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TALANTA · 2021 · IF 6.057

Fabrication of stable multivariate metal-organic frameworks with excellent adsorption performance toward bisphenols from environmental samples

Lizhen Han,Xiaowan Zhang,Dan Li,Mengyuan Li,Peige Qin,Shufang Tian,Youmei Wang,Minghua Lu,Zongwei Cai

As a type of environmental endocrine disrupting chemicals , bisphenols (BPs) have a certain embryonic toxicity and teratogenicity, which can significantly increase the risks of breast cancer, prostate cancer, leukemia and other cancers. In this work, stable multivariate metal-organic frameworks (UiO-66-NH 2 /TCPP x ) were synthesized via in situ one-pot method and used as miniaturized dispersive solid-phase extraction (dμSPE) sorbents for extraction of trace BPs from environmental samples. The phase purity, crystal morphology and physical properties of UiO-66-NH 2 /TCPP x samples were varied by adjusting the mass ratio of TCPP . The extraction performance of UiO-66-NH 2 /TCPP x samples were investigated and UiO-66-NH 2 /TCPP 1.0 exhibited the highest adsorption efficiency. Besides, UiO-66-NH 2 /TCPP 1.0 possessed excellent recycling stability for the adsorption and desorption of BPs more than 20 cycles. The experimental parameters including amount of adsorbent, adsorption time, sample solution pH, temperature, desorption time and desorption solvents which affecting the efficiency of dμSPE were studied, respectively. Good linearity (R 2  > 0.9992) in range of 0.1–200 ng mL −1 was obtained. The detection limits (S/N = 3) and quantification limits (S/N = 10) were achieved at 0.03–0.08 ng mL −1 and 0.1–0.5 ng mL −1 , respectively. The relative standard deviations (RSDs) of intra-day and inter-day ranged from 2.5 to 5.5% and 1.1–6.8%. Enrichment factors were calculated in the range of 303–338. The obtained recoveries of bisphenol F (BPF), bisphenol A (BPA), bisphenol B (BPB) and bisphenol AF (BPAF) were 81.26–91.03% (RSDs = 0.96–6.47%), 82.2–97.27% (RSDs = 0.45–6.15%), 87.56–97.26% (RSDs = 1.1–6.22%) and 82.2–100.8% (RSDs = 0.46–4.07%). The UiO-66-NH 2 /TCPP 1.0 can be employed as potential dμSPE sorbents for the enrichment of trace BPs in the environmental samples.

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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 4 ·1485-1492 · IF 3.288

Metal organic framework/chitosan foams functionalized with polyethylene oxide as a sorbent for enrichment and analysis of bisphenols in beverages and water

Shuo Li,Huizhong Si,Jianshu Li,Mengtian Jia,Xiaohong Hou

In this study, a metal organic framework/chitosan/polyethylene oxide foam (MOFs/CS/PEO foam) was successfully designed and fabricated, in which polyethylene oxide (PEO) acted as a porogen to increase the adsorption capacity of the MIL-53(Al)/CS foam. The inherent characters, e.g. strength and stability, of the modified foam were also significantly improved. As MIL-53(Al) exhibits the highest adsorption capacity in both computations and experiments among the candidates such as MIL-53(Al), MIL-53(Fe), MIL-101(Cr), MIL-101(Fe), UiO-66(Zr), and MIL-100(Fe), the MIL-53(Al)/CS/PEO foam was chosen as a sorbent to develop a vortex assisted solid phase extraction method for the first time. The efficient method was then successfully applied for the extraction of a trace amount of five bisphenols (bisphenol A, bisphenol B, bisphenol C, bisphenol AF and bisphenol F) in beverages and water with plastic containers, followed by high-performance liquid chromatography-fluorescence detection. A satisfactory result of methodology validation was obtained. Under the optimum conditions, the linear ranges were 0.1–20 μg L−1 with the correlation coefficient (r2) ranging from 0.9943 to 0.9977. The method detection limits were in the range of 0.019–0.065 μg L−1. And the recoveries ranged from 72.68 to 104.6% with relative standard deviations smaller than 9.1%. The proposed hybridization foam was durable and environmentally friendly, since it still maintained adsorption ability after being recycled ten times. The novel method proposed in this work could provide technical support in the fields of environmental protection and food safety.

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MICROCHEMICAL JOURNAL · 2018 · IF 2.746

Hollow porous dummy molecularly imprinted polymer as a sorbent of solid-phase extraction combined with accelerated solvent extraction for determination of eight bisphenols in plastic products

Jingjing Zhang,Yu Chen,Wenying Wu,Zhipeng Wang,Yanjie Chu,Xiaohui Chen

In this study, a highly selective and binding hollow porous dummy molecularly imprinted polymer (HPDMIP) was prepared for the separation and determination of bisphenols (BPs) in plastic products using bisphenol AF (BPAF) as dummy template, 4-vinylpyridine as the functional monomer , and MCM-48 as sacrificial support. HPDMIP was characterized by FT-IR spectroscopy, scanning electron microscope, nitrogen adsorption experiment and thermo-gravimetric analysis. Adsorption and selectivity experiments revealed that HPDMIP had a superior adsorption capacity and fast binding kinetics for recognizing BPs. Therefore, a perfect method using HPDMIP as a sorbent material for solid-phase extraction (SPE) was developed, which achieved specific adsorption and enrichment of trace BPs in complex samples. In addition, accelerated solvent extraction (ASE) along with SPE were used as pretreatment method for extracting and concentrating the BPs, and the BPs were determined based on UHPLC–MS/MS. The conditions of ASE and SPE were thoroughly investigated and optimized. Meanwhile, in the ASE proceeding, a Box-Behnken design was applied. Under the optimal conditions, each target analyte had a good linearity between 0.1 and 50 μg·L −1 with regression coefficients in the range of 0.9967–0.9995. Limits of detection and quantification varied from 0.02 to 0.6 μg·L −1 and 0.05 to 2 μg·L −1 , respectively. The spiking recoveries between 50.8 and 138.31% for samples spiked at different concentration levels were achieved. The developed method eliminated the effect of template leakage on quantitative analysis and could be applied to extraction and analysis of BPs in different samples with satisfactory results, which provided a useful tool for further studying the BPs in complex samples.

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TALANTA · 2018 · IF 4.244

Sensitive detection of bisphenol A by coupling solid phase microextraction based on monolayer graphene-coated Ag nanoparticles on Si fibers to surface enhanced Raman spectroscopy

Lu Qiu,Qi Liu,Xiaoliang Zeng,Qin Liu,Xiandeng Hou,Yunfei Tian,Li Wu

In this work, a facile method coupling solid phase microextraction (SPME) with surface enhanced Raman spectroscopy (SERS) was developed for the detection of trace bisphenol A (BPA). Monolayer graphene-coated Ag nanoparticles (Ag NPs) were fabricated on the Si fiber, which made the Si fiber retain functions of both as a SERS-active substrate and SPME fiber to realize in situ rapid determination of BPA. The SERS-active SPME fiber was immersed in water to extract BPA prior to its detection by SERS. The relative standard deviation (RSD) values of the uniformity and the reproducibility of the SERS-active SPME fiber are 14% and 13%, respectively. The characteristic SERS intensity versus BPA concentration showed a linear relationship (R 2 = 0.958). Due to the combination of the SERS method with SPME, this method exhibits extremely high sensitivity and excellent stability for the detection of BPA, with a limit of detection as low as 1 μg L −1 . The method was successfully used for the determination of BPA in water samples with spiked recoveries ranging from 97% to 110%. Compared to the conventional SERS methods used for the detection of BPA, the present method not only retains the advantages of SERS but also provides several unique advantages including preconcentration of analytes, separation of analyte from sample matrices and improvement of sensitivity, thus making its promising application in environmental analysis of BPA.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2017 ·Vol. 409 ·期 8 ·2239-2246 · IF 3.431

In vitro and in silico assessment of the structure-dependent binding of bisphenol analogues to glucocorticoid receptor

Zhang Jie,Zhang Tiehua,Guan Tianzhu,Yu Hansong,Li Tiezhu

Widespread use of bisphenol A (BPA) and other bisphenol analogues has attracted increasing attention for their potential adverse effects. As environmental endocrine-disrupting compounds (EDCs), bisphenols (BPs) may activate a variety of nuclear receptors, including glucocorticoid receptor (GR). In this work, the binding of 11 BPs to GR was investigated by fluorescence polarization (FP) assay in combination with molecular dynamics simulations. The human glucocorticoid receptor was prepared as a soluble recombinant protein. A fluorescein-labeled dexamethasone derivative (Dex-fl) was employed as tracer. Competitive displacement of Dex-fl from GR by BPs showed that the binding affinities of bisphenol analogues were largely dependent on their characteristic functional groups. In order to further understand the relationship between BPs structures and their GR-mediated activities, molecular docking was utilized to explore the binding modes at the atomic level. The results confirmed that structural variations of bisphenol analogues contributed to different interactions of BPs with GR, potentially causing distinct toxic effects. Comparison of the calculated binding energies vs. experimental binding affinities yielded a good correlation ( R 2  = 0.8266), which might be helpful for the design of environmentally benign materials with reduced toxicities. In addition, the established FP assay based on GR exhibited the potential to offer an alternative to traditional methods for the detection of bisphenols.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Carbonized polymer dots-based molecular imprinting: An adsorbent with enhanced selectivity for highly efficient recognition and removal of ceftiofur sodium from complex samples

Li Wang,Lin Liu,Runan Chen,Ya Jiao,Kaixin Zhao,Yongli Liu,Guifen Zhu

Highly selective removal of residual cephalosporin antibiotics from complex systems is crucial for human health and ecological environment protection. Herein, a newly molecularly imprinted polymer adsorbent (CPDs-NH 2 @MIP) with enhanced selectivity for ceftiofur sodium (CTFS) was developed by using the special carbonized polymer dots (CPDs-NH 2 ) as functional monomer . The CPDs-NH 2 has a nano-spherical structure and functionalized groups (C C, −NH 2 ) via the incomplete carbonization polymerization of citric acid , acrylamide and ethylenediamine , which can accurately interact with CTFS by overcoming steric hindrance , resulting in more precisely imprinted sites and reducing non-imprinted regions in MIP. The presented CPDs-NH 2 @MIP exhibited excellent adsorption capacity for CTFS (68.62 mg g −1 ), achieving equilibrium within 10 min, and highly selectivity in mixed solution containing five coexisting substances, with an imprinted factor (5.61). Compared with commercial adsorbents and MIPs prepared with traditional chain functional monomers, the CPDs-NH 2 @MIP showed significant advantage in selective recognition and separation of target. Analysis of microstructure and mechanism proved that usage of the spherical functional monomer generated precise imprinting sites and dense structure in CPDs-NH 2 @MIP, which effectively enhanced the selectivity in complex system combined with hydrogen bonding interaction. The idea of designing and using spherical functional monomer will promote the practicality of molecularly imprinted polymer adsorbents.

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Journal of Environmental Chemical Engineering · 2025 · IF 7.2

Degradation of phoxim by ultrasonic assisted calcium sulfite activated persulfate: Kinetics and mechanisms insights

Zhenjun Xiao,Junlong Zhang,Yijie Lin,Kaixuan Zheng,Zili Lin,Mengyang Niu,Wanlin Lin,Yuchun Hong,Zhongyang Li,Ping Chen,Qingbin Song,Wenying Lv,Guoguang Liu

Developing new technologies to address emerging contaminants are urgently needed. To this end, a novel advanced oxidation system (US/CaSO 3 /PDS) utilizing ultrasound to activate persulfate (PDS) and calcium sulfite (CaSO 3 ) for the effective degradation of emerging contaminants was constructed in this study. The pseudo first-order kinetics constant of Phoxim (PHO) can reach 4.3 × 10 −2 min −1 in US/CaSO 3 /PDS system, revealing the prospects for the treatment of pollutants in water. Electron paramagnetic resonance spectra demonstrated that persulfate anion radicals, hydroperoxyl radicals, hydroxyl radicals, and singlet oxygen were produced in the system. Further, quenching experiments and reactive species probes were used to verify the chemical reaction mechanism of this novel system, and the experimental results highlight the key role of 1 O 2 in the degradation of pollutants thanks to the participation of oxygen. In addition, 11 main products in the PHO degradation process were identified by liquid chromatography-high-resolution precise mass spectrometry, and the possible degradation path of PHO in US/CaSO 3 /PDS system was proposed. US/CaSO 3 /PDS system had high pollutant removal efficiency against a variety of emerging pollutants and was applicable in real water matrix. This study provides a new scheme for the development of advanced oxidation technology based on PDS activation for the removal of refractory emerging pollutants in water.

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FOOD CHEMISTRY · 2024 · IF 8.5

Hydroxyl-functionalized cationic porous organic polymers for efficient enrichment and detection of phenolic endocrine disrupting chemicals in water and snapper

Yiran Dou,Zhi Li,Chenhuan Wang,Qianqian Wang,Zhi Wang,Qiuhua Wu,Chun Wang

Endocrine-disrupting chemicals (EDCs) can disrupt the normal functioning of the endocrine system in organisms, leading to various health issues. Therefore, monitoring EDCs in the environment and food is of significant importance. In this study, a hydroxyl-functionalized ionic porous organic polymer (OH-IPOP) has been synthesized for the first time using 2-benzimidazolemethanol as a monomer. The OH-IPOP exhibited excellent adsorption performance towards phenolic EDCs. An efficient method for determination of phenolic EDCs (p- tert -butylphenol, bisphenol B, bisphenol A and bisphenol F) in environmental water and snapper samples was successfully established by with OH-IPOP as solid-phase extraction sorbent and determination with high-performance liquid chromatography-ultraviolet detection. The method showed good linearity (r 2  > 0.998), low detection limits (0.008–0.020 ng mL −1 for lake water, 1.00–3.00 ng/g for snapper), high recovery rates (82.3–106 %), and good precision (relative standard deviation < 6.6 %), making it a highly efficient adsorbent for the enrichment of EDCs in complex sample matrices.

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JOURNAL OF CHROMATOGRAPHY A · 2025 · IF 4

Magnetic cationic covalent organic framework for efficient enrichment and detection of phenolic endocrine disruptors in foodstuffs

Jiaqi Xu,Wenrui Li,Min Sun,Qianyu Li,Fan Jiang,Yongning Wu,Guoliang Li

Endocrine disrupting chemicals (EDCs) have received significant attention in the food field due to their potential health risks. Herein, we proposed a novel core-shell structure magnetic cationic covalent organic framework (EB-DHTA-iCOF@Fe 3 O 4 ) designed for the efficient enrichment of trace-level EDCs in foodstuffs and analyzed using HPLC-MS/MS. Due to the phenolic EDCs structure possessing hydroxyl functional groups which become protonated under alkaline conditions, resulting in the formation of negatively charged anions. The EB-DHTA-iCOF@Fe 3 O 4 positively charged surface can have a good enrichment effect on EDCs with phenolic structures through electrostatic interactions, π - π interactions, and hydrogen bonding. This unique combination of interactions enhances the iCOF ability to selectively capture and enrich phenolic EDCs from complex matrices, thereby improving the sensitivity and efficiency of their detection in analytical applications. Under optimal magnetic solid-phase extraction (MSPE) conditions, the method showed excellent linearity (5–250 μg kg -1 , R 2 ≥ 0.9993) and a low detection limit (0.03–1.2 μg kg -1 ) for phenolic EDCs, with recovery rates between 86.0 % and 106.8 % and a relative standard deviation under 5.8 %. The approach highlights the potential of the ionic covalent organic framework as an adsorbent for MSPE, offering a promising approach for the detection and analysis of trace-level EDCs in foodstuffs.

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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Mild and friendly preparation of a high-surface porous organic polymers and its application for sensitive detections of endocrine disrupting chemicals

Zhuo Wang,Yuefan Liu,Hao Wang,Weiqian Liang,Zhi-Wei Li,Gangfeng Ouyang

For sample pretreatment technique, the preparation of a stable, practical material with excellent enrichment performance is the core, and especially the preparation of an environmentally friendly adsorbent is desired. The preparation of most materials involves the use of organic solvents, which puts a strain on the environment to a certain extent, and the choice of aqueous solution as the reaction environment for the diazo-coupling reaction has attracted great attention, as a friendly strategy. We prepared the environmentally friendly porous organic polymer (POP) 2,4,6-tris(2,4,6-trihydroxyphenyl)-1,3,5-triazine-4,4′-diaminobiphenyl (CTT-BD) by diazo-coupling reaction, and further fabricated as stable solid phase microextraction (SPME) fiber. It achieved efficient extraction of derivatized bisphenol endocrine disrupting chemicals (EDCs) from water samples with enrichment factors ranging from 1306 to 2781. Under the optimum experimental conditions, the developed method by combining the CTT-BD coated fiber with gas chromatography mass spectrometry (GC–MS), demonstrated a wide linearity (10–10000 ng/L), low limits of detection (2.0–3.0 ng/L) and good reproducibility (relative standard deviations 3.1–8.1 %). Finally, the proposed method has been successfully used for the determinations of EDCs from water samples, and satisfactory recoveries (85.6–118.0 %) were achieved.

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SENSORS AND ACTUATORS B-CHEMICAL · 2018 · IF 5.667

An ultrasensitive electrochemical bisphenol A sensor based on hierarchical Ce-metal-organic framework modified with cetyltrimethylammonium bromide

Jing Zhang,Xiaojian Xu,Lu Chen

This work constructed an ultrasensitive electrochemical bisphenol A (BPA) sensor using hierarchical Ce-metal-organic framework (Ce-MOF) modified with cetyltrimethylammonium bromide (CTAB) as a sensing platform. Ce-MOF had been successfully prepared and conveniently modified with a cationic surfactant (CTAB) via the electrostatic interaction. Ce-MOF and CTAB/Ce-MOF were characterized by scanning electron microscopy, X-ray diffraction, infrared spectrum, thermogravimetric analysis and zeta potentials analysis. CTAB/Ce-MOF suspension was dropped onto glassy carbon electrode (GCE) surface to fabricate CTAB/Ce-MOF/GCE. Combined with preconcentration of BPA of the long alkane chain in CTAB via hydrophobic interaction and electrocatalytic activity of Ce-MOF, the dual amplification made CTAB/Ce-MOF/GCE exhibit high electrochemical response toward the oxidation of BPA, and an electrochemical BPA sensor was constructed based on CTAB/Ce-MOF/GCE by differential pulse voltammetry. The designed BPA sensor had a wide linear range from 0.005 to 50 μmol L −1 and a low detection limit of 2.0 nmol L −1 (S/N = 3). The proposed sensor had excellent reproducibility, stability and anti-interference, and was successfully employed for BPA detection in real samples. This convenient and sensitive sensor proved to be a promising and reliable tool for detecting BPA in food and environmental pollution.

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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Comprehensive assessment of the safety of bisphenol A and its analogs based on multi-toxicity tests in vitro

Juan Wang,Xiangsheng Hong,Wang Liu,Le Zhang,Saihong Yan,Zhitong Li,Jinmiao Zha

As substitutes for bisphenol A (BPA), bisphenol analogs (BPs) have raised concerns due to their frequent environmental detection and unclear safety. Here, the cytotoxicity, endocrine disruption, neurotoxicity, aryl hydrocarbon receptor (AhR) activity, and genotoxicity of nine BPs and BPA were evaluated in three types of cell lines. Over half of the tested BPs exhibited greater cytotoxicity than BPA, with IC50 values showing a linear correlation with Log Kow (R²=0.69). All tested BPs exhibited at least one endocrine-disrupting effect, notably estrogenic, which was observable even at 0.01–0.1   μM. Importantly, BPAF and BPAP exposure had widespread endocrine-suppressing effects. Moreover, all BPs (except BPP) and BPA increased SH-SY5Y cells apoptosis at 1–10   μM. Only BPF and BPP significantly increased 7-ethoxyresorufin-O-deethylase levels, highlighting their notable effects on AhR activity. BPAF significantly induced DNA damage at 1.25   μM, whereas BPA, BPF, and BPP induced damage at 20, 25, and 25   μM, respectively. Finally, ToxPi, a weighted scoring system, was used to rank the comprehensive toxicity of BPs, with 7 of 9 BPs showing higher scores than BPA. Collectively, BPs generally exhibited stronger comprehensive toxicity compared with BPA, emphasizing the urgent need for further research to confirm their potential health implications.

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