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MOLECULES · 2020 ·Vol. 25 ·期 4 ·897 · IF 3.267

NH2-MIL-53(Al) Polymer Monolithic Column for In-Tube Solid-Phase Microextraction Combined with UHPLC-MS/MS for Detection of Trace Sulfonamides in Food Samples

Qian-Chun Zhang,Guang-Ping Xia,Jun-Yi Liang,Xiao-Lan Zhang,Li Jiang,Yu-Guo Zheng,Xing-Yi Wang

In this study, a novel monolithic capillary column based on a NH2-MIL-53(Al) metal–organic framework (MOF) incorporated in poly (3-acrylamidophenylboronic acid/methacrylic acid-co-ethylene glycol dimethacrylate) (poly (AAPBA/MAA-co-EGDMA)) was prepared using an in situ polymerization method. The characteristics of the MOF-polymer monolithic column were investigated by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, Brunauer-Emmett-Teller analysis, and thermogravimetric analysis. The prepared MOF-polymer monolithic column showed good permeability, high extraction efficiency, chemical stability, and good reproducibility. The MOF-polymer monolithic column was used for in-tube solid-phase microextraction (SPME) to efficiently adsorb trace sulfonamides from food samples. A novel method combining MOF-polymer-monolithic-column-based SPME with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was successfully developed. The linear range was from 0.015 to 25.0 µg/L, with low limits of detection of 1.3–4.7 ng/L and relative standard deviations (RSDs) of < 6.1%. Eight trace sulfonamides in fish and chicken samples were determined, with recoveries of the eight analytes ranging from 85.7% to 113% and acceptable RSDs of < 7.3%. These results demonstrate that the novel MOF-polymer-monolithic-column-based SPME coupled with UHPLC-MS/MS is a highly sensitive, practical, and convenient method for monitoring trace sulfonamides in food samples previously extracted with an adequate solvent.Keywords:monolithic capillary column;metal-organic framework;sulfonamides;solid-phase microextraction;ultra-high performance liquid chromatography-tandem mass spectrometry

CAS / MDL: 78-67-1
✓ 已验证 产品关联 DOI PubMed 高影响因子
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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 2 ·1-10 · IF 5.479

An amino-modified metal-organic framework (type UiO-66-NH2) loaded with cadmium(II) and lead(II) ions for simultaneous electrochemical immunosensing of triazophos and thiacloprid

Yang Yong,Cheng Jingli,Wang Biao,Guo Yirong,Dong Xiaowu,Zhao Jinhao

A method is described for simultaneous voltammetric determination of the pesticides triazophos (TRS) and thiacloprid (THD). A glassy carbon electrode (GCE) was modified with a metal-organic framework (type UiO-66-NH 2 ) which has a large specific surface (1018 m 2 ·g −1 ) and contains large amounts of Cd(II) and Pb(II) ions, with adsorption capacities of 230 and 271 mg·g −1 , respectively. The antigen-loaded particles were then bound to antibody, magnetically separated, and analyzed by square wave voltammetry to give signals for Cd(II) and Pb(II) at −0.82 and − 0.56 V (vs. Ag/AgCl) for TRS and THD, respectively. Under optimized conditions, the method has a wide linear range (0.2–750 ng·mL −1 ) and low detection limits (0.07 and 0.1 ng·mL −1 at a S/N of 3 for TRS and THD, respectively). It is perceived that this assay represents a useful tool for simultaneous determination of multiple pesticide residues. The method has a wide scope in that may be extended to monitoring of other small organic pollutants by changing the types of metal ions and by using other antibodies. Schematic presentation of an amino-modified metal-organic framework (type UiO-66-NH 2 ) loaded with Cd(II) and Pb(II) ions for simultaneous electrochemical immunosensing of triazophos (TRS) and thiacloprid (THD). It is based on the fabrication of antigen (Ab)-immobilized UiO-66-NH 2 -based signal tags (a), and of an antibody (Ab)-immobilized magnetic bead (MB-COOH)-based capture probes (b).

✓ 已验证 DOI PubMed 高影响因子
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Foods · 2022 ·Vol. 11 ·期 19 ·3130 · IF 5.561

Development of a Sensitive and Fast Determination Method for Trace Carbaryl Residues in Food Samples Based on Magnetic COF (TpPa-NH2)@Fe3O4 Nanoparticles and Fluorescence Detection

Juanli Du,Hao Wu,Xu Jing,Yonghe Yu,Zhisheng Yan,Jianhai Zhang

Developing a simple and effective method for measuring carbaryl residues in food is urgent due to its widespread use and the associated health risks in agriculture, as well as various defects in existing detection techniques. The COF (TpPa-NH2)@Fe3O4nanocomposite (amino modification) was synthesized via a two-step method and used as an adsorbent for the extraction of carbaryl from food samples in this study. The results indicated that COF (TpPa-NH2)@Fe3O4can rapidly and successfully capture carbaryl directly from samples via π–π stacking and hydrophobic interactions, achieving maximum adsorption within 5 min under a small adsorbent quantity using a fluorescence spectrophotometer. Under the optimized conditions, carbaryl exhibited good linearity in the range of 0.2–120 µg·kg−1, and the limit of detection was 0.012 µg·kg−1. The recoveries of the samples were 96.0–107.4%. This method has broad application prospects for the monitoring of carbaryl in food.Keywords:magnetic solid-phase extraction;COF (TpPa-NH2)@Fe3O4nanocomposite;fluorescence spectroscopy;carbaryl;food samples

✓ 已验证 DOI PubMed 高影响因子
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CHEMOSPHERE · 2025 · IF 8.1

Efficient degradation of aflatoxin B1 and ochratoxin A using dual Z-scheme Sr2MgSi2O7: Eu2+, Dy3+/BiVO4/NH2-UiO-66 heterojunctions with round-the-clock photocatalytic activity

Si-yuan He,Wei Wen,Peng Wu,Zhe Meng

Developing a green and efficient technology for decomposing aflatoxin B 1 (AFB 1 ) and ochratoxin A (OTA) in grains has important theoretical value and application prospects for ensuring food safety. A dual Z-scheme ternary heterojunction photocatalyst, Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ /BiVO 4 /NH 2 -UiO-66 (SBN), was prepared via a self-assembling hydrothermal approach. The SBN heterojunction photocatalyst exhibits round-the-clock photocatalytic activity due to the intrinsic light source of Sr 2 MgSi 2 O 7 : Eu 2+ , Dy 3+ (SMS). Dual Z-scheme mechanism was proposed and validated through detailed analysis of quenching experiments, ESR spectra, band arrangement, and charge transfer processes. The dual Z-scheme mechanism not only promotes the effective transfer and separation of photo generated charge carriers during charge carrier transport, but also maintains significant reduction and oxidation potentials. SBN photocatalyst exhibits stable and persistent photocatalytic performance, significantly enhancing the degradation efficiency of AFB 1 and OTA under all-weather conditions. Experimental data shows that the removal rate of AFB 1 increased from 69.60 % after 60 min of illumination to 83.9 % after 4 h of turning off the light source; At the same time, the removal rate of OTA increased from 64.8 % to 78.1 %. •O 2 − and •OH were identified as key active species in photocatalytic reactions. Based on the analysis of AFB 1 and OTA degradation intermediates and the prediction of degradation sites using density functional theory (DFT), degradation pathways for AFB 1 and OTA were proposed. Collectively, these findings suggest a highly promising practical approach for the detoxification of mycotoxins in grain commodities.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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FOOD CHEMISTRY · 2025 · IF 9.8

Dual-mode fluorescence and colorimetric immunosensing platform based on Au/Pt NPs@NH2-MIL-53(Al) composite for effective detection of enrofloxacin in animal-derived foods

Hongbo Li,Hao Wang,Meiyi Cao,Xing Tong,Shuo Wang,Mingfei Pan

The fluoroquinolone-enrofloxacin (ENR) residue in animal-derived foods poses a significant threat to human health, thereby necessitating developing precise, efficient, and user-friendly detection methods. This study developed a dual-mode fluorescence-colorimetric immunosensing platform using the composite of bimetallic nanoparticles integrated with metal-organic frameworks (Au/Pt NPs@NH 2 -MIL-53(Al)). The Au/Pt NPs with biocompatibility and peroxidase-like activity were modified onto fluorescent NH 2 -MIL-53(Al) and conjugated with Ab 2 to construct signal probes. The platform enables dual-mode quantitative analysis through the competitive binding of ENR and ENR-BSA conjugate to signal probes. It demonstrated a wider linear range (0.08–180 ng/mL) and high sensitivity [LOD: 0.068 ng/mL (fluorescence), 0.066 ng/mL (colorimetric), and 0.074 ng/mL (smartphone-assisted color recognition)]. In real sample analyses, the recoveries ranged from 86.7 % to 106.7 %, with satisfactory stability (RSD ≤ 4.4 %, n  = 3). The dual-signal mode facilitates results self-calibration, enhancing reliability, while smartphone-assisted color recognition enables on-site, convenient screening, offering great potential for ENR detection in complex food matrices.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2024 · IF 20.2

Simultaneously uranium reduction and organics degradation by a drivingpowers enhanced photocatalytic fuel cell based on a UiO-66-NH2 derived zirconia/N-dopped porous carbon cathode

Qingsong Zhang,Qimou Deng,Yaoyao Zhang,Yang Xiao,Chunlei Zhang,Haiyi Gong,Qingming Zeng,Qingyan Zhang,Qingyi Zeng

Unavoidable organics in uranium wastewater or contaminated waters derive great challenges to traditional uranium removal techniques. Here, a drivingpower enhanced photocatalytic fuel cell (DEPFC) is designed by using a carbon felt (CF)-based UiO-66-NH 2 derived zirconia (ZrO 2 )/N-doped porous carbon (ZrON-C/CF) cathode and a monolithic photoanode, composing of a front FTO glass-based BiVO 4 film and a rearmounted Si photovoltaic cell, for effectively oxidizing organics and simultaneously reducing UO 2 2+ from complex wastewater under sunlight illumination. The water contact angle measurements demonstrate that ZrO 2 can improve the hydrophilia of cathode thus increases the contact between UO 2 2+ and cathode. The density functional theory indicates that N-doping can enhance the electronegativity of cathode and increases UO 2 2+ adsorption. Meanwhile, the enhanced UO 2 2+ reduction facilitates the charge separation in BiVO 4 film, therefore enhancing the organic oxidation. Consequently, under AM 1.5 illumination, the designed DEPFC can remove almost 100% of UO 2 2+ and simultaneous degrade 99% organics within 40 min

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ACS Applied Materials & Interfaces · 2026 · IF 7.8

FeN2–CoN2 Dual-Atom Catalyst Derived by Mesoporous NH2-MIL-101 Adsorbing N-Rich Guest Molecules [Co(en)3]3+ for Efficient ORR in Zn–Air Batteries

Xiaopeng Zhang,Lin Chen,Longzhu Li,Xiaoming Yan,Junjiang Bao,Ning Zhang,Gaohong He

The introduction of guest metal molecules into metal–organic frameworks (MOFs) is an outstanding method to prepare dual-atom catalysts (DACs) with good oxygen reduction reaction (ORR) activity. However, most of the MOF-derived dual-atom catalysts reported to date exhibit a microporous structure and, therefore, suffer from the underutilization of active sites and poor mass transfer. This study employed NH2-MIL-101 as a precursor to form defect-bearing mesoporous Fe-NC via one-step pyrolysis for adsorbing [Co(en)3]3+, followed by secondary pyrolysis to generate Fe–Co binuclear site catalysts. The mesopores of NH2-MIL-101 are beneficial to [Co(en)3]3+ introduction and can improve the mass transfer of the ORR. Furthermore, the elevated nitrogen content within the [Co(en)3]3+ complex facilitates the co-coordination of Fe and Co with nitrogen, thereby enhancing the formation of Fe–Co diatomic sites. As a result, the obtained FeCo-NC-40 catalyst showed excellent ORR performance with a half-wave potential of 0.915 V (vs RHE). In addition, the liquid-phase Zn–air battery employing FeCo-NC-40 as the cathode catalyst demonstrated a peak power density of 178.13 mW·cm–2 and achieved a discharge specific capacity of 806.13 mAh·g–1 at 10 mA·cm–2, and there was no significant decay in stability for 10 days of continuous cycling.

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JOURNAL OF SOLID STATE CHEMISTRY · 2026 · IF 3.2

Fabrication of a novel Ag/AgCl/NH2-MIL-53(Fe) heterojunction photocatalyst for enhanced visible-light photocatalytic degradation of rhodamine B and tetracycline: performance and mechanistic investigation

Yuye Li,Tianao Liu,Tingting Du,Congzhi Hu,Youyong Pang,Yongping Liu,Botian Liu,Ling Li,Huidan Lu,Bin Huang

Dyes and antibiotics possess high stability and are resistant to microbial degradation, leading to their persistence in the natural environment. Photocatalysis is an effective and green degradation method. In this work, a novel Ag/AgCl/NH 2 -MIL-53(Fe) (AAF) heterojunction photocatalyst was prepared using a solvothermal method, precipitation method, and photochemical reduction method, which effectively promotes the separation of photogenerated charge carriers. The study shows that the composite consisting of 95 wt% Ag/AgCl/NH 2 -MIL-53(Fe) (AAF-95) can photocatalytically degrade 99.4% of RhB within 15 min and 82.4% of TC within 12 min, achieving higher photocatalytic degradation activity than the individual materials. The main active species involved in the degradation are h + and •O 2 - . Based on Mott-Schottky tests, radical trapping experiments, and UV-vis DRS, a possible photocatalytic degradation mechanism and the advantages are proposed: AAF-95 broadens the light absorption range, and the NH 2 -MIL-53(Fe) increases the specific surface area, thereby enhancing the catalytic reaction activity. The coupling between the heterojunction and the SPR effect promotes the separation of photogenerated charge carriers and lowers the catalytic reaction barrier. These are the reasons for the enhanced photocatalytic degradation capability of the composite.

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BIOSENSORS & BIOELECTRONICS · 2026 · IF 11.8

Magnetic Fe3O4-Au@UIO-66-NH2@toehold probe mediated fluorescent sensor for detecting ovarian cancer-specific circRNA coupled with hybridization chain reaction and the CRISPR-Cas12a system

Lingsong Lu,Yingying Zhang,Bei Liu,Nuo zhou,Dao jun Yu,Ying Wang

Circular RNAs (circRNAs) represent an emerging family of noncoding transcripts defined by closed-loop architecture, which are now established as key participants in the etiology of tumorigenesis and malignant progression. While circRNAs show potential as therapeutic targets and biomarkers, the accurate detection of circRNAs remains challenging due to interference from homologous linear RNAs. In this study, an ultrasensitive method for detecting circ_0051240 based on the sulfhydrated toehold capture probe-initiator assembly-mediated hybridization chain reaction (HCR) and the CRISPR-Cas12a system was developed. The capture probe (with a toehold domain)-initiator strand duplex was ingeniously fabricated to identify the back-splice junction (BSJ) of circRNA. After magnetic enrichment and separation by the Fe 3 O 4 -Au@UIO-66-NH 2 nanocomposite, the initiator strand (H0) was delivered to trigger HCR. The HCR product dsDNA concatemers contained multiply repeated CRISPR-targetable DNA sites that were readily recognized by the CRISPR RNA (crRNA). This specific recognition and binding activated the CRISPR-Cas12a system's collateral endonuclease activity, leading to cleavage of the fluorophore-quencher (FQ) reporters and fluorescence emission at a characteristic wavelength. This design eliminated linear RNA-related interference and enhanced the detection of fluorescence intensity (FI). Under optimal conditions, the proposed HCR/CRISPR-Cas12a method exhibited a wide quantitative measurement range spanning from 45 pM up to 180 nM, achieving a notable limit of detection (LOD) of 0.03 pM. In this study, a novel circRNA sensing strategy capable of accurate and highly sensitive quantification of ovarian cancer-specific circRNA was reported. The proposed method exhibits acceptable performance when compared to present approaches.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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OPTICAL MATERIALS · 2022 · IF 3.754

Synthesis of Z-type heterojunction bifunctional composites with Mn-doped CdS nanoparticles supported on NH2-MIL-125(Ti) for hydrogen evolution and antibiotic degradation under visible light

Yang Wang,Sheng Feng,Changchang Ma,Yun Zhou,Zhiwei Ye,Xiaojun Dai,Xun Cao

In this paper, a novel Mn-doped CdS@NH 2 -MIL-125(Ti) (MC@NT) photocatalytic composites was synthetized through hydrothermal method . Hydrogen desorption and tetracycline and oxytetracycline degradation were performed under visible light to test their photocatalytic activities . The composites were characterized by XRD , FTIR, SEM, TEM, XPS , UV–Vis diffuse reflectance spectroscopy (DRS), EPR , EIS, and transient photocurrent response. From the characterization consequence, it could be seen that Mn-doped CdS was tightly attached to the surface of tetragonal NT in the form of nanoparticles . The MC@NT composites exhibited more promising catalytic activity than pristine monomeric materials. The photocatalytic hydrogen evolution rate reached 3.61 mmol g −1  h −1 . Within 110 min, the degradation efficiencies of TC and OTC were 90% and 88%, respectively. The free radical trapping experiments proved that ·O 2 − and h + were decisive role for degrading pollutants in the degradation catalysis process. Radical trapping experiments and electron spin resonance (ESR) indicated that the Z-scheme heterojunction was formed between Mn-doped CdS and NT, leading to facilitate the migration and shift of photogenerated carriers and holes. Cycling experiments showed that the as-prepared composites have good stability and have good prospects for practical applications. We believe this work will offer new ideas on the future development of efficient heterojunction catalysts for light energy conversion and other applications.

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FUEL PROCESSING TECHNOLOGY · 2022 · IF 8.129

Fabrication of Uio-66-NH2 with 4,6-Diamino-2-mercaptopyrimidine facilitate the removal of Pb2+ in aqueous medium: Nitrogen and sulfur act as the main adsorption sites

Wei Ruan,Haoyun Liu,Hao Wu,Yuan Qi,Mengchang Zhou,Changsong Zhou,Zhen Zhang,Hongmin Yang

In this work, the Zr-based MOF was successfully fabricated with 4,6-Diamino-2-mercaptopyrimidine (DMP) and a novel adsorbent (Uio-DMP) was synthesized for the immobilization of Pb 2+ in aqueous medium . The morphological and structural characteristics of Uio-DMP were characterized by X-ray diffractometer (XRD), Fourier transform infrared (FT-IR), Field emission scanning electron microscopy (FE-SEM), Brunner Emmet Teller (BET), and X-ray photoelectron spectroscopy (XPS). The characterization results showed that the Uio-DMP maintained a pristine crystal structure and the sulfhydryl group was introduced to Zr-based MOF after chemical functionalization. The adsorption behavior of Uio-DMP for Pb 2+ was investigated in different conditions (solution pH, sorbent dose, Pb 2+ concentration, adsorption time, and co-existing ions). The experimental results indicated that the optimal pH was 6, the maximum adsorption capacity was 296.5 mg/g, and the Langmuir model well fitted the Pb 2+ removal process based on adsorption isotherm studies. The adsorption kinetic experiments revealed that the adsorption equilibrium could be achieved at 30 min and the adsorption process was consistent with the Pseudo-second-order model. The co-existing ions had a limited impact on Pb 2+ removal and the removal rate of 71.0% was maintained after five consecutive adsorption-desorption experiments. Furthermore, zeta potential and XPS analysis proved that the removal process of Pb 2+ over Uio-DMP was affected by electrostatic interaction , and nitrogen/sulfur atoms acting as the main adsorption sites. This study provides an insight into the removal of Pb 2+ in aqueous medium and the functionalization of adsorbents.

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BIOINORGANIC CHEMISTRY AND APPLICATIONS · 2022 · IF 4.724

Synthesis of the Magnetically Nanoporous Organic Polymer Fe3O4@SiO2-NH2-COP and Its Application in the Determination of Sulfonamide Residues in Surface Water Surrounding a Cattle Farm

Yuqin Yang,Junjie Miao,Zhendong Yin,Weili Hao,Hongmei Shi,Ling Ma,Tiesheng Shi

Efficient extractions of trace antibiotic residues in the environment are a key factor for accurate quantification of the residues. A new nanoporous material, namely, magnetically covalent organic polymer (MCOP, Fe3O4@SiO2-NH2-COP) was synthesized in this work and was used for magnetic solid-phase extraction (MSPE). The combination of MSPE with high-performance liquid chromatography separation together with ultraviolet detection (HPLC-UV) was established as an effective method for the determination of four sulfonamide (SA) residues in surface water surrounding a cattle farm. The synthesized magnetic material was characterized by SEM, TEM, FT-IR, magnetic properties measurement system (MPMS), and nitrogen gas porosimetry. The material possessed many attractive features, such as a unique microporous structure, a larger specific surface area (137.93 m2·g−1) than bare Fe3O4 (24.84 m2·g−1), high saturation magnetization (50.5 emu·g−1), open adsorption sites, and high stability. The influencing parameters, including pH, the used amount of MCOPs, the type of eluent, adsorption solution, and desorption time, were optimized. Under the optimized conditions, the method conferred good linearity ranges (R2 ≥ 0.9990), low detection limits (S/N = 3, LOD, 0.10–0.25 μg·L−1), and satisfactory recoveries (79.7% to 92.2%). The enrichment factor (EF) for the four SAs was 34.13–38.86. The relative standard deviations of intraday (n = 5) and of interday (n = 3) were less than 4.8% and 8.9%, respectively. The equilibria between extraction and desorption for SAs could be reached within 150 s. The proposed method was sensitive and convenient for detecting SA residues in complex environmental matrices, and the successful application of the new MCOPs as an adsorbent was demonstrated.

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