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Zr-MOF
ACS Sensors · 2023 · IF 8.9

Zr-MOF-Induced Smart Accumulation Enables Surface-Enhanced Raman Spectroscopic Detection of Dioxin at ppt Level in Food Samples

Jie Cheng,Bo-en Li,Jinghui He,Peilong Wang

The fast and economical detection of trace polychlorinated dibenzo-p-dioxins (PCDDs) in food samples by current mass spectrum-based methods is hindered by tedious sample preparation and bulky & expensive analytical instruments. Surface-enhanced Raman spectroscopy (SERS) successfully detects many organic pollutants in foods but not dioxins because the employed metal nanoparticles weakly adsorb hydrophobic PCDDs. Herein, we report the detection of PCDDs in milk with SERS for the first time using a bifunctional substrate consisting of Au nanoparticles embedded in a zirconium-based metal–organic framework shell (AuNP/Zr-MOF). 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD), as the most toxic PCDD, is detected as low as 1.2 parts per trillion (ppt) in real milk samples with massive interfering substances in 30 min, which is the lowest among all reported methods. The aromatic rings of Zr-MOF promote the smart accumulation of TCDD through π–π interactions, and Au–Cl interactions drive TCDD onto Au surfaces. Zr-MOF shells with pore sizes of 12.7 and 20 Å block the accessibility of larger interfering molecules. A one-step apparatus and protocol are established to be superior to traditional methods in terms of time and cost. This work provides new insight into a rational screening method for the detection of persistent organic pollutants in a real sample matrix.

CAS / MDL: 10026-11-6
研究领域: 分析化学 · 食品安全 · 环境科学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2023 ·Vol. 415 ·期 19 ·4767-4777 · IF 4.3

Boronic acid and fructose-1,6-diphosphate dual-functionalized highly hydrophilic Zr-MOF for HILIC enrichment of N-linked glycopeptides

Zhou Xiaoyu,Zhang Hongyan,Wang Li,Wu Ren’an

The HILIC enrichment is a greatly compatible strategy for the extraction of glycopeptides in proteomics. Herein, a boric acid and fructose-1,6-diphosphate (FDP) dual-functionalized Zr-based metal–organic framework material UIO-PBA&FDP (UIO is the abbreviation for the University of Oslo, and PBA is the abbreviation for carboxy phenylboronic acid) was synthesized, characterized with the desirable excellent hydrophilicity and thus was explored for the enrichment of N-linked glycopeptides utilizing the HILIC interaction between the glycopeptides and the hydrophilic UIO-PBA&FDP at a high level of ACN concentration. A total of 359 N-linked glycopeptides corresponding to 104 glycoproteins were identified from only 1 μL of digested human serum by the enrichment of UIO-PBA&FDP, which showed a superiorly high coverage of the identified glycopeptides. The dual hydrophilic functionalized UIO-PBA&FDP could be an efficient HILIC material for the enrichment of N-linked glycopeptides from complex biological samples.

CAS / MDL: 10026-11-6 217305-49-2
研究领域: 蛋白质组学 · 分析化学
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ACS Nano · 2019 · IF 13.903

Quercetin-Modified Metal–Organic Frameworks for Dual Sensitization of Radiotherapy in Tumor Tissues by Inhibiting the Carbonic Anhydrase IX

Tengchuang Ma,Yunduo Liu,Qiong Wu,Lifang Luo,Yali Cui,Xinghua Wang,Xiuwei Chen,Longfei Tan,Xianwei Meng

The development of multifunctional nanoscale radiosensitizers has attracted a tremendous amount of attention, which can enhance the radiosensitization of tumor tissues and reduce unnecessary damage to the surrounding organs. However, the persistent hypoxia environment within the tumor limits their applications in radiotherapy. In this paper, a stable nanocomposite was engineered to overcome the hypoxia properties by using 1,4-benzenedicarboxylic acid produced from a Zr-MOF as a carbonic anhydrase IX (CA IX) inhibitor and quercetin (QU) as a radiosensitizer. QU was encapsulated into the Zr-MOF structure to achieve a synergetic dual sensitization therapy. Zr-MOF-QU exhibits an excellent potential of radiotherapy sensitization characteristics in vitro and in vivo from the γ-H2AX immunofluorescence staining and colony assays. The mechanisms of alleviating hypoxia-induced resistance and sensitizing tumor tissues to improve cell apoptosis from radiation were found to suppress CA IX expressions by the decomposition product from Zr-MOF and boost the sensitivity by QU in radiation therapy. Moreover, there was no significant systemic toxicity during the treatment, and the therapeutic outcome was assessed in animal models. Therefore, our results demonstrate a promising cancer treatment approach in the radiation field.

CAS / MDL: 117-39-5
研究领域: 癌症治疗 · 纳米技术 · 放射生物学 · 药学
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ADVANCED FUNCTIONAL MATERIALS · 2025 · IF 19

Defect Engineering Zr-MOF-Endowed Activity-Dimension Dual-Sieving Strategy for Anti-acid Recognition of Real Phosphoryl Fluoride Nerve Agents

Runqiang Zang,Yuan Liu,Yihang Wang,Lu Feng,Yuansheng Ge,Molin Qin,Yuwan Du,Jinliang Ning,Xiaowei Ma,Xincun Dou

Defect-engineering-involved metal-organic frameworks (MOFs) have been highly valued in many fields due to the enhanced porosity and abundant active sites, but how the systematic modulation on deficiency influencing fluorescent sensing performance is still in its infancy. Here, systematic defect-engineering of MOF-525 is used to modulate the exposure of zirconium (Zr) clusters and the sieving capability of inner channels, enabling precise fluorescent sensing of phosphoryl fluoride nerve agents with specific chemical activity and molecular dimensions. Controllable defects transformed the localized emission of porphyrin into ligand-metal charge transferring (LMCT) due to the gradual loss of the ligand molecules, which is interrupted upon the coordination of nerve agents, triggering a red turn-on fluorescence. Thus, the defective MOF-525 with 60% deficiency effectively discriminates the phosphoryl fluoride nerve agents (e.g., sarin, soman) from similar substances (e.g., tabun, venomous agent X) due to synergistic sieving effect of chemical activity and molecular dimension. It exhibits highly sensitive (0.96 n m /3.8 ppb), rapid (<1 s) response toward target nerve agents and is robust to the environmental interference from the acidic, humid and common fluorescent substances. This work enhances understanding of defect-engineering MOFs and the correpsonding luminescent behavior, paving a new avenue for sensing strategy of trace real nerve agent vapor.

研究领域: 材料科学 · 化学
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ACS Sustainable Chemistry & Engineering · 2025 · IF 7.3

Facile Preparation of Mixed-Matrix Membrane for Highly Selective Separation of CO2 via a Defected Zr-MOF Fluorination-Modified Strategy

Jiacheng Zhang,Xi Sun,Junhao Xin,Li Wang,Yong Fan,Jifu Zheng,Shenghai Li,Jianing Xu,Nanwen Li,Suobo Zhang

To address increasing climate deterioration, it is of great value to prepare highly permselective separation membranes for CO2 enrichment and separation. In this study, zirconium-based metal-organic frameworks (Zr-MOFs) containing defective structures (defected-UiO-66-NH2, D-UN) with a high volume yield (12 g L–1 in a single batch) were prepared at room temperature for the first time using a simple green-synthesis strategy. After the modification with pentafluorobenzaldehyde, the fluorine-containing D-UN (named F-g-UN) nanoparticles showed the characteristics of local and dense distribution of fluorine elements. Due to the optimized CO2 affinity and improved dispersion of fluorination modification, the prepared mixed-matrix membrane (MMM) F-g-UN@AO-PIM-1 achieved synergistic improvement in CO2 permeability and selectivity, exceeding the 2008 Robeson upper bound (CO2 664.1 Barrer and CO2/CH4 34.2) and the 2018 binary CO2/CH4 mixed-gas upper bound (CO2/CH4 28.7). The substantial cause was the introduction of fluorine species, verified by relevant experiments and mechanism analyses such as CO2 adsorption. This work proves the feasibility of using crystal defect engineering and post-treatment strategies to enhance separation functions and offers new insights into designing efficient and low-cost MMMs for gas separation, promoting their application in separation membranes including but not limited to gas separation.

CAS / MDL: 5216-17-1 7647-01-0
研究领域: 材料科学 · 环境科学 · 化学工程
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LWT-FOOD SCIENCE AND TECHNOLOGY · 2025 · IF 6.6

Synergizing Polydopamine-Modified Electrodes with DNA-Anchored UIO-66(Zr) MOF for Ultrasensitive Detection of Horsemeat Adulteration in Camel Meat

Jianmei Li,Yuting Yin,Haiyu Li,Zongyao Zhao,Mengqin Xiang,Yong Tang,Qi Sun

The escalating economic and ethical concerns associated with camel meat adulteration using cheaper horsemeat necessitate the development of rapid, on-site detection technologies that overcome the limitations of conventional laboratory-based methods. In this study, a portable electrochemical DNA biosensor was fabricated by integrating a polydopamine (PDA)-modified screen-printed carbon electrode (SPCE) with a nucleic acid-functionalized UIO-66(Zr) metal-organic framework (MOF). The PDA coating facilitated stable, covalent immobilization of DNA capture probes through Schiff base reactions, while the UIO-66(Zr) MOF functioned as a high-capacity signal amplifier owing to its large surface area and intrinsic redox activity. This synergistic architecture enabled ultrasensitive detection, achieving a limit of 3.57 pmol/L for horsemeat DNA and 0.5 g/kg adulteration in camel meat blends—significantly surpassing the performance of existing detection methods. The biosensor exhibited excellent specificity by distinguishing single-base mismatches, along with high reproducibility (RSD = 4.12%), operational stability over 15 days, and accurate recovery rates ranging from 91.7% to 112.4% in spiked samples. Its disposable electrode format, cost-effectiveness, and compatibility with portable potentiostats underscore its strong potential for on-site meat authentication. Overall, this work provides a practical and scalable solution to combat meat fraud in resource-limited settings and establishes a versatile MOF-electrode nanoassembly platform for advanced food safety monitoring.

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Journal of Analysis and Testing · 2026 · IF 9.4

Zr-MOF/MnO2 Nanozyme with Chelation-Regulated Acitivity: From Sensitive Colorimetric Detection to Smartphone-Readable Paper-Based Assay for Glyphosate

Huang Shan,Liu Xinqi,Huang Aoxiang,Zhuo Yongxiu,Huang Tiantian,Fang Yi,Wei Fuxiang,Xiao Qi

As one of the most extensively applied herbicides globally, glyphosate (GLY) is frequently detected in food and water matrices, raising substantial concerns regarding its potential harm to human health. Addressing this challenge calls for analytical platforms that offer both reliable performance and operational convenience. In this work, a GLY-responsive nanoenzyme was developed by hybridizing Zr-based metal–organic frameworks (Zr-MOF) with manganese dioxide (MnO 2 ). The system capitalizes on the strong chelation between GLY and metal centers, which destabilizes the nanozyme structure and consequently modulates its catalytic activity toward colorimetric readout. The resulting composite enables precise quantification of GLY in solution and can be readily incorporated into paper substrates to support visual, user-friendly sensing. In solution format, the assay achieves a linear response over 0.001–10 mg/mL with a limit of detection (LOD) of 0.9 μg/mL, whereas the paper-based counterpart operates within 0.05–20 mg/mL and affords an LOD of 0.03 mg/mL, making it well-suited for cost-effective field applications. Both detection formats were validated using GLY-spiked fruit and water samples. Recovery rates fell between 90.5% and 110% for the solution-based method, and between 95.3% and 105% for the paper-based strips, with relative standard deviations (RSDs) of less than 15% and 7%, respectively, indicating satisfactory accuracy and reproducibility. Overall, this work presents a versatile strategy that bridges high analytical precision with straightforward operation, meeting the demands of both routine monitoring and point-of-use testing by non-professionals.

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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Zr-MOF encapsulated-magnetic beads-based fast and efficient conjugation strategy for sensitive immunoassays and early diagnosis of rheumatoid arthritis

Meiyun Shang,Juan Hu,Mengjia Shi,Yunpeng Fan,Yuan Zou,Yong Wang,Jinhong Guo,Cuiping Mao

Anti-cyclic citrullinated peptide (anti-CCP) antibodies are key biomarkers for rheumatoid arthritis and vital for its early diagnosis and monitoring. Conventional chemiluminescence immunoassays (CLIA) rely on streptavidin-functionalized magnetic beads (SA-MBs), which suffer from limited binding capacity and require labor-intensive chemical conjugation steps. Here, we report a MBs carrier modified with zirconium (Zr)-based metal-organic frameworks (MB@MOF), enabling rapid and efficient SA functionalization via one-step physicochemical adsorption. Compared to the conventional EDC/NHS method, our approach shortens the modification time by at least sixfold and eliminates the need for chemical crosslinkers. The MB@MOF carrier was constructed by anchoring Zr-MOF nanoparticles, synthesized with TCPE as the organic ligand, onto MBs. This carrier supports stable and dense SA loading while preserving native SA activity, thereby allowing highly sensitive detect anti-CCP antibodies. The developed MB@MOF carrier-based CLIA method achieved a detection limit of 0.1 RU/mL and a linear range of 0.5–200 RU/mL. Clinical validation using 36 clinical serum samples showed strong agreement with results from standard clinical analyzers, achieving an overall diagnostic accuracy of 91.7 %. This strategy significantly simplifies the assay workflow and holds strong potential for high-performance and rapid diagnostics of rheumatoid arthritis in clinical application.

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FOOD CHEMISTRY · 2025 · IF 9.8

Electrochemical aptasensor based on Zr-MOF@Ag nanocomposite for the rapid detection of chloramphenicol in honey, milk and lake water

Zhaoyuan He,Chengxiang Fu,Shuling Meng,Jiaqi Luo,Jieke Qiu,Jianing Huang,Xiaoge Duan,Jiakang He,Jinzi Wang,Hailan Chen

Despite global regulatory bans due to its hematotoxic effects, chloramphenicol (CAP) persists as an illicit veterinary antibiotic in food animals owing to its low cost and broad-spectrum efficacy. Current analytical methods to monitor CAP residues in animal-derived foods face critical limitations: instrumental analyses rely on expensive equipment and specialized operations, while immunoassays lack sufficient sensitivity for regulatory compliance. Here, we develop an ultrasensitive electrochemical aptasensor leveraging a zirconium MOF‑silver nanocomposite (Zr-MOF@Ag), which effectively enhances charge transfer and facilitates aptamer immobilization. Under optimized detection conditions, the electrochemical aptasensor yielded a wide linear range of 1–100 ng/mL (r 2  = 0.990) with an ultralow limit of detection (LOD) of 9.94 pg/mL. Additionally, the sensor showed no cross-reactivity with other veterinary drugs, with RSD of 1.00–0.94 % for intra- and inter-batch repeatability, respectively. The recovery rates of spiked samples ranged from 95.1 to 108.4 %.

CAS / MDL: 50-18-0
研究领域: 分析化学 · 食品安全 · 环境科学 · 纳米材料 · 电化学
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Journal of Environmental Chemical Engineering · 2025 · IF 7.2

Bifunctional Zr-MOF grafted by dicationic ionic liquid and porphyrin for enhanced Lewis acid–base catalysis of cocatalyst-free CO2 cycloaddition

Fangfang Li,Jingya Kong,Ziyuan Fang,Laili Wan,Jing Gu,Changchun Ji,Ying-Hua Zhou

The catalytic transformation of epoxides into cyclic carbonates offers a promising strategy to mitigate excessive CO 2 emissions while producing valuable chemicals. However, attaining high catalytic efficiency and selectivity with MOF-based catalysts under mild conditions continues to be a significant challenge. Additionally, many existing catalytic systems rely on cocatalysts or solvents, compromising sustainability and practicality. In this study, a series of alkyl chain-tunable Zr-MOF catalysts, denoted as TCPP-UiO-66-PDC-DIL(R) (R = Et, Pr, Bu, Pe), were synthesized via a two-step approach. Initially, Zr 4 + ions were coordinated with meso-tetra(4-carboxyphenyl) porphine (TCPP) and 2,5-pyridine dicarboxylic acid (PDC) to create TCPP-UiO-66-PDC. Subsequently, dicationic ionic liquids (DIL) with varying alkyl chains lengths were decorated through post-synthetic modification. Their catalytic performance was assessed for CO 2 -epoxide cycloaddition without the use of cocatalysts or solvents. Among them, TCPP-UiO-66-PDC-DIL(Bu) exhibited the best catalytic performance, achieving a 98 % yield for producing chloropropene carbonate at a low CO 2 pressure (1.0 bar) within 12 h. This exceptional activity was attributed to the synergistic interplay of Lewis-acidic Zr 4+ nodes for epoxide activation, the porphyrin moiety of the TCPP ligand enhancing CO 2 adsorption, and the strong nucleophilicity of bromide anions in DIL to facilitate the halide ion-mediated nucleophilic attack on the epoxide-CO 2 adduct. Additionally, the catalyst demonstrated superior universalities toward other substrates and recyclability. These findings expand the potential of the multifunctional MOF-based heterogeneous catalysts, enhancing their efficiency and sustainability for use in CO 2 conversion.

CAS / MDL: 13520-92-8
研究领域: 催化化学 · 材料科学 · 环境化学 · 绿色化学 · 无机化学 · 有机合成
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Biosensors-Basel · 2025 ·Vol. 15 ·期 5 ·291 · IF 5.6

A Dual-Signal Electrochemiluminescence Sensor for Kanamycin Detection Based on a Self-Enhanced Zr MOF and Single Co-Reactant Competition Mechanism

Yawen Zhu,Xuemei Wang,Zhiyong Yan,Feifei Zhang,Jianfei Xia,Lili Lv,Zonghua Wang

The dual-signal output self-calibration mode reduces the false positive and negative signals of electrochemiluminescence (ECL) aptamer sensors. A competitive dual-signal ECL platform was designed for the ultrasensitive detection of kanamycin (KAN) using a zirconium metal–organic framework (Zr MOF) and Luminol as ECL emitters. To enhance the ECL efficiency, a co-reactant (polyethyleneimine, PEI) was covalently bound to the Zr MOF to achieve self-enhanced ECL. Based on the selective interaction between KAN and its aptamer, the Luminol/KAN/Zr MOF-PEI “sandwich” structure was immobilized on the electrode surface. The competition for PEI between emitters increased the Luminol ECL signal and decreased the Zr MOF’s ECL signal. The ratio in ECL signals between the two competitive emitters enabled the quantitative analysis of KAN, achieving a detection limit as low as 7.86 × 10−4ng/mL. This study elucidated the synergistic mechanism between self-enhanced ECL and ECL competition, offering a novel approach for constructing dual-signal ECL sensors using a single co-reactant.

CAS / MDL: 25952-53-8 74124-79-1
研究领域: 分析化学 · 生物传感 · 环境科学
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JOURNAL OF SEPARATION SCIENCE · 2025 ·Vol. 48 ·期 7 ·e70221 · IF 2.8

Lightweight Spherical Cellulose Aerogels With High Zr-MOF Loadings for the Facile Extraction of Benzodiazepines From Human Urine and Hair Samples

Suling Zhang,Hengli Liu,Xiaoyang Li,Weixuan Yao,Jianbo Ying,Ting Lü,Dong Zhang,Hongting Zhao,Ying Pan

A facile dispersive micro-solid phase extraction (D-μ-SPE) method that uses spherical cellulose aerogels is proposed herein for the trace detection of seven benzodiazepines in biological samples. Zirconium metal–organic framework (MOF) particles were dispersed in the cellulose aerogels to improve the extraction efficiency. The prepared lightweight spherical aerogels (diameter of approximately 2 mm) were easily collected from the solution using a disposable dropper, overcoming the difficult recycling of powdered MOFs. The effect of the MOF loading (39, 56, and 66 wt%) and the organic ligand (terephthalic acid, 2-aminoterephthalic acid, and 4,4′-biphenyldicarboxylic acid) in the Zr-MOF on the extraction ability of the hybrid aerogels towards benzodiazepines was studied. The hybrid aerogel with a UiO-67 loading of 66% showed the best extraction performance primarily because of the enhanced surface area, pore volume, and π–π stacking interactions. Moreover, the UiO-67/cellulose aerogel spheres were mechanically stable and showed reusability for at least eight consecutive extraction cycles. The main factors affecting extraction, such as solution pH, extraction time, type and volume of desorption solvent, and desorption time, were also examined. Under the optimal conditions, the limits of detection ranged from 0.01 to 0.03 µg/L, and the limits of quantification ranged from 0.02 to 0.10 µg/L. The recoveries were 81.8%–104.2% for urine samples and 81.5%–99.5% for hair samples. The results suggest that the spherical aerogel-based D-μ-SPE is a simple and effective method for the quantification of benzodiazepines in biological samples.

CAS / MDL: 83512-85-0
研究领域: 分析化学 · 材料科学 · 生物医学
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