benefits.

研究领域: 材料化学 · 环境科学 · 光催化 · 纳米技术 · 分析化学 · 理论计算化学
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ACS Applied Materials & Interfaces · 2026 · IF 7.8

GSH-Activated Cu-TCPP(Zn)/Ti3C2Tx Nanozymes for Fluorescence Imaging-Guided Synergistic Photodynamic/Chemodynamic Therapy of Oral Squamous Cell Carcinoma

Lidong Wang,Yongyan Sun,Yuting Sun,Changbin Zhang,Guixi Wang,Junnan He,Yan Zhao,Ming Li

Photodynamic therapy (PDT) holds promise for oral squamous cell carcinoma (OSCC) but is limited by the tumor microenvironment─specifically hypoxia, elevated glutathione (GSH), and the lack of tumor-selective photosensitizer activation. To overcome these barriers, we developed a GSH-activated nanoplatform Cu-TCPP(Zn)/Ti3C2Tx for fluorescence imaging-guided synergistic photodynamic/chemodynamic therapy (PDT/CDT). The system is constructed from two-dimensional Cu-TCPP(Zn) MOF nanosheets, where Cu2+ and Zn2+ completely quench the fluorescence and PDT activity of TCPP and surface-anchored Ti3C2Tx MXene. In the TME, overexpressed GSH reduces Cu2+ to Cu+ and abstracts Zn from the Zn–N4 complex, triggering nanocomposite disintegration to restore fluorescence, activate PDT, and simultaneously deplete GSH to reduce antioxidant defense. The resulting Cu+ catalyzes a Fenton-like reaction with endogenous H2O2 to generate •OH for CDT, while Ti3C2Tx acts as a catalase-like nanozyme, decomposing H2O2 into O2 to alleviate hypoxia, promote charge transfer, improve the utilization efficiency of photogenerated electrons, and enhance PDT efficacy. In vitro, the platform showed excellent biocompatibility and GSH-responsive activation, inducing 41.21% apoptosis in CAL-27 cells under 660 nm laser irradiation, significantly outperforming controls. In vivo, the nanocomposite accumulated efficiently in tumors via the EPR effect, suppressed tumor growth, and exhibited no observable systemic toxicity. This work provides a TME-responsive theranostic platform that integrates tumor-specific activation, GSH depletion, hypoxia alleviation, and enhanced ROS generation for precise and effective OSCC treatment.

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TALANTA · 2026 · IF 6.7

Synergistic Ag/Cu-TCPP MOFs–based plasmonic SERS platform for non-invasive and time-resolved monitoring of salivary uric acid

Wenli Chen,Renjie Li,Wenxi Wang,Kaixi Yin,Xiandeng Hou,Li Wu

A facilely fabricated Ag/Cu-TCPP was developed as a SERS substrate. • Saliva uric acid (UA) was quantified with 0.04 μM detection limit. • Synergy in molecular enrichment and EM enhancement improved SERS sensitivity. • Time-resolved monitoring of UA fluctuations in real saliva samples was achieved. Surface-enhanced Raman scattering (SERS) methods offer high sensitivity for uric acid (UA) detection, but efficient molecular enrichment and reliable analysis in complex biological matrices remain challenging. Here, we developed an Ag/Cu-TCPP SERS platform for noninvasive determination of UA in saliva. The platform combined the electromagnetic enhancement provided by Ag nanoparticles (Ag NPs) with the molecular enrichment capability of Cu-TCPP. Density functional theory calculations further indicated that UA can be enriched on Cu-TCPP through weak Cu···O quasi-coordination between the UA carbonyl oxygen and exposed Cu centers, accompanied by interfacial charge redistribution. Consequently, the platform achieved a low detection limit of 0.04 μM and a wide linear range of 0.1–1000 μM. Beyond conventional single-point determination, the platform enabled time-resolved assessment of salivary UA concentration, revealing temporal fluctuations under physiological and feeding-related conditions. These results highlight the potential of MOF-integrated SERS platforms for noninvasive monitoring of small-molecule biomarkers. Download: Download high-res image (242KB) Download: Download full-size image

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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Novel 2D/2D S-scheme heterojunction photocatalyst for peroxymonosulfate activation enables ciprofloxacin ultrafast degradation: High-efficiency photogenerated carrier transport

Yang Wang,Dong Xu,Xuan Yang,Jing-Hui He

Organic pollutants, such as ciprofloxacin (CIP), are ubiquitously detected in wastewater. However, their removal remains a challenge for conventional wastewater treatment technologies. Photocatalysis and peroxymonosulfate activation coupling are considered a promising strategy for the removal of recalcitrant organic pollutants. However, identifying optimal photocatalysts that can effectively couple with peroxymonosulfate activation and induce synergistic degradation of organic pollutants remains a challenge to be addressed. In this work, a novel S-scheme inorganic–organic heterojunction BiVO 4 /Cu-TCPP (BC) was fabricated. In situ X-ray photoelectron spectrum showed that the strong internal electric field of the S-scheme heterojunctions enabled efficient carrier transport. The generated photogenerated electrons could activate the peroxymonosulfate, which further promoted the separation of the carriers. The BC-vis-peroxymonosulfate system achieved 93.1% ciprofloxacin removal in 10 min with apparent rate constants k of 0.2426 min −1 , which is larger than most reported peroxymonosulfate systems. Electron paramagnetic resonance spectra and liquid chromatography mass spectrometry demonstrated that the synergistic coupling of S-scheme heterojunction with peroxymonosulfate activation significantly improved the catalytic activity of the reaction system and enabled rapid CIP removal via both radical and nonradical pathways. The BC-vis-peroxymonosulfate system demonstrated ultra-fast removal of other quinolone antibiotics and organic pollutants and strong environmental adaptability under various conditions, suggesting its great potential for practical application. This study provides new insights for the design of efficient S-scheme heterojunction coupled peroxymonosulfate activation for environmental remediation.

研究领域: 环境科学 · 材料科学 · 化学工程
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