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MIL-53
BIOMEDICAL CHROMATOGRAPHY · 2022 ·Vol. 36 ·期 11 ·e5454 · IF 1.911

A membrane solid-phase extraction method based on MIL-53-mixed-matrix membrane for the determination of estrogens and parabens: Polyvinylidene difluoride membrane versus polystyrene-block-polybutadiene membrane

Yong Zhang,Kaifang Wei,Litao Wang,Guihua Gao

In this work, MIL-53(Al), as an inorganic “filler” component, was embedded in polyvinylidene difluoride (PVDF) and polystyrene-block-polybutadiene (SBS) matrices to prepare two mixed-matrix membranes (MMMs), using a simpler method than that previously reported. The PVDF and SBS membranes retained much of the properties of PVDF, SBS, and native MIL-53(Al). The prepared MMMs were then placed in a vortex-stirred sample solution to develop a membrane solid-phase extraction method to extract estrogens and parabens, which were determined by high-performance liquid chromatography with fluorescence detection. The extraction efficiencies of the two membranes were compared, with the PVDF membrane exhibiting superior performance. In addition, the PVDF membrane was more freestanding and flexible, and its preparation method was also more facile and simple. The extraction conditions were optimized, and the analytical method showed low limits of detection (0.005–0.18 ng/mL), good linearity, and high accuracy, with recoveries ranging from 90.7% to 102.5%. As a result, this membrane solid-phase extraction method indicated its potential for application in aqueous sample pretreatment. For metal–organic framework–based MMM used in this method, in addition to being durable, freestanding, mechanically stable, and possessing a large area, it should also exhibit high metal–organic framework incorporation, good flexibility, and appropriate thickness and weight.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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ANALYST · 2012 ·Vol. 137 ·期 22 ·5411-5419 · IF 4.23

Metal–organic framework MIL-53(Al) as a solid-phase microextraction adsorbent for the determination of 16 polycyclic aromatic hydrocarbons in water samples by gas chromatography–tandem mass spectrometry

Xiang-Feng Chen,Hao Zang,Xia Wang,Jian-Guang Cheng,Ru-Song Zhao,Chuan-Ge Cheng,Xiao-Qing Lu

In this paper, the potential applications of metal–organic framework (MOF) materials as fiber coatings for the solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs) in water samples were explored. Fibers coated with MIL-53(Al, Cr, Fe) materials were fabricated by an adhesive method for SPME. The quantitation was performed by gas chromatography–tandem mass spectrometry (GC–MS/MS) using the multiple reaction monitoring mode. Among the three MIL-53(M) coatings, MIL-53(Al) showed the highest extraction efficiency towards PAHs under the current fabrication procedure. Under optimized conditions, the MIL-53(Al)-coated fiber showed good precision (relative standard deviation <12.5%), low detection limits (0.10 ng L−1 to 0.73 ng L−1, S/N = 3), and good linearity (R2 > 0.98) for aqueous solutions containing 16 PAH . The fiber also offered high thermal and chemical stability. The method developed based on MIL-53(Al) SPME–GC–MS/MS was successfully applied in the analysis of real water samples. Based on the simulation results, the PAHs were adsorbed on MIL-53(Al) primarily through the hydrophobic and π–π interactions between PAHs and the organic linker of the material. The results presented in this paper indicate that water-stable MOF materials have great potential for the SPME of aromatic compounds in water samples.

CAS / MDL: 100-21-0
研究领域: 环境科学 · 分析化学
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NANOTECHNOLOGY · 2024 ·Vol. 35 ·期 42 ·425702 · IF 2.9

Vanadium as a Ti-like mediator boosting electronic transmission in Fe-based MOFs for photocatalytic sterilization

Rui Li,Huilin Hu,Furong Xiong,Xiang Xue,Minqi Wu,Xuan Zuo,Wang Zhang,Xiangliang Pan

Efficient metal–organic frameworks (MOFs) photocatalytic bactericidal catalysts are urgently needed in water purification. Herein, a Fe-MOF (MIL-88B-NH2(V1Fe5) with promoted electron transport was achieved by vanadium (V) ions doping and V/Fe ratio optimization, showing excellent photocatalytic bactericidal activity against E. coli under visible light irradiation (99.92%). The efficient antibacterial mechanism, V as a Ti-like mediator boosting electronic transmission in MIL-88B-NH2(V1Fe5), was revealed by its band structure, transient photocurrent, electrochemical impedance spectroscopy, and scavenger quenching experiments. The enhancement of photocatalytic bactericidal performance of Fe-MOFs by V–ion-doping was confirmed by two other Fe-MOFs, MIL-53-NH2(V1Fe5) and MIL-101-NH2(V1Fe5), with the same metal ions and ligands, both of which have higher performance than the corresponding undoped MOFs. Among them, MIL-88B-NH2(V1Fe5) exhibits the highest photocatalytic bactericidal activity due to its suitable metal clusters ([M(μ3-O)] cluster) and topological structure (three-dimensional rhomboid network structure). This work demonstrated the amplification effect of V ion doping on electron transport in Fe-MOFs photocatalysts.

研究领域: 材料科学 · 环境科学 · 化学 · 光催化
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Simultaneous quantification of six monoamine neurotransmitters in biological samples by magnetic solid-phase extraction coupled with UHPLC-MS/MS using a polyethylenimine-dopamine@NH2-MIL-53(Al)-SiO2@Fe3O4 composite

Yun Wu,Yanqun Yang,Ming Wen,Jing Xie,Linchun Bao,Shuting Yang,Xiangming Luo,Xingyi Wang,Qianchun Zhang

Monoamine neurotransmitters play vital roles in cognitive and various physiological and pathophysiological processes, but their trace levels, small sample volumes, and complex biological matrices in biological samples pose significant analytical challenges. This study developed a novel method for the simultaneous quantification of six monoamine neurotransmitters—tyrosine, vanillylmandelic acid, tryptophan, 3,4-dihydroxyphenylacetic acid, 5-hydroxyindole-3-acetic acid, and homovanillic acid—in human serum and urine. The method utilizes magnetic solid-phase extraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). A multifunctional magnetic composite, polyethylenimine@polymer dopamine hydrochloride@NH 2 -MIL-53(Al)-SiO 2 @Fe 3 O 4 , was synthesized, exhibiting high extraction selectivity and capacity and achieving an extraction range of 9.61–25.4 nmol/mg for the target neurotransmitters. The analytical method, optimized for the aforementioned composite, exhibited robust linearity for all six monoamine neurotransmitters, with correlation coefficients ( R 2 ) exceeding 0.998. The limits of detection (S/N = 3) ranged from 1.1 to 22 ng/L, indicating high sensitivity. Recovery rates for the targeted analytes varied between 94.5 % and 112 %, and relative standard deviations remained within the range of 1.5–9.4 %. These findings confirm that the developed methodology is sensitive, accurate, selective, and reliable for the quantitative determination of trace monoamine neurotransmitters in complex biological samples.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2019 · IF 6.361

Preparation of mixed-matrix membranes from metal organic framework (MIL-53) and poly (vinylidene fluoride) for use in determination of sulfonylurea herbicides in aqueous environments by high performance liquid chromatography

Jiping Ma,Shuang Li,Gege Wu,Shasha Wang,Xiaotong Guo,Liyan Wang,Xiaoyan Wang,Jinhua Li,Lingxin Chen

Novel mixed-matrix membranes (MMM) were prepared from metal-organic frameworks (MOF) (MIL-53) and poly (vinylidene fluoride) (PVDF), viz MIL-53–PVDF MMM, for the simultaneous dispersion membrane extraction (DME) of seven sulfonylurea herbicides (SUs) in aqueous environments followed by high performance liquid chromatography (HPLC) determination. The MIL-53–PVDF MMM was well characterized and major factors influencing DME performances were systematically investigated including membrane type, MOF dosage, eluent type, solution pH, extraction/elution time and salinity, etc. Under optimal conditions, the MIL-53–PVDF MMM based DME coupled with HPLC exhibited excellent linearity within 0.03–10 μg L −1 for chlorimuronethyl and 0.01–10 μg L −1 for other six SUs individual. High enrichment factor of 250 was obtained, as well as low detection limits and quantification limits ranged from 3.75 to 10.30 ng L −1 and 12.49–34.30 ng L −1 , respectively. Furthermore, the method attained high recoveries of 77.20–111.00% at three spiking levels of SUs, with relative standard deviations of 1.28–14.67% in tap water, seawater and surface water samples. Additionally, the MMM was readily separated from water and well regenerated, and could keep about 80% recovery after 25 cycles. Compared to that reported extraction materials, the MIL-53–PVDF MMM possessed the advantages of high enrichment ability, excellent reusability, good practicality and easy separation, indicating it was a promising alternative for the enrichment of SUs from aqueous environments.

CAS / MDL: 7784-27-2 74222-97-2
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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

On-Site Generation of Coreactant on a Solid-State Electrochemiluminescence Electrode for Label-Free Detection of Enterohemorrhagic Escherichia coli in Raw Meat Samples

Zirui Wang,Jilong Zheng,Min Li,Shujia Wang,Zhida Gao,Yan-Yan Song,Chenxi Zhao

Rapid and accurate detection of trace microbial pathogens is essential for human health, environmental monitoring, and food safety. Here, we report the development of a solid-state electrochemiluminescence (ECL) bacterial sensor based on a β-glycosidase (β-Gal)-triggered coreactant generation strategy. Leveraging a three-dimensional TiO2 nanotube array integrated with peroxidase-like MIL-53(Fe), glucose oxidase-like Au nanoparticles, and luminol, this sensor efficiently generates coreactants on-site, enabling sensitive glucose detection. As glucose is the primary product of β-Gal-catalyzed lactose hydrolysis, its concentration directly correlates with β-Gal enzymatic activity, thus allowing for the quantification of β-Gal via ECL signal intensity. Using enterohemorrhagic Escherichia coli (EHEC) as a model of food-borne pathogens, the sensor demonstrates rapid detection (30 min) with an ultralow LOD (0.8 CFU mL–1), representing the most sensitive label-free bacterial ECL sensor reported to date. Furthermore, the ECL electrode was applied for the detection of EHEC on raw salmon slices, underscoring its potential for food safety monitoring.

CAS / MDL: 100-21-0
研究领域: 分析化学 · 生物传感器 · 食品安全 · 纳米技术 · 微生物学 · 电化学
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TALANTA · 2016 · IF 4.035

In-tube solid-phase microextraction based on NH2-MIL-53(Al)-polymer monolithic column for online coupling with high-performance liquid chromatography for directly sensitive analysis of estrogens in human urine

Xialin Luo,Gongke Li,Yufei Hu

In this work, a novel NH 2 -MIL-53(Al) incorporated poly(styrene-divinylbenzene-methacrylic acid) (poly(St-DVB-MAA)) monolith was prepared via chemical fabrication. Moreover, it has been efficiently applied to the in-tube solid-phase microextraction (SPME) for online coupling with high-performance liquid chromatography (HPLC) to the direct determination of five estrogens in human urine samples. The NH 2 -MIL-53(Al)-polymer monolith was suitable for in-tube SPME owing to its good permeability, high extraction efficiency, chemical stability, good reproducibility and long lifetime. The extraction conditions including extraction solvent, pH of sample solution, flow rate of extraction and desorption, and desorption volume were investigated. Under the optimum conditions, the enrichment factors were 180–304 and saturated amounts of extraction were 2326–21393 pmol for estriol , 17β-estradiol, estrone , ethinyl estradiol and progesterone , respectively. The adsorption mechanism was also explored which contributed to its strong extraction to target compounds. The proposed method had low limit of detection (2.0–40   ng/L) and good linearity (with R 2 between 0.9908 and 0.9978). Four endogenous estrogens were detected in urine samples and the recoveries of all five analytes were ranged from 75.1–120% with relative standard deviations (RSDs) less than 8.7%. The results showed that the proposed online SPME-HPLC method based on NH 2 -MIL-53(Al)-polymer monolithic column was highly sensitive for directly monitoring trace amount of estrogens in human urine sample.

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Biomaterials Science · 2024 ·Vol. 12 ·期 19 ·5091-5104 · IF 5.8

Cellulose acetate/metal–organic framework composite beads with macroporous adsorption channels as a novel hemoadsorbent for effective virus capture

Yamin Chai,Wenyan Han,Yanjia Zhang,Yunzheng Du,Biao Wang,Mengya Chen,Nan Li,Wei Luo,Xiaoyu Zha,Lichun Wang,Lailiang Ou

Due to their rapid spread, high variability, and drug-resistant strains, new viral infections are continuously emerging. A lack of effective antiviral drugs and vaccines, resulting in disease and death, has significant socioeconomic consequences. Hemoperfusion can effectively adsorb and remove toxins from the blood, thus purifying the blood and serving as an acute treatment. Therefore, the aim of this study was to construct adsorbents to selectively remove viruses from the blood to quickly treat pathogen infection. We reported on new metal–organic framework (MOF)-polymer beads based on MIL-53(Al) and cellulose acetate (CNC), which were prepared by a one-step phase inversion method and applied as a viral hemo-adsorbent for the first time. The characterization results demonstrated that MIL-53(Al) was well dispersed in the CNC matrix. The adsorption results demonstrated that the capture efficiency of the human immunodeficiency virus (HIV) could exceed 99.93%, and the corresponding infectious titer decreased by approximately 103 times in clinical application. Moreover, CNC/MIL-53 exhibited low hemolysis ratios and good anticoagulant properties. Furthermore, molecular dynamics simulations revealed that the interplay of hydrogen bonding was the governing physisorption mechanism. Overall, CNC/MIL-53 could serve as a new type of hemoperfusion adsorbent for virus removal from blood and provide a new treatment pathway to mitigate epidemics.

研究领域: 生物医学工程 · 材料科学 · 病毒学 · 医疗器械
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TALANTA · 2017 · IF 4.162

A combination of computational−experimental study on metal-organic frameworks MIL-53(Al) as sorbent for simultaneous determination of estrogens and glucocorticoids in water and urine samples by dispersive micro-solid-phase extraction coupled to UPLC-MS/MS

Guihua Gao,Sijia Li,Shuo Li,Yudan Wang,Pan Zhao,Xiangyu Zhang,Xiaohong Hou

In this work, computational and experimental methods were used to study the adsorption of estrogens and glucocorticoids on metal–organic frameworks (MOFs). Computer-aided molecular simulation was applied to predict the adsorption of eight analytes on four MOFs (MIL-101(Cr), MIL-100(Fe), MIL-53(Al), and UiO-66(Zr)) by examining molecular interactions and calculating free binding energies. Subsequently, the four water-stable MOFs were synthesized and evaluated as adsorbents for the target hormones in aqueous solution. As the MOF exhibiting the highest adsorption capacity in both computations and experiments, MIL-53(Al) was chosen as a sorbent to develop a dispersive micro-solid-phase extraction procedure coupled to ultra-performance liquid chromatography tandem mass spectrometry for simultaneous determination of the target analytes in water and human urine samples. Experimental parameters affecting the extraction recoveries, including pH, ionic strength , MIL-53(Al) amount, extraction time, desorption time, and desorption solvent, were optimized. The optimized method provided a linear range of 0.005025–368.6   μg/L with good correlation coefficients (0.9982 ≤ r 2 ≤ 0.9992), and limits of detection (S/N = 3) and quantification (S/N = 10) of 0.0015–1.0   μg/L and 0.005–1.8   μg/L, respectively. The analyte recoveries were in the range of 80.6–98.4% in water samples and 88.4–93.2% in urine samples. Furthermore, MIL-53(Al) showed good stability over 10 extraction cycles (RSD < 10.0%). Good agreement between experimental measurements and computational results showed the potential of this approach for elucidating adsorption mechanisms and predicating extraction efficiencies for MOFs and targets, providing new directions for the development and utilization of MOFs.

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