Bisphenol AF Research Articles

Toxic effects of chronic exposure to BPAF and perturbation of gut microbiota homeostasis in marine medaka (Oryzias melastigma)

Bisphenol AF (BPAF), a substitute for bisphenol A (BPA), exhibits potent endocrine-disrupting properties that pose a serious health hazard to organisms. This study employed marine medaka as a model, subjecting them to different concentrations of BPAF (0.61, 6.65, and 91.88 μg/L) from the embryonic stage for a period of 160 days. Findings showed that 91.88 μg/L BPAF reduced survival rates and altered sex ratios. Furthermore, exposure to BPAF at all concentrations led to a significant increase in body length and weight. Behavioral analysis revealed that BPAF exposure impaired the swimming ability of the medaka. Histological changes included disrupted ovarian development, reduced sperm count, liver inflammation, and intestinal damage. Gene expression analysis revealed impacts on nervous system (e.g., gap43, itr, elavl3), HPG axis (e.g., gthα, erα, 3βhsd), and liver genes (e.g., chgl, vtg2). Additionally, BPAF altered the diversity and richness of gut microbes in marine medaka, leading to significant changes in specific bacterial species and intestinal functions. In conclusion, long-term BPAF exposure induced neurotoxicity, reproductive toxicity, and impaired digestive and immune systems in marine medaka, with sex-specific effects. These results provide further evidence of the potential hazards of BPAF as an environmental pollutant.

The impact of bisphenol AF on skeletal muscle function and differentiation in vitro

Various environmental chemicals have been identified as contributors to metabolic diseases. Bisphenol AF (BPAF), a substitute for bisphenol A, has been associated with changes in glucose metabolism and incidence of type 2 diabetes mellitus in humans. However, its mode of action remains unclear. Considering that skeletal muscle is the primary tissue for glucose utilization and the development of insulin resistance, yet largely neglected in toxicological assessments, we investigated the impact of BPAF on skeletal muscle function and differentiation.We examined the effects of BPAF (0.01–10 μM) on glucose uptake, response to insulin, production of reactive oxygen species (ROS), intracellular calcium, and myocyte differentiation, during hyperglycemia, insulin stimulation, and muscle contraction. We used the rat myoblast cell line L6 differentiated into myotubes, and murine primary isolated muscle fibers.In myotubes and contracting adult fibers, BPAF increased mitochondrial ROS. Basal glucose uptake was increased in myotubes while cells' ability to respond to insulin was decreased. Additionally, in developing myotubes, differentiation markers were downregulated with BPAF, along with impaired formation of tube structures. These effects were primarily observed at 10 μM concentration, which is markedly higher than reported human exposure concentrations.The results provide an insight into potential hazards associated with BPAF in terms of metabolic disruption in skeletal muscle. The developed in vitro methods show promise for future usage in assessments of new chemicals and their mixtures.

Altered mammary gland development and pro-tumorigenic changes in young female mice following prenatal BPAF exposure

Bisphenol A (BPA) is being phased out owing to its endocrine-disrupting effects and is increasingly being replaced by its substitute compounds such as bisphenol AF (BPAF). This study aims to explore the potential adverse outcomes of prenatal BPAF exposure combined with postnatal cross-fostering on the development and long-term health effects of the mammary gland in offspring. The results suggested that prenatal BPAF exposure accelerates the puberty, and induces duct dilatations, angiogenesis, lobular hyperplasia, and enhanced inflammatory cell infiltration in the mammary gland of female offspring. Differentially expressed genes exhibiting time series patterns induced by BPAF exposure were enriched in biological processes related to mammary gland development, epithelial cell proliferation and so on. Notably, 13 breast cancer-related biomarkers including Pgr, Gata3, Egfr and Areg were screened, showing a time-dependent increase in expression. After human homologous gene transformation, TCGA analysis suggested that the human homologues of genes differentially expressed in BPAF-treated mice were associated with increased tumor stages in female patients with breast cancer. Furthermore, postnatal cross-fostering did not completely restore the adverse effects of prenatal BPAF exposure and even showed a reverse tendency. These results imply that prenatal BPAF exposure in utero and postnatally nursing by BPAF exposed dams, have long-term effects on the mammary glands health of female offspring.

Preconception exposure to bisphenol A and its alternatives: Effects on female fecundity mediated by oxidative stress and ovarian reserve.

Various 'Bisphenol A (BPA)-free' alternatives have emerged in numerous personal products in recent years. However, it remains unclear whether BPA analogs affect female fecundity and possible biological mechanisms. We aimed to evaluate the relationships of bisphenol analogs with female fecundability and infertility and whether oxidative stress, inflammation, and ovarian reserve may play a mediation role in such associations. This prospective preconception cohort study included 957 couples who attempted pregnancy. BPA and six alternatives were measured in women's urine samples. Bisphenol analogs-outcome associations were estimated using discrete-time Cox hazards and logistic regression models. A quantile g-computation (QGC) methodology was further applied to assess the joint effects of co-exposure to bisphenol analogs on fecundity. We also quantified three biomarkers, including malondialdehyde (MDA), C-reactive protein and Anti-Müllerian hormone (AMH), to explore possible biological pathways. Using an integrated analytical approach consisting of both single-pollutant and mixture models, we found that BPA and bisphenol AP (BPAP) were significantly associated with decreased fecundability (adjusted fecundability ratio (aFR) = 0.87, 95%CI:0.81, 0.94 for BPA; aFR = 0.64, 95%CI: 0.48, 0.84 for BPAP) and increased risk of infertility (adjusted odd ratio (aOR) = 1.23, 95%CI:1.06, 1.44 for BPA; aOR = 2.27, 95%CI:1.29, 3.99 for BPAP) after controlling for other bisphenol analogs. The link between BPA and prolonged time to pregnancy was more prominent in overweight or obese women and those who had regular menstrual cycles. Bisphenol AF was associated with impaired fecundity in women aged 35 years or older. The mixed effects of bisphenol analogs on fecundity were statistically non-significant. Mediation analysis revealed a significant indirect effect of urinary MDA and serum AMH in bisphenol analogs-induced impaired fecundity, with all average causal mediation effects (ACME) showing statistical significance (PACME < 0.05). Our prospective preconception cohort study suggests that BPA and BPAP may be associated with impaired female fecundity. Increased oxidative stress and decreased ovarian reserve may be the underlying pathways.

Ultrasound-assisted bisphenol AF degradation using in situ generated hydrogen peroxide

Bisphenol AF (BPAF) is degraded through the ultrasound-assisted in situ generation and activation of hydrogen peroxide (H2O2) by the copper(II) catalysed oxidation of hydroxylamine (NH2OH) with dioxygen (O2). Compared to added H2O2, in situ generated H2O2 significantly improves the degradation of BPAF from 46.7% to 94.8% in ∼15 min. The reaction follows a pseudo-first-order kinetic model. This study examines the influence of solution pH, anions, humic acid, and different concentrations of the reactants on BPAF degradation. Mass spectrometry was used to identify the BPAF degradation products, and a degradation pathway is proposed. This work advances the understanding of in situ hydrogen peroxide generation and activation in advanced oxidation (Fenton-like) processes (AOPs).

Gene Expression Modulation of Markers Involved in Bone Formation and Resorption by Bisphenol A, Bisphenol F, Bisphenol S, and Bisphenol AF.

Bisphenol A (BPA) and its analogs (BPF, BPS, and BPAF) are recognized for inducing detrimental effects on various tissues, including bone. The aim of this study is to investigate their impact on information and repair processes, specifically focusing on vascular endothelial growth factor (VEGF), transforming growth factor β1 (TGF-β1), and the receptors for transforming growth factor β (TGFR1, TGFR2, and TGFR3). Human osteoblasts isolated through primary culture from bone samples of healthy volunteers were subjected to cultivation in the presence of various dosage levels (10-5, 10-6, or 10-7 M) of BPA, BPF, BPS, or BPAF for 24 h. Gene expressions of RANKL, OPG, TGF-β1, TGFR1, TGFR2, TGFR3, and VEGF were analyzed by real-time polymerase chain reaction (RT-PCR). All experiments included untreated cells as controls. Expressions of RANKL and OPG were dose-dependently downregulated by the presence of all tested bisphenols (BPs) except for BPAF, whose presence upregulated OPG expression at all three doses. TGF-β1 expression was downregulated by all BP treatments, and TGF-β1 receptor expression was also downregulated as a function of the BP and dose. VEGF expression was downregulated in the presence of BPF and BPAF at all three doses and in the presence of BPA at the two higher doses (10-5, and 10-6 M), but it was not changed by the presence of BPS at any dose. The inhibition of both RANKL and OPG by the BPs, with a higher %inhibition of RANKL than of OPG, appears to rule out BP-induced activation of osteoclastogenesis via RANKL/RANK/OPG. Nevertheless, the effect of the BPs on the expression by osteoblasts of TGF-β1, TGF-β receptors, and VEGF indicates that these compounds can be responsible for major molecular changes in this cell population, contributing to their adverse effects on bone tissue.

The Effects of Bisphenol A and its Analogs on Steroidogenesis in MA-10 Leydig Cells and KGN Granulosa Cells†.

Bisphenols are a family of chemicals used in the manufacture of consumer products containing polycarbonate plastics and epoxy resins. Studies have shown that exposure to bisphenol A (BPA) may disrupt steroidogenesis and induce adverse effects on male and female reproduction, but little is known about BPA replacements. We determined the effects of six bisphenols on the steroidogenic function of MA-10 Leydig cells and KGN granulosa cells by measuring the levels of progesterone and estradiol produced by these cells as well as the expression of transcripts involved in steroid and cholesterol biosynthesis. MA-10 and KGN cells were exposed for 48hours to one of six bisphenols (0.01-50μM): BPA, bisphenol F, bisphenol S, bisphenol AF, bisphenol M, or bisphenol TMC under both basal and dibutyryl cAMP (Bu2cAMP)-stimulated conditions. In MA-10 cells, most bisphenols increased the Bu2cAMP-stimulated production of progesterone. In KGN cells, there was a general decrease in progesterone production, while estradiol levels were increased following exposure to many bisphenols. qRT-PCR analyses revealed that all six bisphenols (≥1μM) upregulated the expression of STAR, a cholesterol transporter, in both cell lines after stimulation. Key transcripts directly involved in steroid and cholesterol biosynthesis were significantly altered in a cell line, chemical, and concentration-dependent manner. The expression of upstream genes was also differentially affected. Thus, BPA and five of its analogs can disrupt steroid production in two steroidogenic cell lines and alter the levels of transcripts involved in this process. Importantly, BPA replacements do not appear to have fewer effects than BPA.

Design of magnetically functionalized hydrogen-bonded organic framework for extraction and enrichment of bisphenols from environmental and human samples

The magnetic functionalized hydrogen bond organic framework named Fe3O4@PFC-11/1 was prepared for the first time and used as sorbent of magnetic solid-phase extraction to enrich bisphenols (BPs) prior to high-performance liquid chromatography analysis. The limits of detection were achieved 0.03–0.07 ng/mL, and the enrichment factors were calculated in the range of 234–296. The adsorption of Fe3O4@PFC-11/1 to BPs can be finished within 10 s. The maximum adsorption capacities of Fe3O4@PFC-11/1 to bisphenol F, bisphenol A, bisphenol B and bisphenol AF were calculated as 249.95, 413.74, 474.38 and 676.06 mg/g, respectively. The main adsorption mechanisms of BPs on Fe3O4@PFC-11/1 are attributed to pore filling, van der Waals force, hydrogen bond and π-π interaction. Finally, BPs were successfully detected in environmental and human samples with satisfactory recoveries (78.2–117.9 %). This work presented combination of Fe3O4 with PFC-1 to obtain a promising magnetic sorbent for extraction and enrichment of trace compounds in complex matrices.

Mitigating Dietary Bisphenol Exposure Through the Gut Microbiota: The Role of Next-Generation Probiotics in Bacterial Detoxification.

Bisphenols, such as bisphenol A and its analogs, which include bisphenol S, bisphenol F, bisphenol AF, and tetramethyl bisphenol F, are chemical contaminants commonly found in food that raise serious health concerns. These xenobiotics can potentially have harmful effects on human health. The gut microbiota plays a crucial role in metabolizing and neutralizing these substances, which is essential for their detoxification and elimination. Probiotic supplementation has been studied for its ability to modulate the gut microbiota's composition and function, enhancing detoxification processes. Next-Generation Probiotics (NGPs) may exhibit better properties than traditional strains and are designed for targeted action on specific conditions, such as obesity. By modulating inflammatory responses and reducing the secretion of pro-inflammatory cytokines, they can significantly improve host health. Research on NGPs' ability to neutralize obesogenic bisphenols remains limited, but their potential makes this a promising area for future exploration. This review aims to understand the mechanisms of the chemical transformation of bisphenol through its interactions with the gut microbiota and the role of probiotics, particularly NGPs, in these processes. Understanding the interplay between bisphenols, gut microbiota, and NGPs may pave the way for strategies to counteract the negative health effects associated with daily and chronic exposure to bisphenols, which is crucial for food safety and consumer health protection.

High‐Throughput Electrospinning of Unmodified and Aminated Poly(Pentafluorostyrene) for Fiber‐Reinforced Proton Exchange Membranes

AbstractThis study demonstrates a high‐throughput fabrication of fiber interlayers for proton exchange membranes based on poly(pentafluorostyrene) (PPFSt) and its aminated derivatives. The fibers are produced by electrospinning, where the parameters are carefully screened. The controlled parameters are solvent composition, weight percentage, voltage, flow rate, and temperature, controlled with a self‐designed heating jacket. The parameters are iterated toward optimized fiber structure and maximum output. The yielded fibers are infiltrated with Nafion and sulfonated polymer from bisphenol AF and decafluorobiphenyl (SFS001) by spray‐coating and doctor blading to obtain the fiber‐reinforced proton exchange membranes. Tensile tests reveal a higher Young's modulus and yield stress than pure Nafion. Here, the basicity of the aminated PPFSt fibers correlates with the Young's modulus due to improved acid‐base interactions between amine groups and sulfonic acid. The acid‐base interactions influence the composite membrane's proton conductivity, varying from 23 mS cm−1 for strongly alkaline fibers to 69 mS cm−1 for non‐basic fibers. These findings can be transferred to fabricating fiber reinforcements beyond routinely used poly(benzimidazoles).

Percutaneous absorption of two bisphenol a analogues, BPAF and TGSA: Novel In vitro data from human skin

Bisphenol AF (BPAF) and TGSA are analogues of Bisphenol A (BPA). BPAF is used in polymer synthesis, while TGSA is applied in thermal papers. The EU classifies BPAF as toxic to reproduction and TGSA as a skin sensitizer. However, TGSA's other health effects remain unclear. BPAF contamination has been noted among electronic waste workers, and TGSA exposure is documented in various professions. Despite the significance of skin contact, data on skin permeation rates for BPAF and TGSA are limited. This study aimed to generate percutaneous absorption data for BPAF and TGSA following OECD guidelines.[14C]-labeled BPAF or TGSA was applied to human skin samples in vitro using Franz diffusion cells for 20 and 40 h, respectively. Key parameters such as steady-state flux, lag time, and skin permeability coefficient (Kp) were calculated. Furthermore, the distribution of the dose across different compartments, particularly within the skin, was evaluated at the conclusion of the experiment. Sequential strippings and epidermis-dermis separation were conducted for BPAF to predict the potential absorption of the remaining dose present within the skin.The permeability coefficients for BPAF and TGSA were found to be 1.9 E−03 and 1.6 E−03 cm/h, with 22% and 23% of the applied doses absorbed, respectively. Both chemicals are classified as "fast" penetrants based on their Kp values. These findings suggest that BPAF and TGSA are absorbed through the skin, highlighting potential occupational risks through dermal exposure. The new percutaneous absorption data will enhance the assessment of the occupational risks.

Effects of Bisphenol A analogues and their mixture on the crab Carcinus aestuarii: Cytotoxicity, oxidative stress and damage, neurotoxicity, physiological responses, and bioaccumulation

Bisphenol A (BPA) analogues are emerging contaminants, whose ecotoxicological profile for aquatic species, particularly marine ones, is little known. In this study, the effects of an environmentally realistic concentration (300 ng/L) of three BPA analogues (BPAF, BPF, and BPS) - alone or as a mixture (MIX) – were evaluated for the first time on the crab Carcinus aestuarii. A multibiomarker approach was adopted to assess the effects of 7 and 14 days of exposure on haemolymph parameters, gill and hepatopancreas biochemical parameters, and physiological responses of crabs. Bioaccumulation of the three bisphenols was also investigated in crabs by UHPLC-HRMS. A significant reduction in total haemocyte counts was recorded in crabs exposed for 7 days to BPAF and MIX and for 14 days to the MIX, whereas an increase was found in crabs treated for 14 days with BPAF. Cell proliferation increased significantly in crabs exposed for 14 days to BPS and MIX. An imbalance of the antioxidant system, as well as oxidative damage, was recorded in gills and hepatopancreas. No neurotoxic effects were observed in crabs. At the physiological level, exposure to MIX increased the respiration rate of crabs. As for bioaccumulation, only bisphenol AF was detected in crabs. Overall, the present study demonstrated that BPA analogues can affect some important cellular parameters, induce oxidative stress and alter physiological responses in crabs.

B4C-Assisted Paper Spray Ionization Mass Spectrometry.

A novel inorganic nonmetallic material boron carbide (B4C) was applied in paper spray ionization to analyze organic molecules in both negative and positive modes. The utilization of B4C has led to a notable enhancement in signal responses for various molecules, including bisphenols and drugs, by approximately two to four times. The limit of detection (LOD) of bisphenol AF and nilotinib standard solutions can reach 1 and 0.5 μg/mL, respectively. Moreover, linear relationships for bisphenol AF was established within the concentration range of 1-100 μg/mL, exhibiting strong correlation coefficients. Recovery experiments for BPAF in water samples from the inlet and outlet of a sewage treatment plant, conducted without any pretreatment, achieved a maximum recovery rate of 98.8% and an RSD below 9.78%.

Heterogeneous Activation of Persulfate by Petal-Shaped Co3O4@BiOI to Degrade Bisphenol AF

In catalytic tests, the results have shown that almost all the BPAF was removed within 30 min when the dosage of Co3O4@BiOI and sodium persulfate (PS) was 0.15 g and 0.1 mM, respectively. Acid conditions inhibited BPAF degradation, but the inclusion of a precise concentration of bicarbonate ions (HCO3−) promoted degradation. The presence of chloride (Cl−), sulfate ions (SO42−), and a high concentration of HCO3− inhibited the degradation process, whereas the addition of nitrate ions (NO3−) had a minor effect on the catalytic process. The presence of free radicals (sulfate (SO4•−), hydroxyl (•OH), and superoxide (O2•−)) and the non-free radical singlet oxygen (1O2) in the Co3O4@BiOI/PS system was determined by electron paramagnetic resonance (EPR) and quenching tests. We propose that the Co(II)/Co(III) and Bi(III)/Bi(V) redox pairs simultaneously activate PS where the Co3O4 and BiOI components work synergistically to promote the rapid oxidative degradation of BPAF in water.

Cytotoxic impacts of seven alternative bisphenols on human in vitro cellular models

Bisphenols (BPs), common in plastics, coatings, and resins, are under scrutiny for potential endocrine disruption. Despite banning bisphenol A (BPA), its perceived safer alternatives may still pose health risks, urging thorough studies on their toxicity mechanisms. This study aimed to investigate the cellular toxicity of the top seven most commonly used BPs, bisphenol S (BPS), bisphenol F (BPF), bisphenol AF (BPAF), bisphenol P (BPP), bisphenol AP (BPAP), bisphenol B (BPB), bisphenol E (BPE) in eight different relevant human in vitro cell models: liver (HepaRG), intestinal (Caco-2), breast (T47D), brain (HMC-3), lungs (MRC-5), kidney (HEK293), endothelial (HMEC-1), and skin (HEK-001) cell lines. BPE manifested the highest cytotoxicity in Caco-2 cells, presenting an EC50 value of roughly 0.2 μM (95% confidence interval). In contrast, HEK293 and HepaRG cells demonstrated significant resilience to BPS (EC50 > 1000 μM). BPAF, BPP, and BPAP had consistently low EC50 values across cell lines (6–27.9 μM, 0.6–134.7 μM, and 3.6–178.8 μM), indicating elevated toxicity. After 24 h, all bisphenols adhered to nominal concentrations except BPAF, BPP, and BPS. BPP's concentration notably decreased (30.82 ± 5.53% of nominal value). The results revealed diverse effects of bisphenol analogs on different cell types. These findings emphasized the considerable cytotoxic potential of specific bisphenol analogs across various human cell models, underlining the necessity for a re-evaluation of their safety and regulatory standards.

Prenatal co-exposure to phthalate metabolites and bisphenols among non-syndromic cleft lip and/or palate in offspring

Phthalate metabolites and bisphenols can cause adverse pregnancy outcomes. However, there is no study to evaluate the associations of prenatal exposure to phthalate metabolites and bisphenols with non-syndromic cleft lip and/or palate (NSCL/P) risk in offspring. A population-based case-control study was conducted in a multicenter setting from 2005 to 2021, enrolling 448 pregnant women. Seven phthalate metabolites and six bisphenols were quantified in placenta using liquid chromatography-tandem mass spectrometry. In the logistic regression analysis, high levels of mono-ethyl phthalate, mono-cyclohexyl phthalate, mono-octyl phthalate, bisphenol A, bisphenol AF, bisphenol AP, and fluorene-9-bisphenol were associated with increased NSCL/P risk with odds ratios (95% confidence intervals) of 1.86(1.07,3.25), 6.56(3.47,12.39), 8.49(4.44,16.24), 8.34(4.32,16.08), 3.19(1.81,5.62), 2.78(1.59,4.86), and 5.16(2.82,9.44). The Bayesian kernel machine regression model revealed that co-exposure to phthalate metabolites and bisphenols was associated with increased NSCL/P risk. Similarly, quantile-based g-computation analysis indicated that each quantile increase in mixture concentration was positively related to higher risk for NSCL/P [odds ratio (95% confidence interval) = 2.98(1.97,4.51)]. This study provides novel evidence that prenatal single and co-exposure to phthalate metabolites and bisphenols were associated with increased NSCL/P risk, suggesting that exposure to phthalate metabolites and bisphenols during pregnancy should be minimized to reduce the incidence of NSCL/P in offspring.

Exposure and potential risks of thirteen endocrine- disrupting chemicals in pharmaceuticals and personal care products for breastfed infants in China

Ingestion of breast milk represents the primary exposure pathway for endocrine-disrupting chemicals (EDCs) in newborns. To elucidate the associated risks, it is essential to quantify EDC levels in both breast milk and infant urine. This study measured the concentrations of 13 EDCs, including parabens (methyl paraben (MP), ethyl paraben (EP), propyl paraben (PP), iso-propyl paraben, butyl paraben, and iso-butyl paraben), bisphenols (bisphenol A (BPA), bisphenol F, bisphenol S, bisphenol AF, and bisphenol Z), triclosan (TCS), and triclocarban, in breast milk and infant urine to assess their potential health effects and endocrine disruption risks. In total, 1 014 breast milk samples were collected from 20 cities across China, along with 144 breast milk samples and 134 urine samples from a mother-infant cohort in Hangzhou. The EDCs were detected using ultra-high-performance liquid chromatography-triple quadrupole mass spectrometry. Endocrine-disrupting potency was evaluated using a predictive method based on EDC affinity for 15 hormone receptor proteins. The toxicological priority index (ToxPi), incorporating population exposure data, was employed to assess health risks associated with exposure to multiple EDCs. Among the 13 EDCs, MP, EP, PP, BPA, and TCS were detected in over 50 % of breast milk samples, with the highest median concentrations observed for MP (0.37 ng/mL), EP (0.29 ng/mL), and BPA (0.17 ng/mL). Across the 20 cities, 0 %–40 % of infants had a hazard index (HI) exceeding 1. Based on affinity prediction analysis and estimated exposure, cumulative endocrine disruption risk intensity was ranked as MP > TCS > BPA > EP > PP. This research highlights the extensive exposure of Chinese infants to EDCs, offering a detailed analysis of their varying endocrine disruption potencies and underscoring the significant health risks associated with EDCs in breast milk.

Synthesis and properties of low dielectric thermotropic liquid crystal polyarylates

In this study, a series of low dielectric liquid crystal polyarylates were designed and synthesized through the acetylation of hydroxyl-containing monomers followed by melt polycondensation with 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA), bisphenol A (BPA), bisphenol AF (BPAF), terephthalic acid (TA) acid and 2,3,5,6-tetrafluoroterephthalic acid (TFTA). The molar ratio of HBA to HNA was controlled at 7:3. The structures of the acetylated monomers and polyarylates were characterized using FTIR and NMR spectroscopy, while the elemental composition of the polyarylates was analysed via XPS. WAXD and POM analyses revealed that the prepared polyarylates exhibit a single crystalline form and are capable of forming liquid crystals. DSC and TGA analyses indicated that the incorporation of bisphenol-type monomers (BPA or BPAF) disrupted the regularity of the main chain, leading to a decrease in both the melting point and thermal stability. Finally, the incorporation of bulky monomers (BPA or BPAF) and fluorinated monomers (BPAF and TFTA) into polyarylates increases free volume and decreases polarization, leading to a significant reduction in the dielectric constant.

Preparation and evaluation of Fe3O4@C@NiCo-LDH@CDs composites for magnetic solid-phase extraction of trace endocrine disruptors.

The widespread use of endocrine disruptors (EDPs) has certain potential hazards to organisms and environments, and it is particularly important to develop effective pretreatment methods before detection of EDPs in complex samples. In this work, a novel magnetic nanocomposite decorated with layered double hydroxides (LDHs) and carbon dots (CDs) was designed and prepared for magnetic solid-phase extraction (MSPE) of EDPs (bisphenol S, bisphenol F, bisphenol A, bisphenol AF, diethylstilbestrol and 4-cumylphenol) combined with high-performance liquid chromatography-ultraviolet (HPLC-UV) detection. The prepared composites were characterized by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS), and the adsorption mechanism towards these EDPs might be mainly based on hydrogen bonds and π-π conjugation. Under the optimized conditions, the proposed method showed limits of detection within 0.05-0.50 μg L-1 and limits of quantitation within 0.2-2.0 μg L-1, and good linearity (R2 ≥ 0.9975) was presented in the range of 0.2-200 μg L-1. Finally, the Fe3O4@C@NiCo-LDH@CDs composite-based MSPE-HPLC-UV method was applied for enrichment and determination of EDPs in water, milk, and tea beverage samples with recoveries in the range of 81.2-119.8% and relative standard deviations below 9.7%.

Assessing the Effects of a Diet of BPA Analogue-Exposed Microalgae in the Clam Ruditapes philippinarum.

In our previous study, we demonstrated that the microalgae Phaeodactylum tricornutum can bioaccumulate bisphenol A analogues. Since this microalgae species is part of the diet of marine filter-feeding organisms, such as bivalves, in this study we tested the hypothesis that a diet based on exposed microalgae can exert negative effects on the clam Ruditapes philippinarum. Microalgae were exposed for 7 days to 300 ng/L of bisphenol AF (BPAF), bisphenol F (BPF), and bisphenol S (BPS), alone or as a mixture (MIX), to allow bioaccumulation. Microalgae were then supplied as food to bivalves. After 7 and 14 days of diet, the effects of exposed microalgae were evaluated on a battery of biomarkers measured in haemolymph/haemocytes, gills and digestive glands of clams. In addition, bioaccumulation of the three bisphenols was investigated in clams by UHPLC-HRMS. The results obtained demonstrated that total haemocyte count (THC) increased in clams following ingestion for 7 days of BPAF- and BPF-exposed microalgae, while BPS-exposed microalgae significantly reduced THC after 14 days of diet. MIX- and BPS-exposed microalgae increased haemocyte proliferation. The diet of exposed microalgae affected acid and alkaline phosphatase activity in clams, with an opposite response between haemolymph and haemocytes. Regarding antioxidants, an increase in catalase activity was observed in clams after ingestion of BPA analogue-exposed microalgae. The results also demonstrated marked oxidative stress in gills, the first tissue playing an important role in the feeding process. Oxidative damage was recorded in both the gills and digestive glands of clams fed BPA analogue-exposed microalgae. Alterations in epigenetic-involved enzyme activity were also found, demonstrating for the first time that BPA analogue-exposed food can alter epigenetic mechanisms in marine invertebrates. No bioaccumulation of BPA analogues was detected in clam soft tissues. Overall, this study demonstrated that a diet of BPA analogue-exposed microalgae can induce significant alterations of some important biological responses of R. philippinarum. To our knowledge, this is the first study demonstrating the effects of ingestion of BPA analogue-exposed microalgae in the clam R. philippinarum, suggesting a potential ecotoxicological risk for the marine food chain, at least at the first levels.