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JOURNAL OF STEROID BIOCHEMISTRY AND MOLECULAR BIOLOGY · 2022 · IF 5.011

Diverse effects of α-/β-estradiol on catalytic activities of human UDP-glucuronosyltransferases (UGT)

Liangliang Zhu,Hui Lv,Ling Xiao,Yanyao Hou,Wenjuan Li,Guangbo Ge,Chunzhi Ai

β-estradiol (β-E2) and α-estradiol (α-E2) act as an endo- and an exon-estrogen in humans, respectively. There is a structural variation in C17-OH configuration of the two estrogens. UDP-glucuronosyltransferases (UGT) are responsible for termination of activities of a variety of endogenous hormones, clinical drugs, and environmental toxicants. The current study was conducted to investigate the effects of the two estrogens towards catalytic activities of UGTs. It was found that β-E2 could decrease activities of UGT1A9 , − 2B4 and − 2B7, with K i values of a few micro-molars. β-E2 could additionally accelerate the activity of UGT2B17 via promoting enzyme-substrate binding and increasing the turn over number . Comparatively, α-E2 displayed much stronger inhibitory potentials towards UGT2B7 and − 2B4, but showed little influence to UGT1A9 and − 2B17. The K i values for inhibition of UGT2B7 in glucuronidation of different substrates by α-E2 were in a nanomolar range that is only about 1/100–1/50 of β-E2. UGT2B7 structural model was fatherly constructed to explore the mechanism underlying dramatically different inhibition selectivity of the two estrogens. Compared to β-E2, α-E2 formed more hydrophobic and hydrogen-bonded interactions with the residues in the active pocket. It is concluded that the configuration of E2–17-OH determines the inhibitory potentials towards UGTs. The results are useful in better understanding ligand selectivity of UGTs, as well as in further development of α-E2 in health protection.

CAS / MDL: 130929-57-6
研究领域: 药理学 · 生物化学 · 分子生物学 · 内分泌学
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JOURNAL OF SEPARATION SCIENCE · 2020 ·Vol. 43 ·期 17 ·3520-3533 · IF 2.878

Monodisperse restricted access material with molecularly imprinted surface for selective solid-phase extraction of 17β-estradiol from milk

Xiaoxiao Wang,Huachun Liu,Zhian Sun,Shanwen Zhao,Yanqiang Zhou,Jianmin Li,Tianpei Cai,Bolin Gong

In this study, novel monodisperse restricted access media-molecularly imprinted polymers were successfully prepared by surface initiated reversible addition-fragmentation chain transfer polymerization using monodisperse crosslinked poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres as the carrier and acryloyl chloride-modified β-cyclodextrin as the hydrophilic functional monomer. The surface morphology, protein exclusion, and adsorption properties of the molecularly imprinted polymers were investigated. The results show that the material has excellent monodispersity and hydrophilicity, and simultaneously exhibit high adsorption capacity, fast binding kinetics, high selectivity, and significant thermal stability. The molecularly imprinted polymers as dispersive solid-phase extraction adsorbent combined with reversed-phase high-performance liquid chromatography was used to selectively enrich, separate, and analyze trace 17β-estradiol in milk samples. The recovery of 17β-estradiol is 88–95% with relative standard deviation of <4%, and the limits of detection and quantification of this method are 2.08 and 9.29 µg/L, respectively. The novel restricted access media-molecularly imprinted polymer adsorbents provide an effective method for the selective extraction and detection of 17β-estradiol directly from complex samples.

研究领域: 分析化学 · 材料科学 · 环境科学
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Scientific Reports · 2012 ·Vol. 2 ·期 1 ·1-8 · IF 0

Polymer-drug conjugates for intracellar molecule-targeted photoinduced inactivation of protein and growth inhibition of cancer cells

Wang Bing,Yuan Huanxiang,Zhu Chunlei,Yang Qiong,Lv Fengting,Liu Libing,Wang Shu

For most molecule-targeted anticancer systems, intracellular protein targets are very difficult to be accessed by antibodies and also most efforts are made to inhibit protein activity temporarily rather than inactivate them permanently. In this work we firstly designed and synthesized multifunctional polymer-drug conjugates (polythiophene-tamoxifen) for intracellular molecule-targeted binding and inactivation of protein (estrogen receptor α, ERα) for growth inhibition of MCF-7 cancer cells. Small molecule drug was conjugated to polymer side chain for intracellular signal protein targeting and simultaneously the fluorescent characteristic of polymer for tracing the cellular uptake and localization of polythiophene-drug conjugates by cell imaging. Under light irradiation, the conjugated polymer can sensitize oxygen to produce reactive oxygen species (ROS) that specifically inactivate the targeted protein and thus inhibit the growth of tumor cells. The conjugates showed selective growth inhibition of ERα positive cancer cells, which exhibits low side effect for our intracellular molecule-targeted therapy system.

CAS / MDL: 57-91-0
研究领域: 药理学 · 肿瘤学 · 生物化学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2024 · IF 5.9

Facile preparation of novel magnetic metal-organic frameworks/Ti3C2Tx composite for efficiently removal of bisphenol A from water samples

Cheng Yang,Yanmei Shi,Lixin Li,Zhihong Chen,Di Zhao,Weixia Zhu,Kai Hu

Bisphenol A (BPA) is widespread in the environment and has a serious impact on human body. In this study, a novel magnetic metal-organic frameworks@Ti 3 C 2 T x composite, noted as Fe 3 O 4 @Ti 3 C 2 T x /MOF, was prepared and used as adsorbent for the removal of BPA from environmental water. The adsorption parameters that affecting the removal efficiency of BPA, such as solution pH, contact time, adsorbent dosage, co-existing inorganic ions, ionic strength, and humic acid were investigated in detail. Accordingly, the removal efficiency of BPA by Fe 3 O 4 @Ti 3 C 2 T x /MOF was as much as 95 %. Adsorption studies showed that the proposed composite can provide a maximum adsorption capacity of 547.43 mg g −1 for BPA within 5 min, which was superior to most of the reported adsorbents. The adsorption process was consistent with the pseudo-second-order kinetics (K 2 , 1.1063 μg mg −1 min −1 ) and Freundlich isotherm model, indicating that the adsorption was depended by chemisorption and the heterogeneous surface. Furthermore, the thermodynamic results demonstrated the exothermic nature of the adsorption process (ΔH θ  = −34.84 kJ mol −1 ). Most importantly, the magnetic properties of the Fe 3 O 4 @Ti 3 C 2 T x /MOF make it easy to collect, so it can be regenerated and reused for at least 4 cycles without significant loss of adsorption efficiency. Overall, the proposed composite can be applied to the efficient removal of BPA from water samples and could be potentially applicable for practical wastewater treatment.

研究领域: 环境科学 · 材料科学
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ANALYTICAL CHEMISTRY · 2024 · IF 6.7

Online Charge-Generation Derivatization by Electrochemical Radical Cations of Thianthrene: Mass Spectrometry Imaging of Estrogens in Biological Tissues

Yingchao Liu,Jiahui Bai,Xiaoxia Dong,Yuqi Cao,Mingmai Bao,Yingjie Lu,Hui Zeng,Lixing Zhan,Yinlong Guo

Estrogens play a significant role in endocrinology and oncology. Although separation methods coupled with mass spectrometry (MS) have emerged as a powerful tool for studying estrogens, imaging the spatial distributions of estrogens is crucial but remains challenging due to its low endogenous concentration and poor ionization efficiency. Charge-generation derivatization, such as N-alkylpyridinium quaternization and S-methyl thioetherification, represents a method wherein neutral molecules involving analytes and derivatization reagents undergo chemical reactions to establish permanent charges directly onto the analytes to improve detection sensitivity. Here, we developed a novel derivatization reagent, thianthrene (TT), which enabled oxidization to radical cations ([TT]•+) using an electrochemical method and completed the online charge-generation derivatization of estrogens on a mass spectrometry imaging platform. In this strategy, [TT]•+ can efficiently and selectively derivatize estrogens via an electrophilic aromatic substitution reaction. Results indicated that derivatization with [TT]•+ can significantly enhance imaging sensitivity (3 orders of magnitude), enabling the visualization of estrogen and its metabolites in ovarian and breast tissues. Furthermore, a higher mass intensity of these estrogens was captured in breast para-cancerous tissues than in cancerous tissues, which might provide estrogens spatial dimension information for further research on the initiation and progression of breast cancer.

研究领域: 生物化学 · 肿瘤学 · 分析化学
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International Journal of Environmental Research and Public Health · 2018 ·Vol. 15 ·期 7 ·1454 · IF 2.145

Adsorption of Trace Estrogens in Ultrapure and Wastewater Treatment Plant Effluent by Magnetic Graphene Oxide

Xianze Wang,Zhongmou Liu,Zhian Ying,Mingxin Huo,Wu Yang

In the current study, graphene oxide, Fe3+, and Fe2+were used for the synthesis of magnetic graphene oxide (MGO) by an in situ chemical coprecipitation method. Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction were used to characterize the well-prepared MGO. The prepared MGO was used as an adsorbent to remove five typical estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethinylestradiol (17α-E2), estriol (E3), and synthetic estrogen (EE2)) at the ppb level from spiked ultrapure water and wastewater treatment plant effluent. The results indicated that the MGO can efficiently remove estrogens from both spiked ultrapure water and wastewater treatment plant effluent in 30 min at wide pH ranges from 3 to 11. The temperature could significantly affect removal performance. A removal efficiency of more than 90% was obtained at 35 °C in just 5 min, but at least 60 min was needed to get the same removal efficiency at 5 °C. In addition, an average of almost 80% of the estrogens can still be removed after 5 cycles of MGO regeneration but less than 40% can be reached after 10 cycles. These results indicate that MGO has potential for practical applications to remove lower levels of estrogens from real water matrixes and merits further evaluation.Keywords:estrogens;magnetic graphene oxide;adsorption;wastewater treatment plant effluent

研究领域: 环境科学 · 材料科学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2014 · IF 3.107

Molecularly Imprinted Polymer on Magnetic Graphene Oxide for Fast and Selective Extraction of 17β-Estradiol

Fangjian Ning,Hailong Peng,Jinhua Li,Lingxin Chen,Hua Xiong

A novel nanosized substrate imprinted polymer (MIPs-GO-Fe3O4) was developed on a magnetic graphene oxide (GO-Fe3O4) surface for selective recognition and fast removal of 17β-estradiol (17β-E2). The characteristics of MIPs-GO-Fe3O4 were evaluated by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy. and vibrating sample magnetometer (VSM). Results suggested that GO had a thin single-layer structure anchoring Fe3O4 nanoparticles and that the imprinted film was coated on the GO-Fe3O4 surface. MIPs-GO-Fe3O4 was sensitive to the magnetic field and could be easily separated using an external magnet. The adsorption results indicated that the kinetic value and binding capacity of MIPs-GO-Fe3O4 were 0.0062 g (mg·min)−1 and 4.378 μmol g–1, respectively. The Langmuir–Freundlich isotherm and pseudo-second-order kinetic models were the main adsorption mechanisms for MIPs-GO-Fe3O4. MIPs-GO-Fe3O4 showed excellent recognition selectivity, as well as enrichment and separation abilities for 17β-E2 in complex matrices. MIPs-GO-Fe3O4 was also used to analyze 17β-E2 in real food samples, and satisfactory recoveries such as 84.20% with relative standard deviation (RSD) of 4.67% at a spike of 0.5 μmol L–1 were obtained. Thus, the MIPs-GO-Fe3O4-based method provided a convenient and practical platform for the separation, enrichment, and removal of 17β-E2 in food samples.

研究领域: 材料科学 · 分析化学 · 环境科学 · 食品科学
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JOURNAL OF CHROMATOGRAPHY A · 2016 · IF 3.926

Preparation of photonic-magnetic responsive molecularly imprinted microspheres and their application to fast and selective extraction of 17β-estradiol

Hailong Peng,Mei Luo,Hua Xiong,Ningxiang Yu,Fangjian Ning,Jieping Fan,Zheling Zeng,Jinhua Li,Lingxin Chen

Photonic-magnetic responsive molecularly imprinted microspheres (PM-MIMs) were prepared by seed polymerization, through suitable functionalization of magnetic nanoparticles for further coating with photoresponsive functional monomer and imprinted layers, and then were successfully applied to the fast and selective extraction of 17β-estradiol (17β-E 2 ) from real samples. The PM-MIMs possessed a sandwich micro-spherical structure containing Fe 3 O 4 core, SiO 2 middle layer, and MIPs shell with thickness of 25   nm. The PM-MIMs displayed excellent photoresponsive properties and could be rapidly separated from solutions under an external magnet. The PM-MIMs had specific affinity towards 17β-E 2 with high adsorption capacity ( Q max   =   0.84   mg   g −1 ) and fast binding kinetics ( K d   =   26.08   mg   L −1 ). The PM-MIMs proved to be an ideal photoswitch with the ability of reversible uptake and release of 17β-E 2 upon alternate 365 and 440   nm irradiation: 45.0% of 17β-E 2 released from the PM-MIMs upon 365   nm irradiation, and 94.0% of the released 17β-E 2 was rebound to the PM-MIMs at 440   nm. Accordingly, the PM-MIMs were applied for fast separation and extraction of 17β-E 2 followed by HPLC-UV determination, presenting the low limit of detection (LOD, S/N   =   3) and quantification (LOQ, S/N   =   10) of 0.18 and 0.62   μmol   L −1 , respectively. The high recoveries for spiked milk powder and drinking water samples were in the range of 97.5–113.0% with relative standard deviations less than 4.4%. This study reasonably combined photonic response, magnetic separation and surface imprinting, which endowed the PM-MIMs with significant advantages of high adsorption capacity and fast binding kinetics, convenient separation and recycled use, and simple rapid eco-benign adsorption/elution processes for template molecules. Thus, the PM-MIMs based method may be a simple, rapid, convenient, cost-effective and environmentally-friendly way for simultaneous separation, enrichment and detection of trace 17β-E 2 in complicated matrices.

研究领域: 分析化学 · 环境科学
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CHROMATOGRAPHIA · 2022 ·Vol. 85 ·期 8 ·733-741 · IF 2.213

Development of an Efficient Solid-Phase Microextraction Monolithic Column for the Analysis of Estrogens in Human Urine and Serum Samples

Zhang Qianchun,Wang Yutong,Yang Bingnian,Bao Linchun,Wu Yun,Wang Xingyi

Estrogen plays a crucial role in various stages of human development and is present in the human body at trace level; therefore, an efficient strategy for the quantitative analysis of trace estrogens is required. However, this analysis is complicated by the presence of extremely complex biological matrices. To address this challenge, a novel method based on monolithic column solid-phase microextraction and ultra-high-performance liquid chromatography-tandem mass spectrometry was developed for the sensitivity analysis of six estrogens: β-estradiol, α-estradiol, 17α-ethynylestradiol, estrone, diethylstilbestrol, and hexestrol, in human urine and serum samples. The method exhibits a low limit of detection (8.6–37 ng L −1 ), with wide linear ranges (0.10–25 μg L −1 ) for each analyte and remarkable correlation coefficients ( R 2  = 0.9953–0.9995). The developed method was successfully used to detect estrogens in urine and serum samples. The six analytes were satisfactorily recovered between 76.2 and 107% with relative standard deviations ranging from 2.5 to 8.3% ( n  = 3). The results demonstrated that the developed method, based on a poly(methacrylic acid/3-acrylamidophenylboronic acid-co-ethylene glycol dimethacrylate) monolithic column, is an effective enrichment approach toward the analysis of trace estrogens in human urine and serum samples. Graphical abstract

研究领域: 分析化学 · 环境科学 · 医学
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ANALYTICA CHIMICA ACTA · 2022 · IF 6.911

Porous capillary monolithic column coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry for fast and effective separation and determination of estrogens

Yanqun Yang,Yipeng Huang,Zhuqiang Wu,Rui Shi,Zhengyi Chen,Guihua Ruan

In this work, a porous capillary monolithic column was simply prepared by in situ thiol-alkyne click polymerization of dipentaerythritol hexakis (3-mercaptopropionate) and dimethyl dipropargylmalonate in fused-silica capillary. The capillary monolithic column shows excellent permeability, high porosity, and thoiether-rich groups, thereby, a high-efficient capacity for trace estrogens from complex samples are obtained via electron-donor-acceptor π-π interaction and hydrophobic interaction. The highest adsorption efficiency for estrogens is achieved at pH = 7.0 with a flow rate of 0.200 mL min −1 . The superior adsorption capacities of the as-prepared capillary column for eight estrogens range from 0.092 mg m −1 to 0.31 mg m −1 . A simple, reliable, and sensitive method for the determination of eight estrogens in biological and environmental samples is developed using the monolithic polymer as in-tube solid-phase microextraction coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry (SPME-UPLC-MS/MS), and the total instrumental analysis time for the SPME-UPLC-MS/MS procedures was about 60 min per sample. The developed method shows a wide linear range (0.0500–5.00 μg L −1 ), and low limits of detection (5.34–9.63 ng L −1 ) for estrogens. The concentrations of estrogens in serum, urine, and pond water samples are found to be no more than 3.69, 0.741, and 1.04 μg L −1 , respectively, and the satisfying recoveries for the eight estrogens range from 80.3% to 113% with relative standard deviations ( n  = 5) of 1.5–9.4%. The established method is highly potential for extraction and analysis of ultratrace target estrogens in complex matrices, such as biological and environmental samples.

研究领域: 分析化学 · 环境科学
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JOURNAL OF HAZARDOUS MATERIALS · 2022 · IF 14.224

MXene−reinforced octahedral PtCu nanocages with boosted electrocatalytic performance towards endocrine disrupting pollutants sensing

Xian Liu,Like Chen,Yang Yang,Liping Xu,Junyong Sun,Tian Gan

Rational tailoring of hollow and porous bimetallic structures with excellent electrocatalytic performance is appealing yet challenging. Further, combining independent bimetallic nanoparticles with flexible two-dimensional substrate by forming stable heterocomplex is still highly desired for electrocatalysis. Herein, hierarchical PtCu alloy octahedrons with hollow interiors and nanosheet-assembled nanoshells were synthesized by a facile and efficient chemical transformation strategy using Cu 2 O as sacrificial templates. Such octahedral PtCu nanocages displayed significantly enhanced electrocatalytic activity owing to their unique hollow and porous architectures which provided easy access for analytes to the catalyst surface. Thereafter, introduction of Ti 3 C 2 T x MXene was realized via simple incubation of Ti 3 C 2 T x in solution containing the 3-aminopropyltriethoxysilane-capped PtCu, and their electrostatic interaction guaranteed the firm adsorption of PtCu nanocages on Ti 3 C 2 T x nanosheets. It turned out that the sensitivity of the hybrid sensor was remarkably improved for electrochemical monitoring of endocrine disrupting pollutants in water, exhibiting ultrawide linear ranges and sub-nanomole detection limits. The eminent electrode performance is attributed to the high specific area, fast electrochemical kinetics, decent electrical catalytic ability, and the synergistic effect between Pt, Cu, and MXene.

研究领域: 材料科学 · 环境科学 · 分析化学
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