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Many studies have shown that it is important to consider the harmful effects of phenolic hormones on the human body. Traditional UV detection has many limitations, so there is a need to develop new detection methods. We demonstrated a simple and rapid surface-enhanced resonance Raman scattering (SERRS) based detection method of trace amounts of phenolic estrogen. As a result of the coupling reaction, there is the formation of strong SERRS activity of azo compound. Therefore, the detection limits are as low as 0.2 × 10−4 for estrone (E1), estriol (E3), and bisphenol A (BPA). This method is universal because each SERRS fingerprint of the azo dyes a specific hormone. The use of this method is applicable for the testing of phenolic hormones through coupling reactions, and the investigation of other phenolic molecules. Therefore, this new method can be used for efficient detection.

This paper reports the application of a carbon paste electrode modified with magnetite nanoparticles and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate in the electroanalytical determination of 17β-estradiol and estriol. These estrogens are potential endocrine disruptors and thus it is relevant the development of devices for their monitoring. Transmission electron microscopy, scanning electron microscopy and zeta potential techniques were applied to characterization of the modifier materials. In cyclic voltammetry experiments, irreversible oxidation peaks were observed for 17β-estradiol and estriol at +0.320 V and +0.400 V, respectively. The anodic currents obtained were approximately three times greater than those provided by the unmodified electrode due to the presence of magnetic nanoparticles and the ionic liquid, which improved the sensitivity of modified electrode. For the analysis, the parameters of the square-wave voltammetry (scan increment, amplitude and frequency) were optimized by Box-Behnken factorial design for each estrogen. For 17β-estradiol in B-R buffer pH 12.0, the calibration plot was linear from 0.10 to 1.0 μmol L −1 , with a detection limit of 50.0 nmol L −1 . For estriol in B-R buffer pH 11.0, the linear range was 1.0 to 10.0 μmol L −1 , with a detection limit of 300.0 nmol L −1 . The modified electrode was applied in the determination of 17β-estradiol and estriol in pharmaceutical formulations and the results were comparable to those obtained using UV/VIS spectrometry. Statistical tests were applied to evaluate the results and it was concluded that there was no significant difference regarding the precision and accuracy of the data provided by the two methods.

Pig farming has a very strong economic importance in Brazil. The residues from this activity are applied to the soil because of their excellent characteristics as biofertilizers. The present study aimed at studying the estrone, 17β-estradiol, and estriol natural hormones, emerging contaminants present in this type of residue that are not mentioned in the current legislation. The characterization of the pig farming effluent presented high concentrations of hormones (mg L −1 ). The objective was to apply the biosorbents to the removal of the hormones in batch systems directly in the manure heaps without affecting the potential of the effluent as a fertilizer. It was verified that the adsorption of hormones using the rice husk biomass in natura and soybean hull in natura, abundant alternative adsorbents, presented a good capacity of removal of hormones. The presence of the organic materials (rice husk and soybean hull) caused few alterations in the biofertilizer characteristics, demonstrating that these adsorbents present a potential of application in batch treatment systems, with possible applications related to pig farming effluents containing natural hormones.

The presence of estrogens in livestock excrement has raised concerns about their potential negative influence on animals and the overall food cycle. This is the first investigation to simultaneously remove estrogens, including estriol (E3), bisphenol A (BPA), diethylstilbestrol (DES), estradiol (E2), and ethinyl estradiol (EE2), from cow manure using a Fenton oxidation technique. Based on the residual concentrations and removal efficiency of estrogens, the Fenton oxidation reaction conditions were optimized as follows: a H2O2 dosage of 2.56 mmol/g, a Fe(II) to H2O2 molar ratio of 0.125 M/M, a solid to water mass ratio of 2 g/mL, an initial pH of 3, and a reaction time of 24 h. Under these conditions, the simultaneous removal efficiencies of E3, BPA, DES, E2, and EE2, with initial concentrations in cow manure of 97.40, 96.54, 100.22, 95.01, and 72.49 mg/kg, were 84.9%, 99.5%, 99.1%, 97.8%, and 84.5%, respectively. We clarified the possible Fenton oxidation reaction mechanisms that governed the degradation of estrogens. We concluded that Fenton oxidation technique could be effective for efficient removal of estrogens in livestock excrement. Results are of great importance for cow manure reuse in agricultural management, and can be used to reduce the threat of environmental estrogens to human health and ecological safety.

Background Light‐initiated chemiluminescent assays (LICA) are homogeneous assays that are sensitive, specific, and free of separation and washing steps and have high throughput and high precision. Methods In this research, we developed a competitive method by LICA to achieve accurate quantification of estradiol (E2) in human serum. E2 competed with estriol (E3) for binding to anti‐human E2 antibodies. E3 was linked to biotin via bovine serum albumin as a linker. As this assay used competition between the labeled tracer and the analyte, an increase in E2 concentration will cause a signal decrease. Results The expected detection range of E2 was 20‐5000 pg/mL. The analytical and functional sensitivities were 7.16 and 13.7 pg/mL, respectively. The intra‐ and inter‐assay coefficients of variation were both below 15%, and the recovery rate ranged from 97.5% to 106.8%. The interference rates ranged from −3.6% to 5.4% and met detection requirements for E2 in hyperbilirubinemia, hemolysis, and lipemia in clinical samples. In addition, the cross‐reactivity rates between E2 and structural analogs and some reproductive hormones varied from 1.9% to 10.6% which showed that LICA is highly specific for E2. Moreover, our results showed high accordance with the IMMULITE 2000 (y = 0.6695x + 47.92, r2 = .843) and VIDAS systems (y = 1.099x − 821.5, r2 = .9392). Conclusion Our data show that the LICA, which is easy to automate, is a promising technique for quantification of E2 in human serum and could be used for clinical detection.

Genistein, a major phytoestrogen of soy, is considered a potential drug for the prevention and treatment of post-menopausal osteoporosis. Mounting evidence suggested a positive correlation between genistein consumption and bone health both in vivo and in vitro. Earlier studies have revealed that genistein acted as a natural estrogen analogue which activated estrogen receptor and exerted anti-osteoporotic effect. However, it remains unclear whether PTH, the most crucial hormone that regulates mineral homeostasis, participates in the process of genistein-mediated bone protection. In the present study, we compared the therapeutic effects between genistein and nilestriol and investigated whether PTH and its specific receptor PTHR1 altered in response to genistein-containing diet in the animal model of ovariectomy. Our results showed that genistein administration significantly improved femoral mechanical properties and alleviates femoral turnover. Genistein at all doses (4.5 mg/kg, 9.0 mg/kg and 18.0 mg/kg per day, respectively) exerted improved bending strength and b-ALP limiting effects than nilestriol in the present study. However, genistein administration did not exert superior effects on bone protection than nilestriol. We also observed circulating PTH restoration in ovariectomized rats receiving genistein at the dose of 18 mg/kg per day. Meanwhile, PTHR1 abnormalities were attenuated in the presence of genistein as confirmed by RT-PCR, Western blot and immunohistochemistry. These findings strongly support the idea that besides serving as an estrogen, genistein could interact with PTH/PTHR1, causing a superior mineral restoring effect than nilestriol on certain circumstance. In conclusion, our study reported for the first time that the anti-osteoporotic effect of genistein is partly PTH/PTHR1-dependent. Genistein might be a potential option in the prevention and treatment of post-menopausal osteoporosis with good tolerance, more clinical benefits and few undesirable side effects.

Unconjugated estriol (uE3) is routinely analyzed in clinical laboratories as risk assessment for Down syndrome. Immunoassays of various types are the most commonly used methods. The accuracies of RIAs and ELISAs for uE3 have been questioned, and to date there have been no independent studies investigating the accuracy of the relatively new chemiluminescent immunoassays. We developed and validated a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for uE3 measurements in serum. Serum samples from patients in the second trimester of pregnancy were used, and uE3 concentrations were measured by LC-MS/MS and the Beckman Coulter Access® 2 and Siemens IMMULITE 2000 automatic chemiluminescent immunoassay analyzers. The LC-MS/MS method was validated and showed limit of detection 0.05 ng/mL; limit of quantification 0.2 ng/mL; linearity of response to 32 ng/mL; total imprecision of 16.2%, 10.4%, and 8.2% for uE3 at 1.10, 4.18, and 8.32 ng/mL, respectively; and analytical recoveries of 95.9%-104.2%. ANOVA of the correlation for LC-MS/MS results vs chemiluminescent immunoassays results showed R(2) = 0.9678 (Access 2 = 0.9305 LC-MS/MS + 0.2177, Sy|x = 0.1786, P < 0.0001), and R(2) = 0.9663 (IMMULITE 2000 = 0.8849 LC-MS/MS - 0.0403, Sy|x = 0.1738, P < 0.0001). Bland-Altman plots of uE3 results revealed concentration-dependent immunoassay biases. Mock risk analysis for Down syndrome showed no apparent difference in the risk assessment outcomes if the adjusted method-specific multiples of the median were used, and the assay imprecision was <10% CV. Standardization of immunoassay methods for uE3 analysis is needed to improve the accuracy of the measurements.

We describe the application of silver nanoparticles (Ag NPs) as matrices for the determination of three estrogens using surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). Because Ag NPs have extremely high absorption coefficients (1.2 × 10 8 M −1 cm −1) at 337 nm, they are effective SALDI matrices when using a nitrogen laser. Three tested estrogens—estrone (E1), estradiol (E2), and estriol (E3)—adsorb weakly onto the surfaces of the Ag NPs, through van der Waals forces. After centrifugation, the concentrated analytes adsorbed on the Ag NPs were subjected directly to SALDI-MS analyses, with the limits of detection for E1, E2, and E3 being 2.23, 0.23, and 2.11 μM, respectively. The shot-to-shot and batch-to-batch variations for the three analytes were less than 9% and 13%, respectively. We validated the practicality of this present approach through the quantitation of E2 in human urine. Using this approach, we determined the concentration of E2 in a sample of a pregnant woman's urine to be 0.16 ± 0.05 μM ( n = 10). Silver nanoparticles as the matrix for determination of estrogens by surface-assisted laser desorption/ionization mass spectrometry.

The main source of natural estrogens to municipal wastewater is human excretions via urine or feces, thus their concentrations in raw wastewater should show positive linear relationship with their human excretions. This study mainly focused on their concentration relationship in raw wastewater. Based on comparison between chemical analyses and predictions through human excretion rates, the observed concentrations of estriol (E₃) in municipal wastewater were found to be noticeably lower than the predicted values. The main cause for the disparity is that substantial conjugated E₃also exists in raw wastewater. This work suggested that monitoring both E₃and its conjugates is necessary to get more accurate E₃removal performance of wastewater treatment plants (WWTPs).

Lipoxin A4 (LXA4), an endogenous anti-inflammatory and immunomodulatory mediator studied in many disease states, is recently appreciated as a potentially significant player in the endometrium. This eicosanoid, synthesized from arachidonic acid via the action of lipoxygenase enzymes, is likely regulated in endometrial tissue during the menstrual cycle. Recent studies revealed that LXA4 acts as an estrogen receptor agonist in endometrial epithelial cells, antagonizing some estrogen-mediated activities in a manner similar to the weak estrogen estriol, with which it shares structural similarity. LXA4 may also be an anti-inflammatory molecule in the endometrium, though its precise function in various physiological and pathological scenarios remains to be determined. The expression patterns for LXA4 and its receptor in the female reproductive tract suggest a role in pregnancy. The present review provides an oversight of its known and putative roles in the context of immuno-endocrine crosstalk. Endometriosis, a common inflammatory condition and a major cause of infertility and pain, is currently treated by surgery or anti-hormone therapies that are contraceptive and associated with undesirable side effects. LXA4 may represent a potential therapeutic and further research to elucidate its function in endometrial tissue and the peritoneal cavity will undoubtedly provide valuable insights.