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MICROCHIMICA ACTA · 2017 ·Vol. 185 ·期 1 ·1-8 · IF 4.58

Magnetic mesoporous polymelamine-formaldehyde resin as an adsorbent for endocrine disrupting chemicals

Song Yuhong,Ma Ruiyang,Jiao Caina,Hao Lin,Wang Chun,Wu Qiuhua,Wang Zhi

A magnetic mesoporous poly(melamine-formaldehyde) composite (Fe 3 O 4 -mPMF) was prepared via grafting poly(melamine-formaldehyde) onto the surface of amino-functionalized magnetite (Fe 3 O 4 ) nanoparticles. The material was characterized by scanning electron micrography, transmission electron microscopy, X-ray diffraction, Fourier transform-infrared spectroscopy, nitrogen adsorption-desorption isotherms, and thermogravimetric analysis. It has a large surface area, a typical mesoporous structure, and a high thermal stability. It was employed as a magnetic sorbent for the solid phase extraction of the following endocrine disrupting chemicals (EDCs): Bisphenol A, 4-tert-butylphenol, 4-tert-octylphenol and nonylphenol. The EDCs were then quantified by HPLC. Under the optimized conditions, the response to the EDCs is linear in the range of 0.5–100 ng·mL −1 , and the limits of detection are 0.02–0.1 ng·mL −1 . The high adsorption capability of the Fe 3 O 4 -mPMF is mainly attributed to multiple interactions including π-stacking, hydrogen bonding, and hydrophobic interactions. The method was applied to the extraction of EDCs from spiked river water and bottled juice samples. The results demonstrated that the Fe 3 O 4 -mPMF is an efficient adsorbent for the extraction of organic compounds with large conjugated π-system, plenty of hydrogen-bonding sites, and strong hydrophobicity. A magnetic mesoporous polymelamine-formaldehyde composite (Fe 3 O 4 -mPMF) was prepared and employed as a magnetic sorbent for the solid phase extraction of endocrine disrupting chemicals from river water and bottled juice samples prior to high-performance liquid chromatographic analysis.

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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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JOURNAL OF STEROID BIOCHEMISTRY AND MOLECULAR BIOLOGY · 2025 · IF 2.5

Benzophenone UV-filters: Inhibition on Human and Rat 17β-hydroxysteroid Dehydrogenase 1 - Insights from 3D-QSAR and Docking Studies

Zhuoqi Chen,Chaochao Gong,Shaowei Wang,Han Lu,Yang Zhu,Ren-shan Ge,Yunbing Tang,Yingfen Ying

Benzophenone (BP) UV-filters have been extensively used for the prevention of UV-induced adverse effects in personal care products. Their potential to interfere with steroidogenesis in the female reproductive system remains uncertain. 17β-Hydroxysteroid dehydrogenase 1 (17β-HSD1) facilitates the conversion of estrone to estradiol, playing a key role in estrogen activation. This study delves into the effects of eleven BPs on human and rat 17β-HSD1, while also analysing the 3D-quntitative structure-activity relationship (3D-QSAR) and the underlying mechanisms. The inhibitory potency of inhibiting human placental 17β-HSD1 was found to be in the order of BP-2 (IC 50 , 11.42 μM) > BP-1 (14.17 μM) > BP-4 (49.05 μM) > BP-6 (63.49 μM) = BP-8 (63.46 μM) > others. BP-1 and BP-2 markedly inhibited estradiol secretion by human placental BeWo cells at ≥ 1 μM. In contrast, the inhibitory strength of suppressing rat ovarian 17β-HSD1 activity was found to be in the order of BP-2 (IC 50 , 13.33 μM) > BP-1 (15.09 μM) > BP-4 (22.68 μM) > BP-12 (31.12 μM) > BP (119.99 μM) > others. Mode action analysis revealed that these BP compounds acted as mixed inhibitors of both human and rat 17β-HSD1. The introduction of a 4-hydroxyl substitution in the benzene ring was found to markedly increase the inhibitory potency against human and rat 17β-HSD1. BP-1 and BP-2 demonstrated the ability to penetrate human BeWo cells and inhibit estradiol secretion at ≥ 1 μM. Docking analysis revealed that the 2-hydroxyl group of BP-1 and BP-2 forms a hydrogen bond with catalytic residue Ser142 of human 17β-HSD1. 3D-QSAR pharmacophore analysis showed that there are hydrophobic regions and hydrogen bond donor can interact with BPs. In conclusion, this study establishes that BP-2 is the most potent inhibitors of human 17β-HSD1 among the BPs under investigation, highlighting a significant difference in the structure-activity relationship.

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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

A reliable fluorescent aptasensor for selective detection of trace estradiol based on metal–organic framework click-grafting aptamers functionalized fabric

Xiaoyun Lei,Yang Li,Lu Yu,Siying Meng,Haitao Xu,Rui Wu,Junhai Liu,Xinxin Zhao,Zuoping Zhao

The presence of trace levels of 17β-estradiol (E2) in food and the environment presents a risk to human health, underscoring the need for the development of sensitive analytical methods to detect and accurately monitor its concentration. In this work, we designed a competitive-type fluorescent aptasensor combined with a novel PVDF@UiO-cDNA electrospun nanofiber for E2 detection. The FAM-labelled aptamer in the samples was partially hybridized with cDNA on the PVDF@PDA electrospun by the alkenylation UiO-66. Upon the presence of E2 in the samples, E2 target selectively binds to aptamer, effectively inhibiting its pairing with the cDNA. This innovative approach seamlessly integrated the high capacity electrospun nanofiber, readily modifiable MOF crystals, and the high specificity of aptamer, resulting in an enhanced response to the E2 target. Under the optimized conditions, the fluorescent aptasensor exhibited a wide linear range of 1–100 nM for E2, achieving a high coefficient of determination (R 2 ) of 0.9929, and a low detection limit (LOD) of 0.33 nM. The stability and reproducibility of electrospun nanofiber were validated through its application to milk and water samples, with recoveries ranging from 96.9 % to 130.2 % and a relative standard deviation (RSD) below 8.1 %. These findings highlight the sensitivity and reliability of the developed aptasensor, demonstrating its potential for monitoring trace E2 levels in food and water environments.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Rational design and synthesis of heterogeneous MOF-on-MOF on natural eggshell membrane for highly efficient extraction of trace steroid estrogens in environmental water

Wei Zhou,Liangtao Xu,Ruxue Chen,Xin Wang,Youping Liu,Xin Di

As an important group of endocrine disrupting compounds, most steroid estrogens (SEs) found in environmental water have adverse health effects on aquatic organisms and humans. Sensitive detection of these SEs is crucial for protecting human health and ecosystem safety. Herein, a novel heterogeneous MOF-on-MOF membrane (ESM@His-ZIF-90@ZIF-8) was rationally designed by sequentially growing histidine-modified ZIF-90 and ZIF-8 on natural eggshell membrane (ESM), and employed as an efficient adsorbent for dispersive membrane extraction (DME) of estrone, estradiol and ethynylestradiol from environmental water. Due to the multiple adsorption sites provided by His-ZIF-90@ZIF-8 and the rapid separation of ESM from solution, the ESM@His-ZIF-90@ZIF-8 exhibited extraordinary extraction efficiency towards the three SEs. The adsorption behavior of the three SEs on the ESM@His-ZIF-90@ZIF-8 followed Langmuir isotherm and pseudo-second-order kinetic models. Notably, the ESM@His-ZIF-90@ZIF-8 showed fast adsorption kinetics with adsorption equilibrium of only 10 min. FT-IR, XPS and DFT calculation revealed that the rapid adsorption was attributed to the synergy of π-π stacking, hydrophobic and hydrogen bonding interactions. Additionally, the ESM@His-ZIF-90@ZIF-8 showed excellent reusability and the extraction efficiency remained above 90 % after 20 cycles of reuse. Under optimal conditions, the ESM@His-ZIF-90@ZIF-8-based DME method coupled with HPLC-UV offered good linearity (R 2  ≥ 0.9941) and low limits of detection of 0.30–0.45 μg L -1 . The method recoveries ranged from 85.0-102 % with RSDs lower than 7.2 %. This study highlighted the promising application of heterogeneous MOF-on-MOF membrane in the field of sample pretreatment.

CAS / MDL: 53-16-7 50-28-2 57-63-6
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TALANTA · 2025 · IF 6.1

Preparation of protein-resistant magnetic molecularly imprinted polymers as solid-phase extraction adsorbents via a one-stone-two-birds strategy for selective enrichment of tetracycline in milk

Yi Hao,Jian Shang,Shuyan Liu,Xuemeng Tian,Xin Yao,Fengjun Liu,Ruizhen Zhu,Yue Wang,Ruixia Gao,Sicen Wang

The widespread presence of antibiotic residues in animal-derived foods poses serious risks to public health and the environment, emphasizing the need for urgent action. This study presented a novel lightweight, popcorn-like magnetic molecularly imprinted polymer (LPR-MMIPs) with protein-resistant properties, for the selective enrichment of tetracycline (TC) antibiotics in milk. During the preparation of LPR-MMIPs, bovine serum albumin (BSA) was used as the functional monomer, and tris(2-carboxyethyl)phosphine (TCEP) served as the reducing agent. Using a “one-stone-two-birds” strategy, TCEP not only converted the α -helical structure of BSA to a β -folded conformation for imprinting on the Fe 3 O 4 carrier, but also etched the Fe 3 O 4 into a lightweight, popcorn-like structure under acidic conditions. The BSA imprinting layer excludes proteins through electrostatic repulsion, and the reduced amount of carrier material significantly enhances the adsorption efficiency ( Q  = 12.7 mg g −1 ), selectivity ( IF  = 3.02, SC  > 1.53), and reusability. Meanwhile, LPR-MMIPs, as solid-phase extraction adsorbents, have been successfully applied to the specific adsorption and separation of TC in real milk samples. The established method exhibits good accuracy, precision, and sensitivity, as evidenced by the low LOD (1.80 ng mL −1 ) and LOQ (5.60 ng mL −1 ), low RSDs (≤5.4 %), and high recovery rates (≥94.5 %). Besides, the method demonstrates excellent practical applicability for milk, offering a novel strategy for the selective enrichment of trace antibiotics in milk.

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