Preparation of ionic porous polymers for extraction of four phenolic endocrine disrupting chemicals from fish and water samples.

In this paper, series of ionic polymers were synthesized by crosslinking alkyl quaternary ammonium salts with 1,4-bis(chloromethyl)benzene. Among them, hyper-crosslinked polymer fabricated with dodecyl dimethyl benzyl ammonium chloride (HCP-DD) as monomer delivered superior adsorption performance for endocrine disrupting chemicals (EDCs). The adsorption mechanism mainly includes π-π stacking, hydrophobic and electrostatic interaction. With HCP-DD as solid phase extraction sorbent, a high performance liquid chromatography-diode array detection method was developed for the detection of four phenolic EDCs in water and fish samples. The detection limits of the method were 0.005-0.02 ng mL-1 for water samples and 3-30 ng g-1 for fish samples. The recoveries of EDCs in water samples and fish samples were 80-119% and 81.3-117% (relative standard deviations <4.4%), respectively. The study not only provides a route for preparation ionic porous polymers, but also highlights the applications of ionic polymers as efficient adsorbent to enrich organic pollutants.

Screening for endocrine disrupting chemicals inhibiting monocarboxylate 8 (MCT8) transporter facilitated thyroid hormone transport using a modified nonradioactive assay.

Early neurodevelopmental processes are strictly dependent on spatial and temporally modulated of thyroid hormone (TH) availability and action. Thyroid hormone transmembrane transporters (THTMT) are critical for regulating the local concentrations of TH, namely thyroxine (T4) and 3,5,3'-tri-iodothyronine (T3), in the brain. Monocarboxylate transporter 8 (MCT8) is one of the most prominent THTMT. Genetically induced deficiencies in expression, function or localization of MCT8 are associated with irreversible and severe neurodevelopmental adversities. Due to the importance of MCT8 in brain development, studies addressing chemical interferences of MCT8 facilitated T3 uptake are a crucial step to identify TH system disrupting chemicals with this specific mode of action. Recently a non-radioactive in vitro assay has been developed to rapidly screen for endocrine disrupting chemicals (EDCs) acting upon MCT8 mediated transport. This study explored the use of an UV-light digestion step as an alternative for the original ammonium persulfate (APS) digestion step. The non-radioactive TH uptake assay, with the incorporated UV-light digestion step of TH, was then used to screen a set of 31 reference chemicals and environmentally relevant substances to detect inhibition of MCT8-depending T3 uptake. This alternative assay identified three novel MCT8 inhibitors: methylmercury, bisphenol-AF and bisphenol-Z and confirmed previously known MCT8 inhibitors.

Applications of the SR4G Transgenic Zebrafish Line for Biomonitoring of Stress-Disrupting Compounds: A Proof-of-Concept Study.

Transgenic zebrafish models have been successfully used in biomonitoring and risk assessment studies of environmental pollutants, including xenoestrogens, pesticides, and heavy metals. We employed zebrafish larva (transgenic SR4G line) with a cortisol-inducible green fluorescence protein reporter (eGFP) as a model to detect stress responses upon exposure to compounds with environmental impact, including bisphenol A (BPA), vinclozolin (VIN), and fluoxetine (FLX). Cortisol, fluorescence signal, and mRNA levels of eGFP and 11 targeted genes were measured in a homogenized pool of zebrafish larvae, with six experimental replicates for each endpoint. Eleven targeted genes were selected according to their association with stress-axis and immediate early response class of genes. Hydrocortisone (CORT)and dexamethasone (DEX) were used as positive and negative controls, respectively. All measurements were done in two unstressed and stressed condition using standardized net handling as the stressor. A significant positive linear correlation between cortisol levels and eGFP mRNA levels was observed (r> 0.9). Based on eGFP mRNA levels in unstressed and stressed larvae two predictive models were trained (Random Forest and Logistic Regression). Both these models could correctly predict the blunted stress response upon exposure to BPA, VIN, FLX and the negative control, DEX. The negative predictive value (NPV) of these models were 100%. Similar NPV was observed when the predictive models trained based on the mRNA levels of the eleven assessed genes. Measurement of whole-body fluorescence intensity signal was not significant to detect blunted stress response. Our findings support the use of SR4G transgenic larvae as an in vivo biomonitoring model to screen chemicals for their stress-disrupting potentials. This is important because there is increasing evidence that brief exposures to environmental pollutants modify the stress response and critical coping behaviors for several generations.

Magnet integrated fabric phase sorptive extraction of selected endocrine disrupting chemicals from human urine followed by high-performance liquid chromatography - photodiode array analysis.

In current paper, a new advanced modification of fabric phase sorptive extraction is introduced for the first time. This advantageous configuration that integrates the stirring and extraction mechanism into a single sample preparation device was originated by equally considering the beneficial role of the increase of extraction kinetics and more specifically of diffusion on the extraction efficiency of the equilibrium based microextraction techniques and the need for integrating and unite processes for better promotion and implementation of the principles of Green Analytical Chemistry. The resulted magnet integrated fabric phase sorptive extraction (MI-FPSE) device was the spearhead to develop a new analytical methodology for the determination of selected very common endocrine disrupting chemicals as model analytes in human urine by high-performance liquid chromatography-photodiode array analysis. More specifically, the sol-gel Carbowax 20 M coated on hydrophilic cellulose fabric substrate, MI-FPSE device was efficiently employed for the establishment of a new extraction protocol before the chromatographic determination. The sample preparation workflow was methodically optimized in terms of the elution solvent mixture, the volume of the sample, the extraction and the elution time, the stirring speed during the extraction, the ionic strength, and the pH of the sample matrix. The chromatographic separation was performed on a Spherisorb C18 column and a gradient elution program within 14 minutes. Mobile phase consisted of 0.05 ammonium acetate aqueous solution and acetonitrile. The method was validated towards linearity, sensitivity, selectivity, precision, accuracy, and stability. LOD and LOQ ranged between 1.05-1.80 and 3.5-6.0 ng/mL, while %RSD values were found lower than 9.0% in all cases. The method was efficiently applied to the bioanalysis of real samples. All the chosen EDCs were measured at high detection levels. The new MI-FPSE device has demonstrated its performance superiority as a magnet integrated stand-alone extraction device and could be considered as a significant improvement in the field of analytical/bioanalytical sample preparation.

Succinic anhydride-based chemical modification making laccase@Cu3(PO4)2 hybrid nanoflowers robust in removing bisphenol A in wastewater.

To prepare a robust biocatalyst and enhance the removal of bisphenol A in wastewater, succinic anhydride was reacted with laccase to obtain succinic anhydride-modified laccase (SA-laccase) and then co-crystallized with Cu3(PO4)2 to form SA-laccase@Cu3(PO4)2 hybrid nanoflowers (hNFs). The activity of SA-laccase@Cu3(PO4)2 reached 5.27 U/mg, 1.86-, 2.88- and 2.15-fold those of bare laccase@Cu3(PO4)2, laccase@Ca3(PO4)2 and laccase@epoxy resin, respectively. Compared with free laccase, the obtained hNFs present enhanced activity and tolerance to pH and high temperature in the removal of BPA. Under the optimum conditions of pH 6.0 and 35 °C, BPA removal reached 93.2% using SA-laccase@Cu3(PO4)2 hNFs, which was 1.21-fold of that using free laccase. In addition, the obtained SA-laccase@Cu3(PO4)2 hNFs retained nearly 90% of their initial catalytic activity for BPA removal after 8 consecutive batch cycles. This efficient method for preparing immobilized laccase can also be further developed and improved to acquire green biocatalysts for removing persistent organic pollutants in wastewater.

Highly sensitive determination of endocrine disrupting chemicals in foodstuffs through magnetic solid-phase extraction followed by high-performance liquid chromatography-tandem mass spectrometry.

BACKGROUND: Endocrine disrupting chemicals (EDCs), proved to be potential carcinogenic threats to human health, have received great concerns in food field. It was essential to develop effective methods to detect EDCs in food samples. The present study proposed an efficient method to determine trace EDCs including estrone (E1), 17ß-estradiol (E2), estriol (E3) and bisphenol A (BPA) based on magnetic solid-phase extraction (MSPE) coupled high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in meat samples. RESULTS: Fe3 O4 @COF(TpBD)/TiO2 nanocomposites were synthesized via functionalization of magnetic covalent organic frameworks (COFs) with titanium dioxide (TiO2 ) nanoparticles, and used as absorbents of MSPE to enrich EDCs. The efficient EDCs enrichment relies on π-π stacking interaction, hydrogen bonding, and the interaction between titanium ions (IV, Ti4+ ) and hydroxyl groups in EDCs, which improves the selectivity and sensitivity. Under the optimized conditions, target EDCs were rapidly extracted through MSPE with 5 min. Combining Fe3 O4 @COF(TpBD)/TiO2 based MSPE and HPLC-MS/MS to determine EDCs, good linearities were observed with correlation coefficient (R2 ) ≥ 0.9989. The limits of detection (LODs) and limits of quantification (LOQs) were 0.13-0.41 µg kg-1 and 0.66-1.49 µg kg-1 , respectively. Moreover, the proposed method was successfully applied to real samples analysis. CONCLUSIONS: The established MSPE-HPLC-MS/MS method was successfully applied to determine EDCs in meat samples with rapidness, improved selectivity and sensitivity. It shows great prospects for EDCs detection in other complicated matrices. © 2020 Society of Chemical Industry.

The new generation PFAS C6O4 does not produce adverse effects on thyroid cells in vitro.

PURPOSE: Per- and poly-fluoroalkyl-substances (PFASs) are synthetic compounds that raised concern due to their potential adverse effects on human health. Long-chain PFAS were banned by government rules in many states, and thus, new emerging PFAS were recently introduced as substitutes. Among these, Perfluoro{acetic acid, 2-[(5-methoxy-1,3-dioxolan-4-yl)oxy]}, ammonium salt (C6O4) was recently introduced to produce a range of food contact articles and literature data about this compound are scanty. The aim of this study was to evaluate the in vitro effects of exposure to C6O4, compared with PFOA and PFOS on thyroid cells. METHODS: FRTL5 rat-thyroid cell lines and normal human thyroid cells (NHT) were incubated with increasing concentrations of C6O4 for 24, 48, 72, and 144 h to assess cell viability by WST-1. Cell viability was confirmed by AnnexinV/PI staining. Long-chain PFAS (PFOA and PFOS) were used at same concentrations as positive controls. The proliferation of cells exposed to C6O4, PFOA, and PFOS was measured by staining with crystal violet and evaluation of optical density after incubation with SDS. Changes in ROS production by FRTL5 and NHT after exposure to C6O4 at short (10, 20, and 30 min) and long-time points (24 h) were evaluated by cytofluorimetry. RESULTS: C6O4 exposure did not modify FRTL5 and NHT cell viability at any concentration and/or time points with no induction of necrosis/apoptosis. At difference, PFOS exposure reduced cell viability of FRTL5 while and NHT, while PFOA only in FRTL5. FRTL5 and NHT cell proliferation was reduced by incubation with by PFOA and PFOS, but not with C6O4. ROS production by NHT and FRTL5 cells was not modified after C6O4 exposure, at any time/concentration tested. CONCLUSIONS: The present in vitro study constitutes the first evaluation of the potential adverse effects of the new emerging PFAS C6O4 in cultured rat and human thyroid cells, suggesting its safety for thyroid cells in vitro.

Enhanced microextraction of endocrine disrupting chemicals adsorbed on airborne fine particulate matter with gas chromatography-tandem mass spectrometric analysis.

A novel double-microextraction approach, combining dispersive liquid-liquid microextraction (DLLME) and vortex-assisted micro-solid-phase extraction (VA-µ-SPE) was developed. The procedure was applied to extract endocrine disrupting chemicals (EDCs) consisting of three phthalate esters (PEs) and bisphenol A (BPA) associated with PM2.5 (airborne particulate matter with aerodynamic diameter ≤ 2.5 µm). Gas chromatography-tandem mass spectrometry (GC-MS/MS) was used for determination of the analytes. These analytes were first ultrasonically desorbed from PM2.5 in a 10% acetone aqueous solution. DLLME was used to first preconcentrate the analytes; the sample solution, still in the same vial, was then subjected to VA-µ-SPE. The synergistic effects provided by the combination of the microextraction techniques provided advantages such as high enrichment factors and good cleanup performance. Various extraction parameters such as type and volume of extractant solvent (for DLLME), and type of sorbent, extraction time, desorption solvent, volume of desorption solvent and desorption time (for µ-SPE) were evaluated. Multi-walled carbon nanotubes were found to be the most suitable sorbent. This procedure achieved good precision with intra- and inter-day relative standard deviations of between 1.93 and 9.95%. Good linearity ranges (0.3-100 ng/mL and 0.5-100 ng/mL, depending on analytes), and limits of detection (LODs) of between 0.07 and 0.15 ng/mL were obtained. The method was used to determine the levels of PEs and BPA in ambient air, with concentrations ranging between below the limits of quantification and 0.48 ng/m3. DLLME-VA-µ-SPE-GC-MS/MS was demonstrated to be suitable for the determination of these EDCs present in PM2.5.

A green air assisted-dispersive liquid-liquid microextraction based on solidification of a novel low viscous ternary deep eutectic solvent for the enrichment of endocrine disrupting compounds from water.

A green air-assisted dispersive liquid-liquid microextraction based on floating organic droplet solidification (DLLME-SFOD) was introduced for the enrichment of five endocrine disrupting compounds (EDCs) from water using a ternary deep eutectic solvent (TDES) as an extracting solvent prior to their determination by HPLC-PDA. The eutectic solvents were synthesized by combining various fatty acids which can concurrently act as both hydrogen bond acceptors (HBA) and hydrogen bond donors (HBD). Adding a third component to classical two-component eutectic solvents allows to purposefully control density, melting point, and viscosity of the synthesized solvents. Ternary and binary eutectic solvents with C9 acid provided excellent extraction efficiency in comparison with other eutectic solvents with C8 acid, while ternary solvents provided superior extraction efficiency to binary ones. Different variables that could influence the microextraction efficiency were optimized applying central composite face-centered design (CCF). At the optimum conditions, the method had low detection limits ranging from 0.96-2.30 µg/L with a preconcentration up to 134-folds. The method showed good linearity from the linear regression with an excellent correlation coefficient (r2 > 0.999). A good inter- and intraday precision (%RSD < 7%) and%recovery > 90% were achieved proving the method high precision and accuracy. Furthermore, the potential of using the TDES for determining the EDCs from five real water samples was proved through the higher extraction efficiency of the EDCs (90.06-104.43%) with results uncertainty < 20% for most of the compounds. Finally, the method greenness was evaluated by Raynie pictogram, analytical eco-scale, and Green Analytical Procedure Index (GAPI) approaches which confirm the superior eco-friendship of our method in comparison with other reported methods.

A solid-phase extraction method for estrogenic disrupting compounds based on the estrogen response element.

A solid-phase extraction (SPE) method for enriching and purifying estrogenic disrupting compounds (EDCs) based on the estrogen response element was established. The estrogen receptor was used for molecular recognition, as it specifically binds EDCs. An estrogen response element was used to maintain the activity of the estrogen receptor. High-performance liquid chromatography (HPLC) was used to quantify the EDCs. This method combined with HPLC was applied to detect three kinds of EDCs, such as bisphenol A (BPA), 17ß-estradiol, and diethylstilbestrol in a liquid milk matrix, with recoveries of 84.1 ± 8.2% to 113.6 ± 2.9%. The limits of detection and quantification of the established method were 1 × 10-6 mg·mL-1 and 5 × 10-6 mg·mL-1. The method was further applied to analyze market samples, including liquid milk, fermented milk, and milk powder. Only BPA was detected from one brand of liquid milk and it was below the regulatory level.

Synthesis of magnetic metal organic framework/covalent organic framework hybrid materials as adsorbents for magnetic solid-phase extraction of four endocrine-disrupting chemicals from milk samples.

RATIONALE: Endocrine-disrupting chemicals (EDCs), widespread and easily ingested through the simple food chain, have been suggested to pose potential carcinogenic threats to human health. Considering food safety and public health, it is urgent to establish a sensitive and effective method to enrich and determine EDCs in food samples. METHODS: Novel hybrid nanocomposites Fe3 O4 @A-TpBD@NH2 -MIL-125(Ti) were synthesized through the formation of amide bonds. The as-prepared Fe3 O4 were innovatively encapsulated with 4-aminobenzoic acid functionalized COF(A-TpBD) to generate bare carboxyl (-COOH), which formed amide bonds with the NH2 -MIL-125(Ti), generating well-defined and hierarchical hybrid materials. The Fe3 O4 @A-TpBD@NH2 -MIL-125(Ti) materials were used as the adsorbents for magnetic solid-phase extraction (MSPE) coupled with high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) to enrich and determine EDCs (E1, E2, E3 and BPA) from milk samples. RESULTS: Fe3 O4 @A-TpBD@NH2 -MIL-125(Ti) exhibited improved adsorption efficiency and selectivity based on π-π stacking interaction, hydrogen bonding, electrostatic interaction, and the interaction between the hydroxyl group in EDCs and titanium ions (IV, [Ti]4+ ). Under the optimized conditions, Fe3 O4 @A-TpBD@NH2 -MIL-125(Ti)-based MSPE coupled with HPLC/MS/MS showed good linearity with correlation coefficient (R2 ) ≥0.9983 and high sensitivity with limits of detection (LODs) in the range of 0.37-0.85 µg/L. Moreover, the developed method was successfully employed to detect EDCs in milk samples. CONCLUSIONS: Fe3 O4 @A-TpBD@NH2 -MIL-125(Ti) possess good adsorption capability and selectivity for EDCs. In addition, the proposed MSPE-HPLC/MS/MS method based on Fe3 O4 @A-TpBD@NH2 -MIL-125(Ti) is effective and sensitive for the determination of EDCs in real samples, which can be used as a robust alternative method to monitor EDCs in complex matrices.

Potential use of two aryl sulfotransferase cell-surface display systems to detoxify the endocrine disruptor bisphenol A.

Bisphenol A (BPA) is one of the most common toxic endocrine disruptors in the environment. A fast, efficient and environmental-friendly method for BPA detoxification is urgently needed. In this study, we show that the enzymatic transformation of BPA into a non-estrogenic BPA sulfate can be performed by the aryl sulfotransferase (ASTB) from Desulfitobacterium hafniense. We developed and compared two Escherichia coli ASTB cell-surface displaying systems using the outer membrane porin F (OprF) and the lipoprotein outer membrane A (Lpp-OmpA) as carriers. The surface localization of both fusion proteins was confirmed by Western blot and flow cytometry analysis as well as the enzymatic activity assay of the outer membrane fractions. Unfortunately, Lpp-OmpA-ASTB cells had an adverse effect on cell growth. In contrast, the OprF-ASTB cell biocatalyst was stable, expressing 70% of enzyme activity for 7 days. It also efficiently sulfated 90% of 5 mM BPA (1 mg/mL) in wastewater within 6 h.

Enhanced removal of bisphenol A from contaminated soil by coupling Bacillus subtilis HV-3 with electrochemical system.

Exposure to endocrine disruptors interferes with the synthesis, release, transport and metabolic activities of hormones, thus impairing human health significantly. Bisphenol A (BpA), an endocrine disruptor, commonly released into the environment by industrial activities and needs immediate attention. This study aims at investigating the process and prospects of deploying bio-electrochemical systems (BES) for the removal of BpA from artificially contaminated soil using Bacillus subtilis HV-3. The BES was setup with desired operating conditions: initial concentration of BpA (80-150 mg/L), pH (3-11) and applied potential voltage (0.6-1.4 V). Under optimized conditions (initial BpA concentration, 100 mg/L; pH 7; and applied voltage 1.0 V), close to 98% degradation of BpA was achieved. The intermediates produced during degradation were analysed using High performance liquid chromatography-Mass spectrometry and the possible degradation pathway was elucidated. Phytotoxicity studies in the remediated soil with Phaseolus mungo confirmed the environmental applicability of the BES system.

Disruption of 17ß-estradiol secretion by persistent organic pollutants present in human follicular fluid is dependent on the potential of ovarian granulosa tumor cell lines to metabolize estrogen.

Endocrine-disrupting chemicals (EDCs), such as perfluorooctanoate, perfluorooctane sulfonate, 2,2-dichlorodiphenyldichloroethylene, hexachlorobenzene, and polychlorinated biphenyl 153 are persistent pollutants that are found in human follicular fluid (FF). These compounds may affect endocrine function, disrupt steroid secretion by granulosa cells, and play a role in granulosa cell tumor (GCT) development. GCTs demonstrate endocrine activity, expressing aromatase and secreting 17ß-estradiol (E2). We aimed to determine the effects of a mixture of EDCs, similar to that found in human FF, on human granulosa tumor cell lines representing the juvenile (JGCT) and adult (AGCT) forms (COV434 and KGN cells, respectively). We found that all the individual compounds and mixtures tested altered granulosa tumor cell function by disrupting E2 secretion. In KGN cells, which possess significantly higher basal aromatase gene expression, and therefore secrete more E2 than JGCT cells, EDC mixtures activated estrogen receptors (ERs) and G protein-coupled receptor-30 signaling, thereby stimulating E2 secretion, without affecting aromatase expression. By contrast, in COV434 cells, which demonstrate higher CYP1A1 expression, a key mediator of estrogen metabolism, than KGN cells, EDC mixtures reduced E2 secretion in parallel with increases in the 2-hydroxyestrogen 1/E2 ratio and CYP1A1 expression, implying an upregulation of E2 metabolism. These results indicate that the EDC mixture present in FF disrupts E2 secretion in JGCT and AGCT cells according to the estrogen metabolic potential of the cell type, involving both classical and non-classical ER pathways.

Prediction of adsorption capacity for pharmaceuticals, personal care products and endocrine disrupting chemicals onto various adsorbent materials.

Adsorption is a common process used to remove pharmaceuticals, personal care products and endocrine disrupting chemicals (PPCPs/EDCs) from water. However, as PPCPs/EDCs cover a wide range of molecules and chemical structures, prediction of the adsorption capacity is very challenging. In this study, a novel model was developed to predict adsorption isotherms of PPCPs/EDCs onto various types of adsorbents using a combination of Polanyi potential theory, molecular connectivity indices (MCIs) and molecular characteristics. Polanyi theory provided the basic mathematical form for the correlation. MCIs, hydrophobicity and H-bond count were used to normalize the Polanyi equation based on the molecular structure and interactions among the chemicals, the adsorbents, and the solution. In total, adsorption data were collected from 158 reports for 55 PPCPs/EDCs onto 306 different adsorbent materials. The correlation was first trained with 46 PPCPs/EDCs adsorbed onto 162 carbonaceous adsorbents (CAs), with 44.8% SDEV. Then the model was employed to predict 46 PPCPs/EDCs onto 118 other CAs and 9 new PPCPs/EDCs onto 23 CAs in ultrapure water, with error from 42 to 48% SDEV. When applying to non-carbonaceous adsorbents, the models can still predict the adsorption of PPCPs/EDCs with 90.09% SDEV. For the first time, a model, the PD - MCI - hydrophobic - H bond model, was developed to predict adsorption of a wide group of complicated PPCPs/EDCs onto a big variety of carbonaceous and non-carbonaceous adsorbents. The proposed model approach may provide a simple means for predicting adsorption capacities of PPCPs/EDCs onto various adsorbents.

Dual stir bar sorptive extraction coupled to thermal desorption-gas chromatography-mass spectrometry for the determination of endocrine disruptors in human tissues.

The validation of a procedure for the determination of six alkylphenols (APs), 4-tert-butylphenol, 4-pentylphenol, 4-tert-octylphenol, 4-hexylphenol, 4-octylphenol and 4-nonylphenol, and three bisphenols (BPs), bisphenol A, bisphenol F and bisphenol Z, in seven human organs and tissues (kidney, liver, heart, lung, spleen, brain and abdominal fat) obtained from eight autopsies is presented. Previously ground samples were treated by salt-assisted liquid-liquid extraction (SALLE) for isolation of the analytes and then pre-concentrated using dual stir bar sorptive extraction (SBSE), allowing two different extraction conditions for the same sample. Finally, thermal desorption was used as the injector system in combination with gas chromatography coupled to mass spectrometry (GC-MS). To determine BPs, derivatization using acetic anhydride was required, although this step was not necessary for the APs. Two parallel extractions of the contaminants with the stir bars were performed, followed by thermal desorption and chromatographic analysis. The procedure provided quantification limits between 0.050 and 4.0 ng g-1 for APs and from 0.26 to 2.6 ng g-1 for BPs. Repeatability and reproducibility values were lower than 15% in all cases. The accuracy of the procedure was established by a recovery study, which provided values in the 85.8-115% range for APs and 83.6-120% for BPs. Samples were analyzed with the proposed methodology and data were processed by ANOVA tests to study the behaviour and bioaccumulation of these compounds in human tissues or organs. In addition, discriminant analysis detected age- and sex-dependent differences in bioaccumulation.

An azine-linked covalent organic framework as stationary phase for separation of environmental endocrine disruptors by open-tubular capillary electrochromatography.

In recent years, covalent organic frameworks (COFs) play an important role in the field of chromatographic separation. However, COFs are used rarely in open-tubular capillary electrochromatography (OT-CEC) so far, and the reported methods have not been applied to actual sample analysis. Herein, a novel azine-linked COF (N0-COF) coated capillary was prepared as OT-CEC separation channel and a new method for separation and detection of environmental endocrine disruptors, i.e., bisphenol A (BPA) and its analogues was established. Under optimal separation conditions, the analytes were baseline separated by the N0-COF coated capillary with 20 min. The intra-day, inter-day and column-to-column relative standard deviations were 0.07-2.99%, 1.05-3.20% and 1.31-5.83% for the migration time; 1.68-5.50%, 1.52-9.24% and 4.04-9.14% for the peak area. The method was further applied to separate and determine BPA and its analogues in beverage samples, and the recovery ranged from 91.0-112.0%.

OECD approaches and considerations for regulatory evaluation of endocrine disruptors.

Identifying the potential endocrine disruptor hazard of environmental chemicals is a regulatory mandate for many countries. However, due to the adaptive nature of the endocrine system, absence of a single method capable of identifying endocrine disruption, and the latency between exposure to endocrine disrupting chemical during sensitive life stages and the manifestation of adverse responses, satisfying the regulatory requirement needed to identify a chemical as an endocrine disruptor is a challenge. There are now a variety of validated regulatory tests that can be used in combination to provide evidence that a chemical affects the oestrogen, androgen, thyroid, and steroidogenic pathways of vertebrates, but most rely (at least to some extent) on animal testing and require considerable cost and time to produce the necessary data. Emerging research methods are able to evaluate other endocrine pathways, incorporate more sensitive endpoints, and combine multiple alternative methods to predict in vivo outcomes. Some research approaches may also bridge gaps that have been identified in current endocrine regulatory testing. For the near term, considering new endpoints in a regulatory context may require adding them to existing test methods in order to establish relationships between the traditional and the innovative. From the outset, endocrine testing has always required integration of multiple methods that provide data on different levels of biological organisation, thus, the area of endocrine disruption is particularly adaptable to adverse outcome pathway (AOP) frameworks and integrated test methods built around AOPs. Herein, we provide a review of the status of endocrine disruptors in the OECD context, examples where innovation from research is needed to improve or bridge gaps in endocrine testing, and suggestions for regulators and researchers to facilitate uptake of innovate methods for endocrine disruptor regulatory testing. The increase in several human complex human disorders that include an endocrine component and the alarming decrease in wildlife biodiversity are commanding directives to include the best, most informative, innovative approaches to accelerate the rate and throughput of chemical evaluation for endocrine disruption.

Adsorptive removal of endocrine disrupting compounds from aqueous solutions using magnetic multi-wall carbon nanotubes modified with chitosan biopolymer based on response surface methodology: Functionalization, kinetics, and isotherms studies.

Recently, the presence of endocrine disrupting compounds in the environment has emerged as a global and ubiquitous problem. In this study, a novel synthesis of magnetically carbon nanotube modified with biological polymeric was successfully prepared. The effect of different parameters on the Bisphenol A (BPA) adsorption was studied. A prediction model for BPA adsorption was extended based on the Central Composite Design. Also, the prepared biopolymeric nanotubes were characterized by FT-IR, XRD, TEM, FE-SEM. The surface morphology of nanocomposite was observed, increased carbon nano tube size, and the levels after surface deposition were completely covered by chitosan proteins. The results of our experiments showed that optimum adsorption conditions was achieved at t = 76 min, BPA concentration 6.5 mg/L, adsorbent dosage 1 g/L and pH = 6.2.The data obtained in this study followed the Langmuir isotherm model and the pseudo-second order model. The maximum monolayer adsorption capacity of nanocomposite for BPA was 46.2 mg/g at 20 °C. This study showed that the adsorption of BPA onto nanocomposite was spontaneous and thermodynamically desirable.

A multi-residue method for determination of 36 endocrine disrupting chemicals in human serum with a simple extraction procedure in combination of UPLC-MS/MS analysis.

Much attention has been paid to endocrine disrupting chemicals (EDCs) due to their widespread presence in various environmental matrices, and endocrine disrupting potential even at low concentrations. However, little is known about the multiple EDCs exposure to human and related adverse effects on health, which warrants a multi-residue method for simultaneous determination of EDCs in human samples such as serum. In this study, we developed and validated a novel method for determination of 36 EDCs (8 bisphenols, 7 parabens, 2 antimicrobials, 5 benzophenones, and 14 phthalate metabolites) in human serum with ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). Two extraction methods (liquid liquid extraction (LLE), and LLE coupled with solid phase extraction (SPE) clean-up) were compared, and eleven solvents and two SPE cartridges were optimized for extraction and clean-up procedure, respectively. Recoveries of target compounds spiked in human serum at three levels of concentrations (0.5, 2.5 and 10 ng/mL) ranged from 45.8% to 120%, and the relative standard deviations (RSDs) were lower than 20%. The linearity of the labeled dilution calibration curve was good with correlation coefficient ranging from 0.995 to 0.999, and the limits of quantification (LOQs) were between 0.002 and 0.532 ng/mL. Low RSDs of intra-day (0.1-12.7%) and inter-day (0.2-13.3%) revealed the accuracy and precision of the quantification. The method was successfully applied to determine the target EDCs in human serum samples from 14 randomly selected individuals. The developed method is a promising method for routine measurement of EDCs in human serum.