Diethylstilbestrol Modifies the Structure of Model Membranes and Is Localized Close to the First Carbons of the Fatty Acyl Chains.

The synthetic estrogen diethylstilbestrol (DES) is used to treat metastatic carcinomas and prostate cancer. We studied its interaction with membranes and its localization to understand its mechanism of action and side-effects. We used differential scanning calorimetry (DSC) showing that DES fluidized the membrane and has poor solubility in DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) in the fluid state. Using small-angle X-ray diffraction (SAXD), it was observed that DES increased the thickness of the water layer between phospholipid membranes, indicating effects on the membrane surface. DSC, X-ray diffraction, and 31P-NMR spectroscopy were used to study the effect of DES on the Lα-to-HII phase transition, and it was observed that negative curvature of the membrane is promoted by DES, and this effect may be significant to understand its action on membrane enzymes. Using the 1H-NOESY-NMR-MAS technique, cross-relaxation rates for different protons of DES with POPC (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine) protons were calculated, suggesting that the most likely location of DES in the membrane is with the main axis parallel to the surface and close to the first carbons of the fatty acyl chains of POPC. Molecular dynamics simulations were in close agreements with the experimental results regarding the location of DES in phospholipids bilayers.

An ultrasensitive electrochemiluminescence aptasensor for the detection of diethylstilbestrol based on the enhancing mechanism of the metal-organic framework NH2-MIL-125(Ti) in a 3,4,9,10-perylenetetracarboxylic acid/K2S2O8 system.

In this work, a sensitive and selective electrochemiluminescent aptasensor was proposed based on the enhancing mechanism of the metal-organic framework NH2-MIL-125(Ti) in a 3,4,9,10-perylenetetracarboxylic acid/K2S2O8 system for a diethylstilbestrol assay. Herein, 3,4,9,10-perylenetetracarboxylic acid was selected as the major luminophore, and the metal-organic framework NH2-MIL-125(Ti) displayed a large specific surface area to immobilize abundant PTCA molecules to facilitate electrochemiluminescence efficiency. Besides, the metal-organic framework NH2-MIL-125(Ti) was used as a novel catalyst in the 3,4,9,10-perylenetetracarboxylic acid/K2S2O8 system, which could react with the co-reactant K2S2O8 to produce more SO4˙-. In addition, we introduced the amino-aptamer of diethylstilbestrol; due to the specific binding affinity between the aptamer and diethylstilbestrol, a selective electrochemiluminescent aptasensor for diethylstilbestrol was thus developed here. Under the optimal conditions, a wide detection range from 1.0 fM to 1.0 µM with a low detection limit of 0.28 fM (S/N = 3) was obtained. More importantly, the residual diethylstilbestrol in water was detected by the developed aptasensor; this confirmed that this method has good performance and potential applications in real samples.

Hapten Synthesis and the Development of an Ultrasensitive Indirect Competitive ELISA for the Determination of Diethylstilbestrol in Food Samples.

An ultrasensitive indirect competitive enzyme-linked immunosorbent assay (ic ELISA) using monoclonal antibodies (mAbs) was developed for the specific detection of diethylstilbestrol (DES) residues. To establish an ELISA based on mAbs, hapten diethylstilbestrol mono-carboxypropyl-ether (DES-MCPE) was chemically synthetized and then conjugated to bovine serum albumin (BSA) for immunization in mice. This ic ELISA was further optimized for DES determination. The sensitivity of the ic ELISA was found to be 0.49 µg/kg and the limit of detection was 0.075 µg/kg. DES residues in salmon meat and pork were tested with the recovery range from 74.0 to 85.2% and the coefficient of variation (CV) was less than 10%. Parallel analysis of DES samples from salmon meat showed comparable results from the ic ELISA with high-performance liquid chromatography. The ic ELISA provides a useful screening method for the quantitative detection of DES residues in animal-derived food.

Novel hapten design, antibody recognition mechanism study, and a highly sensitive immunoassay for diethylstilbestrol in shrimp.

Over the past few years, there has been a lack of progress in the quality of diethylstilbestrol (DES) antibodies used in immunoassay. In this study, a new immunizing hapten was designed for remarkably sensitive and specific antibody generation against diethylstilbestrol. By introducing a benzene ring instead of the traditional linear chain alkane as the hapten spacer, a more specific immune reaction was induced in the process of immunization. The developed polyclonal antibodies were characterized using the indirect competitive enzyme-linked immunosorbent assay (icELISA). Under optimized conditions, the half maximal inhibitory concentration (IC50) of the best polyclonal antibody was 0.14 ng/mL and it displayed low cross-reactions (CRs) with the structural analogs such as hexestrol (HEX) and dienestrol (DI). The molecular modeling and quantum chemical computation revealed that the lowest CR of the DES antibody to DI was mainly due to the huge three-dimensional conformational difference between DES and DI. Finally, a highly sensitive icELISA method based on the polyclonal antibody was developed for the determination of DES in shrimp tissue. The limit of detection (LOD) was as low as 0.2 µg/kg in shrimp and the recoveries in the spiked samples ranged from 83.4 to 90.8% with the coefficient of variation less than 13.8%. These results indicated that the use of an aromatic ring as the immunizing hapten spacer arm could be a potential strategy for the enhancement of anti-DES antibody sensitivity, and the established icELISA was applicable to the trace detection of DES in shrimp. Graphical abstract.

Preparation of magnetic molecularly imprinted polymers for the rapid detection of diethylstilbestrol in milk samples.

BACKGROUND: Diethylstilbestrol (DES) residues are harmful to human health because of their potential carcinogenic properties. Therefore, it is important to develop a fast and efficient pretreatment method to prevent their harmful effects on human health and the environment. RESULTS: In this paper, two types of magnetic molecularly imprinted polymers (MMIPs) of DES were prepared by bulk polymerization and the sol-gel method, respectively. The synthetic materials were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. Adsorption capacities of the bulk and sol-gel MMIPs were investigated. A rapid detection method was developed using the two types of MMIPs as sorbents, coupled to high-performance liquid chromatography, for the determination of DES residues in milk samples. Under optimized conditions, the limit of detection (S/N = 3) of both methods for DES was 2.0 µg L-1 ; and the linear response range to DES was 0.1-500 mg L-1 . The milk samples were analyzed according to this method with good recoveries of 88.3-97.6 and 90.5-103.5% for the two types of MMIPs, respectively. CONCLUSIONS: The method described had high sensitivity and high selectivity, and could prove to be a new method for the rapid determination of DES residues in milk samples. © 2019 Society of Chemical Industry.

Multi-Residue Method for the Analysis of Stilbene Estrogens in Milk.

The rapid analysis of stilbene estrogens is crucially important in the environment, food and health sectors, but quantitation of lower detection limit for stilbene estrogens persists as a severe challenge. We herein described a homologous and sensitive fluorescence polarization (FP) assay based on estrogen receptor α ligand binding domain (ER-LBD) to monitor stilbene estrogens in milk. Under optimal conditions, the half maximal inhibitory concentrations (IC50) of the FP assay were 9.27 nM, 12.94 nM, and 22.38 nM for hexestrol, dienestrol and diethylstilbestrol, respectively. And the corresponding limits of detection (LOD) values were 2.94 nM, 2.89 nM, and 3.12 nM. Finally, the assay was applied to determine the stilbenes in milk samples where the mean recoveries ranged from 95.76% to 112.78% and the coefficients of variation (CV) below 12.00%. Furtherly, we have focused our study on high cross-reactivity phenomena by using two in silico approaches, including molecular docking analysis and topology analysis. Overall, docking results show that several residues in the hydrophobic pocket produce hydrophobic interactions with the tested drug molecules, which contribute to the stability of their binding. In this paper, we conclude that the FP method is suitable for the rapid detection of stilbenes in milk samples, requiring no expensive analytical equipment or time-consuming sample preparation. This work offers a practical approach that applies bioscience technology in food safety testing and improves analytical speed and laboratory efficiency.

Characterization and application of molecularly imprinted polymer-coated quantum dots for sensitive fluorescent determination of diethylstilbestrol in water samples.

Molecularly imprinted silica layers coated to quantum dots (MIP-QDs) were successfully fabricated and applied as the fluorescence probe for highly selective and sensitive determination of diethylstilbestrol (DES). Scanning electron microscopy, Transmission electron microscopy, and Fourier transform infrared spectroscopy indicated successful grafting of molecularly imprinted silica layers onto the surface of QDs. Furthermore, the fluorescence assay based on the MIP-QDs showed excellent selectivity and fluorescence quenching capability in optimal conditions and a good linear relationship was obtained in the range of 2.0 × 10-4-10.0 mg/L with a correlation coefficient of 0.9980. The limit of detection of 5.9 × 10-5 mg/L was acquired. Good recoveries ranging from 95.5% to 107.5% were achieved with relative standard deviations (RSD) below 8.4% for seawater and river water samples. The fabricated MIP-QDs were successfully employed as the recognition and response element of an microtitration 96-well fluorescence detection system. Good recoveries ranging from 82.9% to 102.0% with RSDs below 10.0% were obtained for seawater and river water samples. Results demonstrate that simple, rapid, and sensitive DES determination method based on MIP-QDs can be successfully applied to DES residue detection in seawater and river water samples.

Analysis of Diethylstilbestrol Residues in Chicken Using Surface-Enhanced Raman Spectroscopy (SERS) Coupled with Multivariate Analysis.

Estrogen residues, including diethylstilbestrol in chicken, are one of the main food safety concerns all over the world owing to a series of negative effects on the human body. Surface-enhanced Raman spectroscopy (SERS) coupled with multivariate analysis was applied to detect rapidly diethylstilbestrol residues in chicken. The detection conditions, including the sizes of colloidal gold nanoparticles (Au NPs) and the additional amounts of Au NPs, chicken extract containing diethylstilbestrol, and magnesium sulfate solution, as well as the adsorption time, were optimized by a single factor experiment to obtain a better detection effect of diethylstilbestrol residues in chicken. Partial least squares regression (PLSR) was the best quantitative model for the detection of diethylstilbestrol residues in chicken by comparing four chemometric models. Diethylstilbestrol residues in chicken could be predicted by PLSR with the low root mean square error (RMSE = 0.4128 mg/L), and the high determination coefficient (R2 = 0.9811) and ratio of prediction to deviation (RPD = 7.2566) for the test set. A novel approach, which has the potential for the analysis of other estrogen residues in meat, was developed to detect rapidly the diethylstilbestrol residues in chicken by using SERS coupled with multivariate analysis.

[Determination of four phenolic estrogens in water samples by pressure-assisted electrokinetic injection coupled with capillary electrophoresis].

A capillary electrophoresis (CE) method was developed for the simultaneous separation and determination of four phenolic estrogens (PEs), in which pressure-assisted electrokinetic injection (PAEKI) was adopted as the on-line concentration method to enrich the PEs. Several parameters affecting PAEKI conditions such as injection voltage and injection time, were systematically investigated and compared with the usual parameters. Under the optimized PAEKI conditions (-9 kV, 0.3 psi (ca. 2.1 kPa), 0.4 min), the four PEs separated completely within 7 min. Good linearities were attained in the range of 0.05-5 mg/L for hexestrol and dienestrol, and 0.1-10 mg/L for bisphenol A and diethylstilbestrol, with correlation coefficients (r) over 0.9936. The limits of detection (S/N=3) were 0.0071-0.017 mg/L, and enrichment factors ranged from 11 to 15 compared to normal hydrodynamic injection. The combined micellar electrokinetic chromatographic-PAEKI method developed was used to determine the PEs in tap water and lake water samples; limits of quantification (S/N=10) of 0.029-0.064 mg/L and 0.033-0.079 mg/L were attained, respectively, by the two sample types. Furthermore, recoveries ranged from 75.6% to 110.1% with relative standard deviations (n=5) within 4.6%-11.8%. To use this PAEKI method, researchers would only need to adjust the parameters of the CE apparatus to perform on-line enrichment of analytes, without using other reagents; this demonstrates the simplicity, rapidity, and highly automated nature of this method.

A competitive photoelectrochemical immunosensor for the detection of diethylstilbestrol based on an Au/UiO-66(NH2)/CdS matrix and a direct Z-scheme Melem/CdTe heterojunction as labels.

A novel photoelectrochemical (PEC) bioassay protocol for diethylstilbestrol (DES) was systematically proposed. The Au/UiO-66(NH2) hybrid with countless active sites was fabricated using an in situ reduction strategy and was subsequently decorated with CdS nanoparticles (NPs) by a sequential chemical bath deposition process. The resulting Au/UiO-66(NH2)/CdS composites were exploited as a sensing matrix for the first time. The excellent photocurrent response of the as-prepared hybrid under visible light is attributed to its improved photo-electric conversion efficiency due to the local surface plasma resonance (LSPR) effect of Au and the matching energy-level structure between UiO-66(NH2) and CdS. In addition, the competitive strategy for the detection of DES was devised by employing the direct Z-scheme Melem/CdTe heterojunction covalently conjugated with bovine serum albumin (BSA)-DES as signal tags. As a consequence, a cascade-like band-edge level was obtained, which could effectively promote the transfer of photogenerated charges and markedly improve the photocurrent. On the basis of the above strategy, the concentrations of DES could be detected through the competitive binding of DES antibodies (Anti-DES) with either Melem/CdTe/BSA-DES or free DES. Under optimal conditions, the linear range for the detection of DES was 0.1 pg mL-1 to 20 ng mL-1. The detection limit was as low as 0.06 pg mL-1 (S/N = 3). Furthermore, the designed PEC DES-sensing approach has acceptable selectivity, reproducibility, and stability and offers great promise for the detection of small molecules in biomedical, food and environmental samples.

A novel electrochemical sensor based on Fe3O4-doped nanoporous carbon for simultaneous determination of diethylstilbestrol and 17ß-estradiol in toner.

In this paper, Fe3O4-doped nanoporous carbon (Fe3O4-NC) was synthesized through the carbonization of Fe-porous coordination polymer (Fe-PCP), which are also known as metal-organic framework (MOF), and fabricated into an electrochemical sensor for simultaneous analysis of diethylstilbestrol (DES) and 17ß-estradiol (E2) in toner. Fe3O4-NC was characterized by scanning electron microscope (SEM), powder X-ray diffraction (pXRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, N2 adsorption-desorption and so on. It is of great practical significance to achieve the simultaneous determination of the two estrogens because estrogens are co-existing in many real samples. The simultaneous determination of two common estrogens, DES and E2, was achieved through electro-catalytically oxidization at a Fe3O4-NC modified glassy carbon electrode (Fe3O4-NC/GCE). The peak currents of DES and E2 increased linearly as their concentrations increasing from 0.01 to 12 µmol/L and from 0.01 to 20 µmol/L, with detection limits of 4.6 nmol/L and 4.9 nmol/L (S/N = 3), respectively. This work was focused on the simultaneous determination of the two estrogens in toner. Furthermore, the recoveries of DES and E2 were 91.2-110%, in actual toner samples. The experimental results manifest that the sensor with a stronger anti-interference ability can be used for the simultaneous detection of DES and E2 in the actual toner sample.

Ultrasensitive competitive method-based electrochemiluminescence immunosensor for diethylstilbestrol detection based on Ru(bpy)32+ as luminophor encapsulated in metal-organic frameworks UiO-67.

In this work, Ru(bpy)32+ encapsulated in metal-organic frameworks (MOFs) UiO-67 (Ru(bpy)32+/UiO-67) as luminophor was easily prepared and firstly applied in constructing an electrochemiluminescence (ECL) immunosensor to efficiently estimate diethylstilbestrol (DES). The competitive method-based ECL immunosensor platform was fabricated by amino-silicon dioxide which possesses large surface area. The poriness of UiO-67 was splendid so that Ru(bpy)32+ could be easily encapsulated. Ru(bpy)32+/UiO-67 with excellent ECL luminescence signal existed large specific surface area for easily labeled with antibodies. DES competed with bovine serum albumin-diethylstilbestrol (BSA-DES) for binding to antibody-specific sites in the constructed immunosensor. However DES was micromolecule, which was easier to bond to antibodies than BSA-DES. The ECL signal was gradually decreases with the increase of the concentration of DES. Under optimal conditions, the proposed immunosensor exhibited a wide linear range from 0.01 pg mL-1 to 50 ng mL-1 with a low detetion limit of 3.27 fg mL-1 (S/N = 3). The novel fabricated immunosensor with interference immunity and high stability may cause an attractive approach for the other targets determination.

Simultaneous determination of environmental estrogens: Diethylstilbestrol and estradiol using Cu-BTC frameworks-sensitized electrode.

It is quite important to monitor environmental estrogens in a rapid, sensitive, simple and cost-effective manner due to their wide existence and high toxicity. Using 1,3,5-Benzenetricarboxylic acid (H3BTC) as the ligand and copper ions as the center, Cu-BTC frameworks with surface area of 654.6m(2)/g were prepared, and then used to construct a novel electrochemical sensing platform for diethylstilbestrol (DES) and estradiol (E2). On the surface of Cu-BTC frameworks, two oxidation waves at 0.26V and 0.45V are observed for DES and E2, and the oxidation signals are improved greatly. The prepared Cu-BTC frameworks not only enhance the accumulation efficiency of DES and E2, but also improve their electron transfer ability. The influences of pH value, modification amount of Cu-BTC and accumulation time were examined. As a result, a highly-sensitive, rapid and convenient electrochemical method was developed for the simultaneous determination of DES and E2, with detection limit of 2.7nM and 1.1nM. The practical applications manifest this new sensing system is accurate and feasible.

Multiplug filtration cleanup method with multi-walled carbon nanotubes for the analysis of malachite green, diethylstilbestrol residues, and their metabolites in aquatic products by liquid chromatography-tandem mass spectrometry.

The food safety supervision in aquatic products has raised public concern in recent years. In this study, a liquid chromatographic-tandem mass spectrometric (LC-MS/MS) method for the simultaneous quantification and identification of four residues of the ever widely used analytes (including malachite green, leucomalachite green, diethylstilbestrol, and dienestrol) in aquaculture samples was developed. For sample preparation, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was used, which was initially developed for pesticide residue analysis. For cleanup procedure, low-temperature cleanup method was combined with multiplug filtration cleanup (m-PFC) method based on multi-walled carbon nanotubes (MWCNTs). The volume of water, extraction solvent, cleanup sorbents, and m-PFC procedure were optimized for carp, striped bass, and giant salamander matrices. It was validated by analyzing four residues in each matrix spiked at three concentration levels of 0.5, 5, and 50 µg/kg (n = 5). The method was successfully validated according to the 2002/657/EC guidelines. After optimization, spike recoveries were within 73-106 % and <15 % relative standard deviations (RSDs) for all analytes in the tested matrices. Limits of quantification (LOQs) for the proposed method ranged from 0.10 to 0.50 µg/kg. Matrix-matched calibrations were performed with the coefficients of determination >0.998 between concentration levels of 0.5 and 200 µg/kg. The developed method was successfully applied to the determination of residues in market samples. Graphical abstract Flow chart of multi-plug filtration cleanup combined with low-temperature cleanup method.

Occurrence and removal of phenolic endocrine disrupting chemicals in the water treatment processes.

This paper evaluated the occurrence and removal efficiency of four selected phenolic endocrine disrupting chemicals (bisphenol A (BPA), octylphenol (OP), nonylphenol (NP) and diethylstilbestrol (DES)) in two drinking waterworks in Jiangsu province which take source water from Taihu Lake. The recombined yeast estrogen screen (YES) and liquid chromatography tandem mass spectrometry (LC-MS/MS) were applied to assess the estrogenicity and detect the estrogens in the samples. The estrogen equivalents (EEQs) ranged from nd (not detected) to 2.96 ng/L, and the estrogenic activities decreased along the processes. Among the 32 samples, DES prevailed in all samples, with concentrations ranging 1.46-12.0 ng/L, BPA, OP and NP were partially detected, with concentrations ranging from nd to 17.73 ng/L, nd to 0.49 ng/L and nd to 3.27 ng/L, respectively. DES was found to be the main contributor to the estrogenicity (99.06%), followed by NP (0.62%), OP (0.23%) and BPA (0.09%). From the observation of treatment efficiency, the advanced treatment processes presented much higher removal ratio in reducing DES, the biodegradation played an important role in removing BPA, ozonation and pre-oxidation showed an effective removal on all the four estrogens; while the conventional ones can also reduce all the four estrogens.

Evaluation of graphene-based sorbent in the determination of polar environmental contaminants in water by micro-solid phase extraction-high performance liquid chromatography.

A facile method of extraction using porous membrane protected micro-solid phase extraction (µ-SPE) with a graphene-based sorbent followed by high performance liquid chromatography-ultraviolet detector was developed. The reduced graphene oxide (r-GO) (1mg), synthesized from graphite oxide, was enclosed in a polypropylene bag representing the µ-SPE device, which was used for the extraction of estrogens such as estrone, 17ß-estradiol, 17α-ethynylestradiol and diethylstilbestrol in water. The r-GO obtained was identified and characterized by Fourier transform infrared, transmission electron microscopy, scanning electron microscopy and thermogravimetric analysis. The sorbent was loaded with sodium dodecyl sulfate by sonication to prevent agglomeration in aqueous solution. With this method, low limits of detection of between 0.24 and 0.52 ng L(-1) were achieved. For estrogen analysis a linear calibration range of 0.01-100 µg L(-1) was obtained, with the coefficients of determination (r(2)) higher than 0.992. This proposed method was successfully applied to determine estrogens in water.

Determination of diethylstilbestrol in seawater by molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography.

An effective and highly selective molecularly imprinted material was prepared by suspension polymerization for the isolation and pre-concentration of synthetic estrogen diethylstilbestrol (DES) in seawater. The obtained MIPMs were proved to have more uniform size and porous structure, with maximum adsorption capacity of 8.43 mg g(-1) almost two times more than NIPMs (4.43 mg g(-1)). The MIPMs showed no significant deterioration of the adsorption capacity after five rounds of regeneration. An off-line molecularly imprinted solid phase extraction (MISPE) method followed by HPLC-DAD was proposed for the detection of DES in seawater, and recoveries were satisfactorily higher than 77%. Four seawater samples in aquaculture area were analyzed and 0.61 ng mL(-1) DES was detected in one sample. The result demonstrated that this method can be used for the rapid separation and clean up of trace residual of DES in seawater.

Determination of Estrogens in Milk Samples by Magnetic-Solid-Phase Extraction Technique Coupled With High-Performance Liquid Chromatography.

A magnetic-solid-phase extraction method coupled with high-performance liquid chromatography and diode array detection has been developed for simultaneous determination of 3 estrogens in milk samples. In this work, Fe3O4 NPs were synthesized by a simple chemical co-precipitation reaction, and the surface of Fe3O4 was modified with cetyltrimethyl ammonium bromide (CTAB; designed as Fe3O4@CTAB). The synthesized Fe3O4@CTAB NPs were characterized by Fourier transformed infrared spectroscopy, scanning electron microscopy, and transmission electron microscope. Fe3O4@CTAB NPs have high binding affinity toward estrone (E1), 17ß-estradiol (17ß-E2), and diethylstilbestrol (DES). Fe3O4@CTAB NPs can be easily separated from sample solutions using an external magnet due to the high super-paramagnetic property. The separation, preconcentration procedure is fast and will be completed in 2 min. Estrogens linear dynamic ranges were achieved in the range of 10 to 1000 ng/mL with regression coefficients (R(2)) higher than 0.9992. The limits of detection were between 0.26 and 0.61 ng/mL. Parameters influencing the recoveries were investigated and optimized. The proposed method was used for the determination of E1, 17ß-E2, and DES in milk samples, and recoveries were ranged from 91.3% to 105.0%, with the relative standard deviations in the range of 2.7% to 4.0%.

Performance of metal-organic framework MIL-101 after surfactant modification in the extraction of endocrine disrupting chemicals from environmental water samples.

The research presented in this paper explored the modification and application of a metal-organic framework, MIL-101, with nonionic surfactant-Triton X-114 in dispersive solid-phase extraction for the preconcentration of four endocrine disrupting chemicals (estrone, 17α-ethynylestradiol, estriol and diethylstilbestrol) from environmental water samples. Triton X-114 molecules could be adsorbed by the hydrophobic surface of the MIL-101 crystals, and thus improved the dispersibility of MIL-101 in aqueous solution by serving as a hydrophilic coating. Cloud point phase separation from Triton X-114 accelerated the separation of extracts from the aqueous matrix. The proposed method combines the favorable attributes of strong adsorption capacity resulting from the porous structure of MIL-101 and self-assembly of Triton X-114 molecules. Post-extraction derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide was employed to facilitate the quantitative determination of the extracts by gas chromatography-mass spectrometry. The main factors affecting the preparation of modified MIL-101, and extraction of the analytes, such as the amount of surfactant, the ultrasonic and vortex durations, solution pH and desorption conditions, were investigated in detail. Under the optimized conditions, the present method yielded low limits of detection (0.006-0.023 ng/mL), good linearity from 0.09 to 45 ng/mL (coefficients of determination higher than 0.9980) and acceptable precision (relative standard deviations of 2.2-13%). The surface modified MIL-101 was demonstrated to be effective for the extraction of the selected estrogens from aqueous samples, giving rise to markedly improved extraction performance compared to the unmodified MIL-101.

Dietary exposure to endocrine disrupting chemicals in metropolitan population from China: a risk assessment based on probabilistic approach.

The intake of contaminated foods is an important exposure pathway for endocrine disrupting chemicals (EDCs). However, data on the occurrence of EDCs in foodstuffs are sporadic and the resultant risk of co-exposure is rarely concerned. In this study, 450 food samples representing 7 food categories (mainly raw and fresh food), collected from three geographic cities in China, were analyzed for eight EDCs using high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). Besides estrone (E1), other EDCs including diethylstilbestrol (DES), nonylphenol (NP), bisphenol A (BPA), octylphenol (OP), 17ß-estradiol (E2), 17α-ethinylestradiol (EE2), and estriol (E3) were ubiquitous in food. Dose-dependent relationships were found between NP and EE2 (r=0.196, p<0.05), BPA (r=0.391, p<0.05). Moreover, there existed a correspondencebetween EDCs congener and food category. Based on the obtained database of EDCs concentration combined with local food consumption, dietary EDCs exposure was estimated using the Monte Carlo Risk Assessment (MCRA) system. The 50th and 95th percentile exposure of any EDCs isomer were far below the tolerable daily intake (TDI) value identically. However, the sum of 17ß-estradiol equivalents (∑EEQs) exposure in population was considerably larger than the value of exposure to E2, which implied the underlying resultant risk of multiple EDCs in food should be concern. In conclusion, co-exposure via food consumption should be considered rather than individual EDCs during health risk evaluation.