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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 27 ·13207-13212 · IF 3.925

Preparation of a boronate affinity-functionalized metal–organic framework material for selective recognition and separation of glycoproteins at physiological pH

Baoyue Zhang,Xue Chen,Jianghua He,Bailin Guo,Sheng Bi,Feng Zhang,Miaomiao Tian

Glycoproteins play an important role in biological processes such as protein folding, information transmission, nerve conduction, and molecular recognition. Therefore, designing and developing an adsorbent with high adsorption capacity for glycoproteins are of great importance. In this study, a novel boronate affinity material (Zr-MOF@S-S@B) has been prepared by combining a Zr-MOF, a disulfide covalent bond (–S–S–), and 4-mercaptophenylboronic acid (4-MPBA) for the selective enrichment and elution of glycoproteins at physiological pH. The affinity between boronic acid and cis-diol leads to a high adsorption capacity of 625.5 mg g−1 to the composite material for ovalbumin (OVA). At the same time, Zr-MOF@S-S@B is reusable and has a large specific surface area. Furthermore, the material contains disulfide bonds that can release surface-binding glycoproteins specifically under physiological pH conditions, thus effectively avoiding the reduction of glycoprotein activity. The method is successfully used for the enrichment of OVA in egg white samples and protein powder, which has broad application prospects in the study of glycoproteins.

CAS / MDL: 2127-03-9
研究领域: 材料科学 · 生物化学 · 分析化学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2025 · IF 6.2

Fe,Zr-MOF Nanozyme-Enhanced Dual-Recognition System: Integrating Molecularly Imprinted Polymers and Aptamers for Colorimetric Detection of Chlorpyrifos

Chunqi Yu,Yingqi Wang,Ke Wang,Shuai Zhang,Xiaopeng Hu,Yiwei Liu,Jiajia Xi

Chlorpyrifos (CPF) poses severe environmental and health risks, driving the need for on-site monitoring tools. This study presents a novel dual-recognition colorimetric sensor for ultrasensitive detection of CPF by coimmobilizing molecularly imprinted polymers (MIPs) and aptamers onto bimetallic Fe,Zr-MOF composites. The resulting Fe,Zr-MOF/Apt/MIP hybrid synergistically merges the structural robustness of MIPs with the conformational specificity of aptamers, while also functioning as both a nanocarrier and a peroxidase mimic. Notably, CPF binding sterically hinders substrate diffusion to catalytic sites, enabling quantitative detection via dose-dependent inhibition of TMB oxidation. The optimized sensor exhibits exceptional performance: a broad linear range (1–120 ng mL–1), ultralow detection limit (0.105 ng mL–1), and high specificity against interferents. When validated with complex matrices (apples, pears, and cabbage), it achieved satisfactory recoveries (91.0–110.0%). This work establishes a field-deployable strategy for on-site pesticide monitoring in food and environmental safety.

CAS / MDL: 108-67-8
研究领域: 环境科学 · 分析化学 · 纳米技术 · 食品安全 · 生物传感器
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Catalysts · 2022 ·Vol. 13 ·期 1 ·40 · IF 4.501

Synthesis of Silicotungstic Acid/Ni-Zr-O Composite Nanoparticle by Using Bimetallic Ni-Zr MOF for Fatty Acid Esterification

Qiuyun Zhang,Mengmeng Hu,Jialu Wang,Yanting Lei,Yaping Wu,Qing Liu,Yongting Zhao,Yutao Zhang

In this study, the bimetallic Ni-Zr MOF-derived nickel-zirconium oxide (Ni-Zr-O)-impregnated silicotungstic acid (HSiW) nanocomposite catalyst (HSiW@Ni-Zr-O) was prepared via a hydrothermal procedure followed by a pyrolysis treatment, and its structural, morphological, and surface components and oxidation states were characterized by using XRD, FTIR, TPD-NH3, SEM, TEM, N2physisorption, and XPS analyses. Then, the nanocomposite catalysts were successfully applied to the esterification of oleic acid (OA) with methanol. According to its characteristics, the obtained HSiW@Ni-Zr-O-1 catalyst would generate larger pores, a higher acidity, and active interfaces at the calcining temperature of 300 °C. Therefore, HSiW@Ni-Zr-O-1 exhibits an excellent catalytic activity of 95.2% under optimal reaction conditions. Additionally, the catalyst can be reused with a good catalytic activity after nine cycles. This study highlights the opportunity of using bimetallic MOFs as precursors to the synthesis of highly nanoporous metal oxide, which supports the larger-industrial scale production of biofuels.Keywords:silicotungstic acid;MOF;nickel-zirconium oxide;esterification;biofuels;catalysis

研究领域: 化学工程 · 材料科学 · 能源科学
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MICROCHIMICA ACTA · 2026 ·Vol. 193 ·期 2 ·125 · IF 5.4

Rapid detection of probiotics in aquaculture using a fluorescent ligand sensor based on a Zr-MOF@Methylene blue composite

Ye Jiaqing,Shen Hao,Wu Jiacai,Feng Bin,Yu Shaoning

We constructed a novel fluorescent aptasensor based on Zr-MOF@MB composite material for rapid and highly sensitive detection of probiotics Bacillus subtilis and Lactobacillus acidophilus in shrimp aquaculture. The sensor utilizes a zirconium-based metal–organic framework to load the signal molecule methylene blue (MB) and immobilizes specific aptamers via Zr–O–P bonds to form a gating structure. In the presence of the target bacteria, a conformational change in the aptamer triggers the release of MB, leading to a decrease in fluorescence intensity, thereby enabling quantitative determination of the bacteria. The method completes detection within 30 min, with a linear range of 10¹ to 10⁷ CFU/mL and detection limit of 7 CFU/mL for B. subtilis and 10 CFU/mL for L. acidophilus . The developed sensor is simple to operate and highly sensitive, providing a reliable tool for effective monitoring of probiotics in shrimp aquaculture and offering new insights for the development of aptamer-based sensors for microbial detection in complex matrices.

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INORGANIC CHEMISTRY · 2026 · IF 4.6

Zr-MOF Nanoparticles Crafted from Conjugated Imidazolyl Carboxylic Acid Ligands for Sensitive Fluorescence Detection of 2,4-DNP and PNA

Fangfang Chen,Xiudu Zhang,Wensen Du,Chengcheng Ye,Meng Liu,Jun Du,Yonghong Ni

2,4-Dinitrophenol (2,4-DNP) and p-nitroaniline (PNA), as hazardous nitroaromatic explosives and persistent organic pollutants, exhibit high toxicity, nonbiodegradability, and carcinogenicity. Exposure to these compounds can cause severe health issues, including cardiovascular, neurological, and renal damage. In this study, a novel zirconium-based metal–organic framework (Zr-MOF, denoted as Zr-BPBI) was synthesized via a solvothermal reaction using the ligand 4,4′,4″,4‴-([1,1′-biphenyl]-4,4′-diyldi(1H-imidazole-2,4,5-triyl))tetrabenzoic acid (H4BPBI) and ZrCl4. The investigations showed that the original synthetic parameters, including surfactant concentration, acid type, reaction time, and temperature, could strongly affect the morphology, particle size, and fluorescence performance of the as-prepared Zr-BPBI. Interestingly, under excitation at 422 nm, the as-prepared Zr-BPBI nanoparticles (Zr-BPBI-NP) emitted blue luminescence centered at 502 nm, which demonstrated exceptional sensitivity toward PNA and 2,4-DNP with rapid fluorescence quenching responses (within 30 s for 2,4-DNP and 15 s for PNA). Simultaneously, common interfering substances (e.g., small molecules and ions) did not affect the above detection, suggesting high selectivity of the as-prepared Zr-BPBI-NP fluorescent probe. The corresponding limits of detection were 0.36 μM for 2,4-DNP and 0.4 μM for PNA. Obviously, the present Zr-BPBI-NP fluorescent probe is a new option for the highly sensitive and selective detection of PNA and 2,4-DNP in actual aqueous environments.

✓ 已验证 DOI PubMed 高影响因子
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

UiO-66(Zr) MOF enhances pH sensitivity of carboxymethyl fiber colorimetric films incorporated with anthocyanins for monitoring fish freshness

Weibo Lu,Huangwei Ye,Yike Zhu,Yuhan Li,Huan Li,Qing Shen,Jian Chen

The non-destructive, real-time, and visual assessment of fish freshness is crucial for maintaining food quality and safeguarding public health. In this study, a pH-sensitive and colorimetric enhancement film was developed using a carboxymethyl cellulose/anthocyanin/metal-organic framework (CMC-BA-UIO). The concentration of UIO-66 in the film-forming solution significantly influences the mechanical properties and ammonia responsiveness of the indicator film, with the CMC-BA/2.5%UIO-66 variant exhibiting optimal performance. When utilized for real-time fish freshness monitoring at 4 °C, the CMC-BA/2.5%UIO-66 indicator film demonstrated a distinct color transition from purple to yellow, which exhibited a strong correlation with the rot index (TVB-N) of the fish. These findings indicate that the developed indicator film has potential applications in intelligent packaging for monitoring food shelf life, providing a visual alert to producers and consumers regarding food spoilage.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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FUEL · 2025 · IF 7.5

Post-synthetic acid treatment of aqueous synthesized bimetallic Ce/Zr MOF-801 enables efficient oxidative desulfurization of model fuels

Liang Chu,Zhaokun Wang,Zhaohui Liu,Teng Zhao,Liyan Wang,Mu Yang,Ge Wang

Host-guest catalysts are promising for tailored applications but require innovative synthesis strategies. Herein, we report the first ambient aqueous-phase synthesis of bimetallic Ce/Zr MOF-801, followed by acid post-treatment. Utilizing defect engineering, Ce species are preferentially exposed within the robust Zr-MOF-801 substrate. This structural modification substantially enhances the host–guest catalyst’s oxidative desulfurization (ODS) performance. We systematically investigate synthesis parameters, spatiotemporal yield, and defect characterization, and refines catalytic conditions. Post-acid-treated Ce/Zr-MOF-801-H displays augmented external surface area (189 m 2 g −1 ), and exposed acidic sites while upholding the outstanding intrinsic stability of the Zr-MOF-801 substrate. Under optimal conditions (60 °C, 6 min), Ce/Zr-MOF-801-H completely eliminates dibenzothiophene (1000 ppm S), with a turnover frequency of 39.3 h −1 and catalytic activity of 53.2 mmol g −1 h −1 , far surpassing Zr-UiO-66-H. It maintains a desulfurization rate of 96.6% after five cycles. FTIR spectroscopy, quenching experiments, and ESR spectroscopy reveal that the exposed Ce sites serve dual roles: (1) activating the substrate by reducing the electron density of sulfur atoms and (2) facilitating H 2 O 2 into hydroxyl and superoxide radicals, driving ODS. This strategy not only advances industrial ODS applications but also sheds light on the synthesis of MOF-based host–guest catalysts.

研究领域: 材料科学 · 催化化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

A high-efficiency electrochemical biosensor based on AuNPs@Zr-MOF and enzyme-free cascade signal amplification for microRNA detection

Xin Xie,Peng Chen,Jingxi Wang,Ding Wang,Daxiu Li,Beibei Kou,Wenjiao Zhou

Herein, a novel electrochemical biosensor on the basis of MB/AuNPs@Zr-MOF signal probe and enzyme-free cascade signal amplification was fabricated for the ultrasensitive detection of colorectal cancer (CRC)-associated miR-92a-3p. Impressively, compared with the traditional electrochemical probes, MB/AuNPs@Zr-MOF not only exhibits high loading for electroactive substances, but also shows enhanced electronic conductivity, thereby generating stable and high electrochemical signal. Meanwhile, under the assistance of the target-induced enzyme-free cascade signal amplification including multicomponent nuclease (MNAzyme) recycle catalytic and catalytic hairpin assembly (CHA), the sensitivity of proposed biosensor was further improved. Additionally, the DNA tetrahedral scaffold (TDNs) was served as an electrode support interface, which could greatly reduce the non-specific adsorption and improve the analytical performance. As a result, the developed biosensor enabled the miR-92a-3p with a detection limit as low as 0.36 fM. This work provided an efficient method to increase the sensitivity and the stability of electrochemical sensing platforms, showing great potential for the detection of biomarker and disease diagnosis.

研究领域: 生物传感器 · 纳米技术 · 电化学 · 癌症诊断 · 分子生物学 · 生物分析化学
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ACS Sustainable Chemistry & Engineering · 2019 · IF 6.97

Dual-Emitting EY@Zr-MOF Composite as Self-Calibrating Luminescent Sensor for Selective Detection of Inorganic Ions and Nitroaromatics

Yankun Li,Zihao Wei,Ye Zhang,Zhifen Guo,Dashu Chen,Peiyun Jia,Peng Chen,Hongzhu Xing

A dual-emitting dye@MOF composite has been synthesized by incorporating a fluorescent dye eosin Y (EY) within a UiO-type zirconium-based metal–organic framework (Zr-MOF) through a synthetic encapsulation method. The Zr-MOF prevents the aggregation of EY molecules and keeps EY molecules stably included after synthesis. As expected, an energy transfer from Zr-MOF to EY molecules occurred because of the good overlap between the emission of Zr-MOF and the absorption of EY. As a result, the obtained EY@Zr-MOF composite features a weak blue emission at 446 nm and a strong yellow emission at 553 nm. By using the relative height of the two emission peaks replacing absolute peak height as detecting signals, EY@Zr-MOF composite acts as a self-calibrating luminescent sensor for selectively detecting Fe3+, Cr2O72–, and 2-nitrophenol. Furthermore, the observed fluorescence responses of the composite toward analyte are highly stable and reversible after recycling experiments. To the best of our knowledge, this is the first example of a dye@MOF-implicated self-calibrating sensor for Fe3+, Cr2O72–, and 2-nitrophenol detection.

CAS / MDL: 17372-87-1 15086-94-9
研究领域: 材料科学 · 分析化学 · 环境科学
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Rational Design of a Zr-MOF@Curli-Polyelectrolyte Hybrid Membrane toward Efficient Chemical Protection, Moisture Permeation, and Catalytic Detoxification

Jing Liu,Heguo Li,Bin Yan,Chao Zhong,Yue Zhao,Xuan Guo,Jinyi Zhong

Developing high-performance protective materials is important for soldiers and civilians who are exposed to the atmosphere of highly toxic chemical warfare agents (CWAs). Polyelectrolyte membranes are promising candidates with excellent chemical resistance and moisture permeability, but they cannot efficiently degrade CWAs. Here, we design and prepare a hybrid membrane through in situ growth of catalytically active zirconium-based metal–organic frameworks (Zr-MOFs) on a polyelectrolyte membrane mediated by biofilm-inspired curli nanofibers (CNFs). Superior to the bare polyelectrolyte membrane, the prepared MOF-808@CNF-PQ hybrid membrane exhibits improved rejection of the nerve agent simulant dimethyl methyl phosphonate (DMMP) vapor and permeation of the water vapor by 113 and 45%, respectively. The water/DMMP selectivity of the hybrid membrane reaches 498.6, approximately 13 times that of the commercial polyelectrolyte membrane Nafion 117. In addition, the hybrid membrane possesses appreciable catalytic activity for the hydrolysis of the nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP) with a half-life of ∼38 min. Nanomechanical characterization results based on atomic force microscopy (AFM) techniques demonstrate the critical role of CNFs in mediating Zr-MOF nucleation and the dominant effect of electrostatic interactions on self-assembly of CNFs on polyelectrolyte base. It is also confirmed that the Zr-MOF toppings serve as the key components in physically adsorbing and chemically degrading the DMNP molecules through multiple strong intermolecular interactions. Our work offers a rational strategy to develop advanced membranes toward efficient chemical protection, moisture permeation, and catalytic detoxification against CWAs.

研究领域: 材料科学 · 化学工程 · 环境科学 · 生物技术
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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 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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