Hepatitis B virus RNAs co-opt ELAVL1 for stabilization and CRM1-dependent nuclear export.

Hepatitis B virus (HBV) chronically infects 296 million people worldwide, posing a major global health threat. Export of HBV RNAs from the nucleus to the cytoplasm is indispensable for viral protein translation and genome replication, however the mechanisms regulating this critical process remain largely elusive. Here, we identify a key host factor embryonic lethal, abnormal vision, Drosophila-like 1 (ELAVL1) that binds HBV RNAs and controls their nuclear export. Using an unbiased quantitative proteomics screen, we demonstrate direct binding of ELAVL1 to the HBV pregenomic RNA (pgRNA). ELAVL1 knockdown inhibits HBV RNAs posttranscriptional regulation and suppresses viral replication. Further mechanistic studies reveal ELAVL1 recruits the nuclear export receptor CRM1 through ANP32A and ANP32B to transport HBV RNAs to the cytoplasm via specific AU-rich elements, which can be targeted by a compound CMLD-2. Moreover, ELAVL1 protects HBV RNAs from DIS3+RRP6+ RNA exosome mediated nuclear RNA degradation. Notably, we find HBV core protein is dispensable for HBV RNA-CRM1 interaction and nuclear export. Our results unveil ELAVL1 as a crucial host factor that regulates HBV RNAs stability and trafficking. By orchestrating viral RNA nuclear export, ELAVL1 is indispensable for the HBV life cycle. Our study highlights a virus-host interaction that may be exploited as a new therapeutic target against chronic hepatitis B.

Hepatitis B virus hijacks TSG101 to facilitate egress via multiple vesicle bodies.

Hepatitis B virus (HBV) chronically infects 296 million individuals and there is no cure. As an important step of viral life cycle, the mechanisms of HBV egress remain poorly elucidated. With proteomic approach to identify capsid protein (HBc) associated host factors and siRNA screen, we uncovered tumor susceptibility gene 101 (TSG101). Knockdown of TSG101 in HBV-producing cells, HBV-infected cells and HBV transgenic mice suppressed HBV release. Co-immunoprecipitation and site mutagenesis revealed that VFND motif in TSG101 and Lys-96 ubiquitination in HBc were essential for TSG101-HBc interaction. In vitro ubiquitination experiment demonstrated that UbcH6 and NEDD4 were potential E2 ubiquitin-conjugating enzyme and E3 ligase that catalyzed HBc ubiquitination, respectively. PPAY motif in HBc and Cys-867 in NEDD4 were required for HBc ubiquitination, TSG101-HBc interaction and HBV egress. Transmission electron microscopy confirmed that TSG101 or NEDD4 knockdown reduces HBV particles count in multivesicular bodies (MVBs). Our work indicates that TSG101 recognition for NEDD4 ubiquitylated HBc is critical for MVBs mediated HBV egress.

Histone acetyltransferase 1 is a succinyltransferase for histones and non-histones and promotes tumorigenesis.

Lysine succinylation (Ksucc) is an evolutionarily conserved and widespread post-translational modification. Histone acetyltransferase 1 (HAT1) is a type B histone acetyltransferase, regulating the acetylation of both histone and non-histone proteins. However, the role of HAT1 in succinylation modulation remains unclear. Here, we employ a quantitative proteomics approach to study succinylation in HepG2 cancer cells and find that HAT1 modulates lysine succinylation on various proteins including histones and non-histones. HAT1 succinylates histone H3 on K122, contributing to epigenetic regulation and gene expression in cancer cells. Moreover, HAT1 catalyzes the succinylation of PGAM1 on K99, resulting in its increased enzymatic activity and the stimulation of glycolytic flux in cancer cells. Clinically, HAT1 is significantly elevated in liver cancer, pancreatic cancer, and cholangiocarcinoma tissues. Functionally, HAT1 succinyltransferase activity and the succinylation of PGAM1 by HAT1 play critical roles in promoting tumor progression in vitro and in vivo. Thus, we conclude that HAT1 is a succinyltransferase for histones and non-histones in tumorigenesis.

Construction and Evaluation of Alginate Dialdehyde Grafted RGD Derivatives/Polyvinyl Alcohol/Cellulose Nanocrystals IPN Composite Hydrogels.

To enhance the mechanical strength and cell adhesion of alginate hydrogel, making it satisfy the requirements of an ideal tissue engineering scaffold, the grafting of Arg-Gly-Asp (RGD) polypeptide sequence onto the alginate molecular chain was conducted by oxidation of sodium periodate and subsequent reduction amination of 2-methylpyridine borane complex (2-PBC) to synthesize alginate dialdehyde grafted RGD derivatives (ADA-RGD) with good cellular affinity. The interpenetrating network (IPN) composite hydrogels of alginate/polyvinyl alcohol/cellulose nanocrystals (ALG/PVA/CNCs) were fabricated through a physical mixture of ion cross-linking of sodium alginate (SA) with hydroxyapatite/D-glucono-δ-lactone (HAP/GDL), and physical cross-linking of polyvinyl alcohol (PVA) by a freezing/thawing method, using cellulose nanocrystals (CNCs) as the reinforcement agent. The effects of the addition of CNCs and different contents of PVA on the morphology, thermal stability, mechanical properties, swelling, biodegradability, and cell compatibility of the IPN composite hydrogels were investigated, and the effect of RGD grafting on the biological properties of the IPN composite hydrogels was also studied. The resultant IPN ALG/PVA/CNCs composite hydrogels exhibited good pore structure and regular 3D morphology, whose pore size and porosity could be regulated by adjusting PVA content and the addition of CNCs. By increasing the PVA content, the number of physical cross-linking points in PVA increased, resulting in greater stress support for the IPN composite hydrogels of ALG/PVA/CNCs and consequently improving their mechanical characteristics. The creation of the IPN ALG/PVA/CNCs composite hydrogels' physical cross-linking network through intramolecular or intermolecular hydrogen bonding led to improved thermal resistance and reduced swelling and biodegradation rate. Conversely, the ADA-RGD/PVA/CNCs IPN composite hydrogels exhibited a quicker degradation rate, attributed to the elimination of ADA-RGD by alkali. The results of the in vitro cytocompatibility showed that ALG/0.5PVA/0.3%CNCs and ADA-RGD/PVA/0.3%CNCs composite hydrogels showed better proliferative activity in comparison with other composite hydrogels, while ALG/PVA/0.3%CNCs and ADA-RGD/PVA/0.3%CNCs composite hydrogels displayed obvious proliferation effects, indicating that PVA, CNCs, and ADA-RGD with good biocompatibility were conducive to cell proliferation and differentiation for the IPN composite hydrogels.

IFN-α2b inhibits the ethanol enriched-HBV cccDNA through blocking a positive feedback loop of HBx/MSL2/cccDNA/HBV/HBx in liver.

Hepatitis B virus (HBV) is a major risk factor for liver diseases, in which HBV covalently closed circular DNA (cccDNA), as the genomic form that templates viral transcription, plays crucial roles in sustaining viral persistence. Clinically, the excessive ethanol intake accelerates the progression of liver diseases with HBV infection. Here, we supposed that ethanol might trigger HBV cccDNA in the liver. Interestingly, we observed that the ethanol remarkably elevated the levels of HBeAg, HBsAg, HBV DNA and cccDNA in HBV-expressing hepatoma cells. Mechanically, the ethanol increased the levels of HBx and MSL2 in vivo and in HBV-expressing HepG2 cells, but not in HBV-free HepG2 cells. Moreover, the down-regulation of MSL2 by small interference RNA could block the ethanol-promoted HBV cccDNA in HepG2.2.15 cells. As a commonly administered treatment for HBV, the effect of IFNα on ethanol-triggered HBV cccDNA remains poorly understood. Strikingly, we showed that the treatment with IFN-α2b inhibited the ethanol-promoted cccDNA through depressing MSL2 in the cells. Thus, we conclude that IFN-α2b inhibits the ethanol-enriched HBV cccDNA through blocking a positive feedback loop of HBx/MSL2/cccDNA/HBV/HBx. Our finding provides new insights into the mechanism by which IFN-α2b inhibits ethanol-enhanced HBV cccDNA. Therapeutically, IFNα may contribute to the cccDNA induced by ethanol in liver.

Aspirin inhibits the proliferation of hepatoma cells through controlling GLUT1-mediated glucose metabolism.

Aspirin can efficiently inhibit liver cancer growth, but the mechanism is poorly understood. In this study, we report that aspirin modulates glucose uptake through downregulating glucose transporter 1 (GLUT1), leading to the inhibition of hepatoma cell proliferation. Our data showed that aspirin significantly decreased the levels of reactive oxygen species (ROS) and glucose consumption in hepatoma cells. Interestingly, we identified that GLUT1 and HIF1α could be decreased by aspirin. Mechanically, we demonstrated that the -1008/-780 region was the regulatory element of transcriptional factor NF-κB in GLUT1 promoter by luciferase report gene assays. PDTC, an inhibitor of NF-κB, could suppress the expression of GLUT1 in HepG2 and H7402 cells, followed by affecting the levels of ROS and glucose consumption. CoCl2-activated HIF1α expression could slightly rescue the GLUT1 expression inhibited by aspirin or PDTC, suggesting that aspirin depressed GLUT1 through targeting NF-κB or NF-κB/HIF1α signaling. Moreover, we found that GLUT1 was highly expressed in clinical HCC tissues relating to their paired adjacent normal tissues. Importantly, we observed that high level of GLUT1 was significantly correlated with the poor relapse-free survival of HCC patients by analysis of public data. Functionally, overexpression of GLUT1 blocked the PDTC-induced or aspirin-induced inhibition of glucose metabolism in HepG2 cells. Conversely, aspirin failed to work when GLUT1 was stably knocked down in the cells. Administration of aspirin could depress the growth of hepatoma cells through controlling GLUT1 in vitro and in vivo. Thus, our finding provides new insights into the mechanism by which aspirin depresses liver cancer.

Hepatitis B virus X protein-elevated MSL2 modulates hepatitis B virus covalently closed circular DNA by inducing degradation of APOBEC3B to enhance hepatocarcinogenesis.

Chronic hepatitis B virus (HBV) infection is a leading cause in the occurrence of hepatitis B, liver cirrhosis, and liver cancer, in which nuclear HBV covalently closed circular DNA (cccDNA), the genomic form that templates viral transcription and sustains viral persistence, plays crucial roles. In the present study, we explored the hypothesis that HBV X protein (HBx)-elevated male-specific lethal 2 (MSL2) activated HBV replication by modulating cccDNA in hepatoma cells, leading to hepatocarcinogenesis. Immunohistochemical analysis revealed that the expression of MSL2 was positively associated with that of HBV and was increased in the liver tissues of HBV-transgenic mice and clinical HCC patients. Interestingly, microarray profiling identified that MSL2 was associated with those genes responding to the virus. Mechanistically, MSL2 could maintain HBV cccDNA stability through degradation of APOBEC3B by ubiquitylation in hepatoma cells. Above all, HBx accounted for the up-regulation of MSL2 in stably HBx-transfected hepatoma cell lines and liver tissues of HBx-transgenic mice. Luciferase reporter gene assays revealed that the promoter region of MSL2 regulated by HBx was located at nucleotide -1317/-1167 containing FoxA1 binding element. Chromatin immunoprecipitation assay validated that HBx could enhance the binding property of FoxA1 to MSL2 promoter region. HBx up-regulated MSL2 by activating YAP/FoxA1 signaling. Functionally, silencing MSL2 was able to block the growth of hepatoma cells in vitro and in vivo. CONCLUSION: HBx-elevated MSL2 modulates HBV cccDNA in hepatoma cells to promote hepatocarcinogenesis, forming a positive feedback loop of HBx/MSL2/cccDNA/HBV. Our finding uncovers insights into the mechanism by which MSL2 as a promotion factor in host cells selectively activates extrachromosomal DNA. (Hepatology 2017;66:1413-1429).

Detection and identification of transformer winding strain based on distributed optical fiber sensing.

At present, transformer winding strain monitoring is divided mainly into off-line detection and on-line detection. Due to the interference of the complex electromagnetic environment, on-line detection has not been widely used. Although off-line detection is more mature, it can not accurately judge the winding strain form. Based on the above problems, this research investigated a strain gauge strain detection method based on distributed fiber optic sensing, and proposes a winding strain identification method based on the S-transform and an extreme learning machine (ELM). First, the deformation of the winding in the process of transformer operation is simulated, and the corresponding Brillouin frequency shift is collected. Then, the time-frequency analysis of the strain signal is carried out using an S-transform, and the transformed time-frequency feature is extracted as the input sample to the neural network. An ELM was used for training identification. Experimental results show that the method can effectively identify the common winding deformation form, and that the recognition effect is better and the accuracy is high.

Direct Electrophysiological Mapping of Shape-Induced Affective Perception.

Visual information may convey different affective valences and induce our brain into different affective perceptions. Many studies have found that unpleasant stimuli could produce stronger emotional effects than pleasant stimuli could. Although there has been a notion that triangle is perceived as negative and circle as positive, there has been no systematic study to map the degrees of valence of shapes with different affective perceptions. Here, we employed four shapes (ellipse, triangle, and line-drawn happy and angry faces) to investigate the behavior and electrophysiological responses, in order to systematically study shape-induced affective perception. The reaction time delay and the event-related potential (ERP), particularly the early ERP component, were applied to find the associations with different affective perceptions. Our behavioral results showed that reaction time for angry face was significantly shorter than those for the other three types of stimuli (p < 0.05). In the ERP results, P1, N1, P2, and N2 amplitudes for angry face were significantly larger than those for happy face. Similarly, P1, N1, P2, and N2 amplitudes for triangle were significantly larger than those for ellipse. Particularly, P1 amplitude in the parietal lobe for angry face was the strongest, followed by happy face, triangle, and ellipse. Hence, this work found distinct electrophysiological evidence to map the shape-induced affective perception. It supports the hypothesis that affective strain would induce larger amplitude than affective ease does and strong affective stimuli induce larger amplitude than mild affective stimuli do.

A Feasibility Study of Transformer Winding Temperature and Strain Detection Based on Distributed Optical Fibre Sensors.

The temperature distribution and deformation of the transformer windings cannot be measured in a distributed manner by the traditional method and failure location cannot be performed. To solve these problems, we present a transformer winding temperature and strain based on a distributed optical fibre sensing detection method. The design of the optical fibre winding composite model is developed and simulated winding temperature rise test and local deformation test distinguish between measuring the winding temperature and the strain curve. The test results show that the distributed optical fibre can transmit wire strain efficiently. Optical fibres, in the process of winding, have a certain pre-stress. Using the Brillouin⁻Raman joint measuring method, one can effectively extract the optical fibre temperature and strain information and measure the length of the winding direction of the temperature and strain distribution curve to a temperature measurement precision of ±2 °C and strain detection accuracy of ±50 µÎµ. The system can carry out local hot spot and deformation localisation, providing new ideas for the transformer winding state monitoring technology.

In-situ hydrothermal synthesis of titanium dioxide nanorods on titanium wire for solid-phase microextraction of polycyclic aromatic hydrocarbons.

Titanium dioxide nanorods were prepared on the surface of titanium wire by hydrothermal synthesis for use as a solid-phase microextraction (SPME) fiber. The morphology of the SPME coating was observed by scanning electron microscopy (SEM). Employed in conjunction with gas chromatography (GC), the fiber was investigated with five polycyclic aromatic hydrocarbons (PAHs) and three terphenyls in direct-immersion extraction mode. Various parameters were optimized, such as the extraction time, the stirring rate, the extraction temperature, the ionic strength of the sample solution, and the desorption time. Under the optimized conditions, the SPME-GC analytical method achieved a low detection limit (0.003 µg L-1) and wide linear ranges (0.01-100 µg L-1 and 0.01-200 µg L-1) along with good correlation coefficients (0.9892-0.9962). The established method was also used to analyze rainwater and an aqueous solution of coal ash. The results indicated that this fiber could be applied in real-world environmental monitoring. The proposed fiber also exhibited excellent durability. Graphical Abstract The schematic diagram of experimental process.

Mesoporous titanium oxide with high-specific surface area as a coating for in-tube solid-phase microextraction combined with high-performance liquid chromatography for the analysis of polycyclic aromatic hydrocarbons.

Stainless-steel wires coated with mesoporous titanium oxide were placed into a polyether ether ketone tube for in-tube solid-phase microextraction, and the coating sorbent was characterized by X-ray diffraction and scanning electron microscopy. It was combined with high-performance liquid chromatography to build an online system. Using eight polycyclic aromatic hydrocarbons as the analytes, some conditions including sample flow rate, sample volume, organic solvent content, and desorption time were investigated. Under optimum conditions, an online analysis method was established and provided good linearity (0.03-30 µg/L), low detection limits (0.01-0.10 µg/L), and high enrichment factors (77.6-678). The method was applied to determine target analytes in river water and water sample of coal ash, and the recoveries are in the range of 80.6-106.6 and 80.9-103.5%, respectively. Compared with estrogens and plasticizers, extraction coating shows better extraction efficiency for polycyclic aromatic hydrocarbons.

Facile and efficient poly(ethylene terephthalate) fibers-in-tube for online solid-phase microextraction towards polycyclic aromatic hydrocarbons.

Poly(ethylene terephthalate) (polyester) fibers as solid-phase microextraction (SPME) adsorbent were directly filled in a poly(ether ether ketone) (PEEK) tube, for online analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples, coupled with high-performance liquid chromatography. The facile, economic, and environmental polyester fibers-in-tube SPME device exhibited high extraction efficiency, good selectivity for PAHs, and satisfactory durability. Under optimum conditions, the polyester fibers provided satisfactory enhancement factors in the range of 307-1646, and low detection limits ranging from 0.01 to 0.03 µg L(-1). The linearity was in the range of 0.03-80 µg L(-1) with correlation coefficients (r) ranging from 0.9978 to 0.9997. Limit of quantification was defined as a concentration of the analytes with a ten-time signal-to-noise ratio (S/N = 10) and was in the range of 0.03-0.1 µg L(-1). The intra-day and inter-day precisions for quantitative analysis were investigated and the relative standard deviation (RSD) was lower than 5.8 and 6.9 %, respectively. Extraction repeatability was also investigated and its RSD was in the range of 3.8-7.8 %. Finally, the fiber-in-tube SPME device was successfully applied to analyze PAHs in water samples. Graphical abstract Schematic diagrams of polyester fibers-in-tube device and the automated in-tube SPME-HPLC system.

Hollow fiber membrane-coated functionalized polymeric ionic liquid capsules for direct analysis of estrogens in milk samples.

Protein removal process is always time-consuming for the analysis of milk samples. In this work, hollow fiber membrane-coated functionalized polymeric ionic liquid (HF-PIL) capsules were synthesized and used as solid-phase microextraction (SPME) sorbent for direct analysis of estrogens in milk samples. The functionalized PIL monolith sorbent was obtained by copolymerization between 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate IL monomer and 1,6-di(3-vinylimidazolium) hexane bishexafluorophosphate IL-crosslinking agent. A group of four capsules were installed as SPME device, to determine four kinds of estrogens (estrone, diethylstilbestrol, hexestrol, and 17α-ethynylestradiol) in milk samples, coupled to high performance liquid chromatography. Extraction and desorption conditions were optimized to get satisfactory extraction efficiency. Good linearity was obtained in the range of 5-200 µg L(-1). The limits of detection were 1 µg L(-1) for diethylstilbestrol and 2 µg L(-1) for 17α-ethynylestradiol, estrone, and hexestrol. The present method was applied to analyze the model analytes in different milk samples. Relative recoveries were in the range of 85.5-112%. The HF-PIL SPME capsules showed satisfactory extraction efficiency and high resistance to sample matrix interference.

Graphene oxide reinforced polymeric ionic liquid monolith solid-phase microextraction sorbent for high-performance liquid chromatography analysis of phenolic compounds in aqueous environmental samples.

A graphene oxide reinforced polymeric ionic liquids monolith was obtained by copolymerization of graphene oxide doped 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate monomer and 1,6-di-(3-vinylimidazolium) hexane bihexafluorophosphate cross-linking agent. Coupled to high-performance liquid chromatography, the monolith was used as a solid-phase microextraction sorbent to analyze several phenolic compounds in aqueous samples. Under the optimized extraction and desorption conditions, linear ranges were 5-400 µg/L for 3-nitrophenol, 2-nitrophenol, and 2,5-dichlorophenol and 2-400 µg/L for 4-chlorophenol, 2-methylphenol, and 2,4,6-trichlorophenol (R(2) = 0.9973-0.9988). The limits of detection were 0.5 µg/L for 3-nitrophenol and 2-nitrophenol and 0.2 µg/L for the rest of the analytes. The proposed method was used to determine target analytes in groundwater from an industrial park and river water. None of the analytes was detected. Relative recoveries were in the range of 75.5-113%.

Development of a carbon-nanoparticle-coated stirrer for stir bar sorptive extraction by a simple carbon deposition in flame.

Stir bar sorptive extraction is an environmentally friendly microextraction technique based on a stir bar with various sorbents. A commercial stirrer is a good support, but it has not been used in stir bar sorptive extraction due to difficult modification. A stirrer was modified with carbon nanoparticles by a simple carbon deposition process in flame and characterized by scanning electron microscopy and energy-dispersive X-ray spectrometry. A three-dimensional porous coating was formed with carbon nanoparticles. In combination with high-performance liquid chromatography, the stir bar was evaluated using five polycyclic aromatic hydrocarbons as model analytes. Conditions including extraction time and temperature, ionic strength, and desorption solvent were investigated by a factor-by-factor optimization method. The established method exhibited good linearity (0.01-10 µg/L) and low limits of quantification (0.01 µg/L). It was applied to detect model analytes in environmental water samples. No analyte was detected in river water, and five analytes were quantified in rain water. The recoveries of five analytes in two samples with spiked at 2 µg/L were in the range of 92.2-106% and 93.4-108%, respectively. The results indicated that the carbon nanoparticle-coated stirrer was an efficient stir bar for extraction analysis of some polycyclic aromatic hydrocarbons.

Gold-functionalized stainless-steel wire and tube for fiber-in-tube solid-phase microextraction coupled to high-performance liquid chromatography for the determination of polycyclic aromatic hydrocarbons.

A fiber-in-tube solid-phase microextraction device based on a gold-functionalized stainless-steel wire and tube was developed and characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. In combination with high-performance liquid chromatography, it was evaluated using six polycyclic aromatic hydrocarbons as model analytes. Important parameters including sampling rate, sample volume, organic solvent content and desorption time were investigated. Under optimized conditions, an online analysis method was established. The linearity was in the range of 0.15-50 µg/L with correlation coefficients ranging from 0.9989 to 0.9999, and limits of detection ranged from 0.05 to 0.1 µg/L. The method was applied to determine model analytes in mosquito-repellent incense ash and river water samples, with recoveries in the range of 85-120%.

[Fast Determination of Auramine â ¡, Basic Orange â ¡ and Metanil Yellow in Bean Products on Surface Enhanced Raman Spectroscopy and Use High Pergormance Liquid Chromatography-Tandem Mass Spectrometry to Verify]

This experiment adopts Surface Enhanced Raman Spectroscopy (SERS) to quickly detect auramine Ⅱ, basic orange Ⅱ and metanil yellow in bean products. It uses High Performance Liquid Chromatography (HPLC)-tandem mass spectrometry to verify. The best extraction solvent is methanol-water (Seven plus three) solution. Before classification, extracting the bean products withAccelerated Solvent Extaction (ASE) and purifying it with Gel Permeation Chromatography(GPC), which improves the extraction efficiency, improves the detection sensitivity, reduces the dosage of extraction solvent and effective in the matrix of macromolecular distractors.ASE and GPC conditions are optimized. This study of three types of pigment surface enhanced Raman spectra characteristic peak of the ownership certification. The characteristic peak of auramine Ⅱ, basic orange Ⅱ and metanil yellow is respectively 652, 995 and 983 cm-1; he method detection limit is 3.0, 1.0 and 4.0 mg·kg-1. Three quantitative characteristic peak of pigment had a good linear relationship with pigment concentration，Recovery of this experiment was 83.48%～92.59% range, relative standard deviation less than 7.2%. The method is characterized by simple pretreatment, short analysis period and high sensitivity, etc. The method provides a reliable reference for food pigment detection.

Development of a functionalized polymeric ionic liquid monolith for solid-phase microextraction of polar endocrine disrupting chemicals in aqueous samples coupled to high-performance liquid chromatography.

Ionic liquids (ILs) have been efficiently used as a "designer sorbent" in sample preparation. A novel 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate IL monomer was synthesized and copolymerized with 1,6-di(3-vinylimidazolium) hexane bishexafluorophosphate IL as cross-linking agent to prepare a cross-linked polymeric ionic liquids (PILs) monolith. Coupled to high-performance liquid chromatography (HPLC), the PILs monolith was used as a solid-phase microextraction (SPME) sorbent to extract some polar endocrine disrupting chemical (EDCs) such as estrogens, bisphenol A, and phthalate esters in aqueous samples. Preparation and extraction conditions were investigated and optimized to obtain satisfactory extraction efficiency. Limits of detection (LODs) of the proposed method for three steroid estrogens and bisphenol A were 0.25 and 0.2 µg L(-1), respectively, which were lower than or comparable to some other sample preparation methods. Intra- and inter-day repeatability for all the analytes was 2.2-12%. The monolith-to-monolith repeatability was 7.4-15%. The extraction performance of the method for analysis of target estrogens in treated domestic wastewater was investigated and compared with a dispersive liquid-liquid microextraction (DLLME) method. The proposed SPME method provided better sensitivity and higher resistance to matrix interferences.

Nanostructured copper-coated solid-phase microextraction fiber for gas chromatographic analysis of dibutyl phthalate and diethylhexyl phthalate environmental estrogens.

A novel nanostructured copper-based solid-phase microextraction fiber was developed and applied for determining the two most common types of phthalate environmental estrogens (dibutyl phthalate and diethylhexyl phthalate) in aqueous samples, coupled to gas chromatography with flame ionization detection. The copper film was coated onto a stainless-steel wire via an electroless plating process, which involved a surface activation process to improve the surface properties of the fiber. Several parameters affecting extraction efficiency such as extraction time, extraction temperature, ionic strength, desorption temperature, and desorption time were optimized by a factor-by-factor procedure to obtain the highest extraction efficiency. The as-established method showed wide linear ranges (0.05-250 µg/L). Precision of single fiber repeatability was <7.0%, and fiber-to-fiber repeatability was <10%. Limits of detection were 0.01 µg/L. The proposed method exhibited better or comparable extraction performance compared with commercial and other lab-made fibers, and excellent thermal stability and durability. The proposed method was applied successfully for the determination of model analytes in plastic soaking water.