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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Modifying of magnetic UiO-66-NH2 as a new nanosorbent by thermo-alkali-hydrolysis technology for highly efficient enrichment and determination of quercetin in apple peel

Ruimiao Chang,Huichun Wang,Shumian Liu,Yijing Dong,Guangbin Zhang,Anjia Chen,Ruiping Zhang,Yong Li

For rapid separation of quercetin from apple peel, a novel magnetic nanomaterial was prepared by a simple and economical thermal alkaline hydrolysis method in this study. This magnetic nanomaterial was obtained by mixing and then heating magUiO-66-NH 2 (magnetic University of Oslo 66-NH 2 ) with 0.05 mol·L −1 KOH aqueous solution, and was named magUiO-66-NH 2 -MH 0.05 (magUiO-66-NH 2 -mixed heating 0.05 ), which has better magnetic properties, thermal stability, pore capacity and average pore size than magUiO-66-NH 2 . The obtained magUiO-66-NH 2 -MH 0.05 had strong adsorption capacity for quercetin, and the maximum adsorption capacity was 65.30 mg·g −1 . MagUiO-66-NH 2 -MH 0.05 tends to be monolayer-layer adsorption for quercetin, and electron sharing or transfer may occur during the adsorption process. Compared with naringenin, naringin and gallic acid, magUiO-66-NH 2 -MH 0.05 showed good recognition ability for quercetin, and the recovery rate was good. After 7 cycles, the removal rate of magUiO-66-NH 2 -MH 0.05 for quercetin was 96.3 % of the initial adsorption capacity. A magnetic solid-phase extraction method coupled with High-Performance Liquid Chromatography based on magUiO-66-NH 2 -MH 0.05 was successfully used for rapid separation and determination of quercetin in apple peel. This study will help to discover the experimental law of the treatment of UiO-66-NH 2 nanomaterials by hot alkaline hydrolysis, reveal the reaction mechanism, and expand the application of UiO-66-NH 2 nanomaterials in food analysis.

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JOURNAL OF HAZARDOUS MATERIALS · 2025 · IF 11.3

Amino-functionalized MIL-101(Fe)-NH2 as efficient peracetic acid activator for selective contaminant degradation: Unraveling the role of electron-donating ligands in Fe(IV) generation

Renjie Pan,Zongchen Li,Tian-Yang Zhang,Qi Fu,Zheng-Xiong Zheng,Jun Shi,Jian Lu,Chen-Yan Hu,Yu-Lin Tang,Mohamed Gamal El-Din,Bin Xu

Peracetic acid-based advanced oxidation processes (PAA–AOPs), which generate various reactive radicals, have garnered substantial attention for degradation emerging contaminants (ECs). However, nonselective radical-based PAA–AOPs often suffer from interference by water matrix components, causing low contaminants removal efficiency. This study explores the use of amino-(NH 2 )-functionalized metal–organic frameworks (MIL-101(Fe)-NH 2 ) as heterogeneous catalysts for PAA activation, enabling the generation of high-valent iron- (Fe)–oxo species (Fe(IV)) capable of efficiently degrading ECs (80 −100 %, within 30 min). The Fe(II) clusters in MIL-101(Fe)-NH 2 , modulated by electron-donating −NH 2 groups, play a pivotal role in Fe(IV) generation. Scavenger and probe experiments confirmed Fe(IV) as the primary reactive species responsible for ECs degradation. Density functional theory calculations demonstrated that the four-electron transfer to generate Fe(IV) has lower free energy than the two-electron transfer to generate organic radicals (e.g., CH 3 COO • and CH 3 C(O)OO • ). Furthermore, thermodynamically unfavorable CH 3 COO • desorption further promotes Fe(IV) generation. The PAA/MIL-101(Fe)-NH 2 system efficiently degraded SMX ( k app = 121.2 −287.2 M −1 s −1 ) and other ECs ( k app = 40 −432 M −1 s −1 ) with minimal interference from water matrix components and excellent reusability. This study demonstrates that MIL-101(Fe)-NH 2 is a robust catalyst for PAA activation and provides a novel approach for selectively generating Fe(IV) for ECs degradation.

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NEW JOURNAL OF CHEMISTRY · 2024 ·Vol. 48 ·期 21 ·9702-9708 · IF 2.7

Preparation of chiral metal–organic framework L-his-MIL-53-NH2@SiO2 composite by in situ growth and chiral post-modification strategies for HPLC enantiomeric separation

An-Xu Ma,Cai-Fang Liu,Yu-Lan Zhu,Zong-Hong Luo,Hong-Mei Zhou,Yue Zhang,Bang-Jin Wang,Jun-Hui Zhang,Sheng-Ming Xie,Li-Ming Yuan

In this work, a chiral core–shell microspheres composite, L-his-MIL-53-NH2@SiO2, was prepared through in situ growth and chiral post-modification strategies. The core–shell microspheres were applied as a novel chiral stationary phase for HPLC enantiomeric separation. Various racemates were separated on the L-his-MIL-53-NH2@SiO2 packed column using n-hexane/isopropanol as the mobile phase. The chiral column showed excellent separation efficiency for fourteen chiral compounds, including alcohols, alkanes, esters, phenols, ketones, and organic acids. The influence of injection mass and temperature on the separation performance of the chiral column were investigated. The relative standard deviations (n = 5) of the retention time and peak area by repeated separation of benzoin are 0.28% and 0.63%, respectively. The results show that the L-his-MIL-53-NH2@SiO2 packed column exhibited good reproducibility and stability. In addition, the chiral resolution ability of the L-his-MIL-53-NH2@SiO2 packed column was compared with that of a commercial chiral column (Chiralpak AD-H). The L-his-MIL-53-NH2@SiO2 packed column exhibits unique advantages in chiral separations that can be complementary to the commercial chiral column. It was demonstrated that the chiral core–shell microspheres composite L-his-MIL-53-NH2@SiO2 prepared based on in situ growth and chiral post-modification strategies has great potential for enantiomeric separation by HPLC.

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TALANTA · 2025 · IF 6.1

A highly sensitive SERS sensor based on magnetic-enrichment Ag@Fe3O4/UiO-66-NH2 for detection and solar photo-reduction of hexavalent chromium in water environment

Ao Chen,Yiwen Gui,Kuang Luo,Ning Cai,Jumei Li

In this study, a novel magnetic composite, Ag@Fe 3 O 4 /UiO-66-NH 2 (Ag@FUN), was developed by incorporating a porous metal-organic framework (MOF), UiO-66-NH 2 , which offers selective enrichment capabilities and facilitates solar-driven photoreduction of Cr(VI). The surface coverage of silver nanoparticles on Ag@FUN was precisely controlled by adjusting the AgNO 3 feed concentration, enabling tunable SERS sensitivity. SERS measurements revealed that the Ag@FUN composites exhibited strong signal intensity for Cr(VI), along with excellent signal reproducibility and storage stability. These composites were capable of detecting Cr(VI) at concentrations of as low as 7.81 × 10 -8 M in tap water and 8.89 × 10 -8 M in pond water. The remarkable SERS performance is attributed to the porous MOF structure, which enriches Cr(VI) via Zr–O coordination, electrostatic interactions, and pore-filling effects. Importantly, under simulated sunlight, Ag@FUN effectively reduced Cr(VI) within 70 minutes. The composites also demonstrated outstanding recyclability, retaining their SERS sensitivity and photocatalytic efficiency through five consecutive "detection–reduction" cycles. Overall, the Ag@FUN composites developed in this work exhibit high SERS sensitivity and robust photocatalytic activity, offering significant potential for environmental monitoring and ecological remediation.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Preparation of MIL-101(Cr)-NH2/chitosan tip foam and its application in pipette tip solid-phase extraction of puerarin and its metabolites in rat serum

Yong Zhang,Jing Wang,Ying Liu,Xuemeng Wu,Lina Gao,Guihua Gao

In this study, a tip foam named as MIL-101(Cr)-NH₂/chitosan (MIL-101(Cr)-NH₂/CS) was prepared by cross-linking chitosan (CS) with MIL-101(Cr)-NH₂ using glutaraldehyde as the cross-linking agent. After freeze-drying, the internal structure of the MIL-101(Cr)-NH₂/CS foam became porous, thereby exposing more MIL-101(Cr)-NH₂, enriching binding sites, ensuring efficient adsorption, and allowing smooth passage of the sample solution. This also facilitates the inhalation and extrusion of the sample solution. Based on the unique advantages of the MIL-101(Cr)-NH₂/CS foam, a method combining pipette tip solid-phase extraction (PT-SPE) with high-performance liquid chromatography equipped with a fluorescence detector (HPLC-FLD) was established for the detection of puerarin and its metabolites (e.g., daidzein and equol) in rat serum. The method exhibited good linearity in the range of 0.5 to 5000 ng/mL, with limits of detection (LOD), lower limits of quantification (LLOQ), and limits of quantification (LOQ) ranging from 0.2 to 15 ng/mL, 0.5 to 50 ng/mL, and 1 to 100 ng/mL, respectively. The relative standard deviations (RSDs) of intra-day and inter-day precision for puerarin, daidzein, and equol were less than 19.8 %, meeting relevant regulatory requirements. The extraction recoveries of puerarin, daidzein, and equol ranged from 80.17 % to 91.70 %, 80.02 % to 87.41 %, and 80.29 % to 85.39 %, with corresponding RSDs of 3.2 % to 10.4 %, 11.2 % to 13.8 %, and 7.9 % to 11.1 %. These results indicate that the developed method meets the methodological requirements for the quantitative analysis of biological samples. The application of MIL-101(Cr)-NH₂/CS foam in PT-SPE further expands the application scope of metal-organic frameworks (MOFs) in solid-phase extraction (SPE) and provides a reference for PT-SPE technology in handling small-volume samples in complex matrices.

CAS / MDL: 67-56-1 75-05-8
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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

Reasonable construction of low migration energy barrier and continuous proton transfer channels via bimetallic MOFs nanofibers (MIL-(Cr Al)–NH2) for its composite proton exchange membrane

Lei Li,Hengji Liu,Yuanyuan Wang,Gang Wang,Yongde Guo,Weimin Kang

Reasonable construction of low migration energy barrier and continuous proton transfer channel is the key to improving the performance of composite proton exchange membranes. In this paper, we prepared a novel bimetallic MOFs (MIL-(Cr Al)–NH 2 ) nanofibers (MCANs) consisting of Cr and Al elements by electro-blown spinning method (EBS) and hydrothermal synthesis, and subsequently introduced them into non-fluorinated sulfonic acid polymer sulfonated polysulfone (SPSF) matrix to obtain composite proton exchange membranes (MCANs@SPSF). Importantly, MCANs successfully constructed relatively long-range continuous unsaturated metal site proton transfer channels provided by the Cr-based MOFs, thereby reducing the proton migration energy barrier in the MCANs@SPSF, which confirmed by the density functional theory (DFT) calculation. In detail, DFT studies indicated that the migration energy barrier between H + and MCANs was 1.677 eV, while that of single Al-based MOF (MAN) and single Cr-based MOF (MCN) were 1.879 eV and 1.762 eV respectively. The existence of efficient low migration energy barrier and continuous proton transfer channels made the proton conduction efficiency of MCANs@SPSF greatly improved, that was under the condition of 80 °C and 100 % RH, the proton conductivity of MCANs@SPSF reached the maximum value of 0.358 S cm −1 and the power density reached 104 mW cm −2 . Moreover, MCANs@SPSF-5 displayed best DMFC durability performance with only 14.65 % voltage loss under 24h test. In addition, due to the acid-base pair interaction between MCANs and SPSF enhanced the interface binding force between the two phases, meanwhile, the pore structure of MOFs also had a certain adsorption effect on methanol, thus reducing the methanol permeability, and the addition of 5 wt% MCANs in SPSF was tested to reduce the methanol permeability to 5.53 × 10 -7  cm 2  s −1 . Overall, this work provided a new strategy for construction of low migration energy barrier and continuous proton transfer channels, which was beneficial for the development of high performance proton exchange membranes.

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MICROCHIMICA ACTA · 2025 ·Vol. 192 ·期 7 ·1-12 · IF 5.3

A bifunctional UIO-66-NH2@ RhB-based fluorescence and colorimetric dual-mode ratiometric sensor and hydrogel-based smart phone–assisted naked eye detection of perfluorooctanesulfonate (PFOS)

Aham Emmanuel Chigozie,Ravikumar A.,Feng Weiwei,Arunjegan A.,Hu Zhang,Zhang Zhen,Zhao Hongjun

A bifunctional fluorescent and colorimetric sensor based on UiO-66-NH₂@RhB was developed for the highly sensitive detection of perfluorooctanesulfonate (PFOS), a persistent environmental pollutant. The sensing mechanism relies on the inner filter effect (IFE), where Rhodamine B (RhB) modulates the fluorescence of UiO-66-NH₂, enabling effective PFOS recognition. In the presence of PFOS, UiO-66-NH 2 @RhB exhibits dual emissions in blue fluorescence at 448 nm and red fluorescence at 565 nm at a single excitation wavelength. Upon the addition of increasing concentrations of PFOS, the blue fluorescence intensity increased and a small change was observed in the red fluorescence intensity. Besides, UiO-66-NH 2 @RhB solutions display an excellent colorimetric response for PFOS and produce an obvious color change from red to colorless. The method demonstrated high sensitivity, achieving linear detection ranges of 1–10 nM with detection limits of 0.84 nM (fluorescence) and 0.91 nM (colorimetry). Furthermore, the dual-sensing platform successfully detected PFOS in real water samples with satisfactory outcomes. Its integration with a portable smartphone further enables intelligent, real-time, on-site monitoring and is successfully applied to monitoring PFOS in environmental samples. This study not only broadens the application of MOFs but also provides valuable insights for designing multifunctional sensors for diverse analytical applications. Graphical abstract

✓ 已验证 产品关联 DOI PubMed 高影响因子
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POLYMER COMPOSITES · 2024 · IF 4.8

Enhanced thermal conductivity of polypropylene/polyamide 6 composites via optimizing the selective distribution of h-BN and NH2-CNTs hybrid fillers within the co-continuous structure

Xinyi Jing,Linggong Meng,Tong Liu,Xinming Ye,Shuai Yang,Zhichao He,Wensheng Wang,Jie Li,Yingchun Li

Achieving high thermal conductivity in composites with low filler content is a major challenge in current research. In this paper, polypropylene (PP) and polyamide 6 (PA6) were used as polymer matrix, and the hybrid thermal conductive filler, formed by hexagonal boron nitride (h-BN) and aminated carbon nanotubes (NH 2 -CNTs), was integrated into matrix for the fabrication of thermal conductive composites (PP/PA6/h-BN and PP/PA6/h-BN@CNTs) via two-step melt blending technology. The thermal conductive fillers were selectively distributed in a phase of the polymer matrix with a co-continuous structure, forming a thermal conductive path with a three-dimensional network structure. The results show that when the content of h-BN reaches 25 wt%, the thermal conductivity of the PP/PA6/h-BN and PP/PA6/h-BN@CNTs composites was 199% and 300% higher than that of PP/PA6, respectively. Through testing the volume resistivity of the composites, it was confirmed that PP/PA6/h-BN@CNTs composites maintain good electrical insulation. Both composites demonstrated remarkable thermal conductivity and outstanding electrical insulation. This research provides a facile way to prepare highly thermal conductivity polymer composites with excellent processing performances and electrical insulation. Highlights h-BN@CNTs hybrid fillers with sandwich structure were prepared. A two-step blending method was used to control the selective distribution of hybrid fillers in a phase of the polymer matrix with a co-continuous structure. The hybrid filler formed a thermal conductive path with a three-dimensional network structure in the collective. PP/PA6/h-BN@CNTs composites demonstrated remarkable thermal conductivity, outstanding electrical insulation and favorable processing performances.

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CARBON · 2022 · IF 11.307

Uncovering the optimal pyrolysis temperature of NH2-MIL-88B-derived FeOX/Fe@porous carbon composites for the ultrasensitive electrochemical detection of baicalin in natural plant samples

Jiao Li,Yuefan Wang,Chenxi Wang,Yilin Wang,Yaqi Yang,Jia Chen,Chunyan Li,Yixi Xie,Pengcheng Zhao,Junjie Fei

Baicalin obtained from natural plants has essential medical value, so the development of accurate and sensitive quantitative methods for it is one of the most important tasks. Here, the FeO X /Fe@porous carbon composite (Fe@C) was synthesized by solvothermal method and carbonized at different temperatures under an N 2 atmosphere, and an electrochemical sensor designed based on this material was applied to the accurate and rapid determination of baicalin. According to the results of physical and electrochemical characterization, Fe@C at different pyrolysis temperatures exhibited different morphologies and different electrochemical properties , while the Fe@C pyrolyzed at 800 °C had the optimum performance. Compared with NH 2 -MIL-88B, the pyrolysis greatly reduces the charge transfer internal resistance of the material and has a larger porosity and specific surface area, resulting in an eminent electrochemical signal for the detection of baicalin. The sensor Fe@C-800/GCE not only has a linear range of 4 nM–700 nM with a low limit of detection of 1.16 nM for the detection of baicalin, but also has outstanding repeatability, anti-interference and stability for the detection of baicalin in several natural plant samples and herbal medicines samples. This work presents several pyrolytic NH 2 -MIL-88B as electrochemical sensors for the detection of baicalin for the first time, providing a novel idea for the application of MOFs derivatives in environmental analysis.

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CRYSTENGCOMM · 2015 ·Vol. 17 ·期 11 ·2376-2388 · IF 4.034

A family of 3D UO22+–5-X-1,3-dicarboxylate (X = –H, –NO2, –NH2, –OH) hybrid materials: structural relevance with variation of substituent groups and photochemical properties

Xiang-Sheng Zhai,Wen-Gang Zhu,Wei Xu,Ya-Jing Huang,Yue-Qing Zheng

Four new 3D uranyl complexes, [(UO2)2(H2O)(ipa)2]·9H2O (1), [(UO2)2(H2O)(nip)2]·H2O·Et3NH (2), [(UO2)2(H2O)(aip)2]·Et3NH (3) and [(UO2)(hip)]2·17H2O (4) (H2ipa = isophthalic acid, H2nip = 5-nitroisophthalic acid, H2aip = 5-aminoisophthalic acid, H2hip = 5-hydroxyisophthalic acid, Et3N = triethylamine), were hydrothermally synthesized. Structural analyses reveal that compounds 1–4 consist of pentagonal bipyramidal uranyl monomers bridged via acid inkers to form a structural motif, [(UO2)2L2], serving as the foundation of the 3D framework. Two structural motifs adopt different arrangement modes to connect to two types of chains. For 1–3, uranium atoms and carboxyl groups being from two types of chains respectively are coordinated to build similar 3D frameworks, while for 4, one type of chain links to the 3D architecture by the bond of the uranium atoms and –OH of the 5-hydroxyisophthalic acid ligand. The different guest molecules and structure assemblies displayed by the four compounds are a function of the variation of substituent groups of 5-X-1,3-benzenedicarboxylic acid (X = –H, –NO2, –NH2, –OH). Furthermore, the photocatalytic properties of 2 and 4 for degradation of rhodamine-B (RhB) upon xenon lamp irradiation have been examined. Elemental analysis, infrared spectroscopy, DRS and luminescence properties were also discussed.

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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Construction of Fe(III) doping modified AgI/NH2-MIL-68(In/Fe) Z-scheme heterojunction photocatalysts through unique internal and interfacial charge transmission and separation efficiency

Jiamin Wei,Qing Wang,Mian He,Shuai Li,Yunan Zhang,Yang Yang,Shipeng Luo,Lianshe Fu,Xin Wang,Tinghai Yang

The development of highly efficient strategy to facilitate comprehensive charge transmission and effective spatial charge separation is expected as a promising approach to improve photocatalytic performance. Herein, the Fe(III) doping modified AgI/NH 2 -MIL-68(In/Fe) Z-scheme heterojunction (ANM-x composite) with unique internal and interfacial charge transmission performance was fabricated by a facile ion exchange precipitation method. The optimized ANM-50 composite exhibits the maximum photocatalytic activity for the degradation of tetracycline, which is about 9.54, 2.61 and 1.86 times higher than that of pure NH 2 -MIL-68In, NH 2 -MIL-68(In/Fe) and AgI, respectively. The characterization results displayed that Ag nanoparticles (NPs) were generated during the photocatalytic procedure, which not only served as a charge transfer-highway, but also reduced the charge flow energy barrier, thereby accelerating charge transfer efficiency and consolidating the stability of the Z-scheme heterojunction. Mechanism exploration reflected that the superior photocatalytic performance was associated with synergetic effect among the introduced Fe(III), constructed ANM Z-scheme heterojunction and the generated Ag NPs, which significantly expands visible light response range and promotes more effective internal and interfacial charge separation. This research not only designs an efficient photocatalyst for decomposing tetracycline, but also opens a new perspective for rational developing Z-scheme heterojunction with unique internal and interfacial charge flow steering.

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POLYMER ENGINEERING AND SCIENCE · 2014 ·Vol. 55 ·期 3 ·614-623 · IF 1.441

Preparation of polypropylene and polystyrene with ?NCO and ?NH2 functional groups and their applications in polypropylene/polystyrene blends

Hao Li,Xian-Ming Zhang,Shi-Yang Zhu,Wen-Xing Chen,Lian-Fang Feng

Isocyanate- and amine-functionalized polypropylene (PP) and polystyrene (PS) were prepared through grafting and copolymerization method. These compounds are used as precursors for PP-graft-PS (PP-g-PS) copolymers and reacted at the matrix interface of PP/PS blends. Functionalized polymer structures were characterized by 1 H NMR and FTIR spectroscopy. The effects of the synthesized compatibilizer on the rheological and morphological behavior of PP/PS blends were investigated systematically. Results showed that the functional polymer was successfully synthesized, and the additional two different compatibilizer systems dramatically decreased the size of the dispersed phase domains in PP/PS blends. Compared with the uncompatibilized blends, compatibilized blends exhibited a slightly higher crystallization temperature because the melting points of the blend components were not evidently affected by the addition of compatibilizer, as revealed by differential scanning calorimetry. The compatibilizer effect on the PP/PS blends was reflected through rheological property and dynamic mechanical analysis. POLYM. ENG. SCI., 55:614–623, 2015. © 2014 Society of Plastics Engineers

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