Search

The endocrine disrupting compound Bisphenol and its analogues are widely used in food packaging products and can cause serious health hazards. The protein, Lysozyme (Lyz), showing anti-microbial properties, is used as a "natural" food and dairy preservative. Herein, we explored the interaction between Lyz and Bisphenol S (BPS) by multi-spectroscopic and theoretical approaches. Lyz interacts with BPS through static quenching, where hydrophobic force governed the underlying interaction. Molecular docking results reveal that tryptophan plays a vital role in binding, corroborated well with near UV-CD studies. A decrease in the radius of gyration (from 1.43 nm to 1.35 nm) of Lyz substantiates the compactness of the protein conformation owing to such an interaction. This structural alteration experienced by Lyz may alter its functional properties as a food preservative. Consequently, this can degrade the quality of the food products and thereby lead to severe health issues.

Bisphenol A is a synthetic compound widely used in industry, in the production of polycarbonate, epoxy resins, and thermal paper, among others. Its annual production is estimated at millions of tons per year, demonstrating its importance. Despite its wide application in various everyday products, once in the environment (due to its disposal or leaching), it has high toxicity to humans and animal life, and this problem has been well known for years. Given this problem, many researchers seek alternatives for its monitoring in matrices such as natural water, waste, food, and biological matrices. For this, new advanced materials have been developed, characterized, and applied in creative ways for the preparation of samples for the determination of bisphenol A. This article aims to present some of these important and recent applications, describing the use of molecularly imprinted polymers, metal and covalent organic frameworks, ionic liquids and magnetic ionic liquids, and deep eutectic solvents as creative solutions in sample preparation for the long-standing problem of bisphenol A determination.

BACKGROUND: Emerging micro‐pollutants (EMPs) in water have received much attention due to their potential hazards to human health and ecological security. Ferrate has been researched in recent years to remove both particulate and dissolved impurities (including EMPs) from water, and its promising performance has been attributed to the high oxidation capacity and coagulation functions. However, limited research has compared ferrate with coagulation alone in the treatment of EMPs, which is one of the major objectives of this study. RESULTS: Three emerging micro‐pollutants (EMPs), imidacloprid (IMP), bisphenol‐S (BS), and azithromycin (AZM) were chosen for this study. In all cases, ferrate outperformed to ferric chloride in the removal of the EMPs. For a given ferrate dose of 0.05 mM, 99% of BS, 85% of AZM, and 78% of IMP were removed for a start concentration of 10 μg L⁻¹. However, if the start concentration was 1000 μg L⁻¹, removal efficiency was decreased to 82% for BS, 62% for AZM, and 22% for IMP. pH 5 was favorable to the EMP removal by ferrate for the study conditions. Although higher removals of IMP, BS, and AZM were achieved by ferrate in comparison to those by ferric chloride, only 20% DOC removal was achieved by the ferrate. The formation of various oxidation products in the degradation process resulted in the disparity of the solution toxicity; that of BS was reduced but those of IMP and AZM increased after ferrate treatment. Nevertheless, the toxicity of ferric chloride treated samples was all increased. CONCLUSION: Ferrate has higher efficiency comparing with FeCl₃ to remove IMP, BS, and AZM. Degradation of the EMPs by ferrate was more efficient in acidic conditions (pH 5) and at the EMPs' lower initial concentrations for the given conditions. IMP was more resistant to the ferrate treatment compared to BS and AZM under the same conditions. Overall, 20% DOC reduction was achieved by ferrate for pH 5. Finally, the toxicity of BS can be reduced but those of IMP and AZM were increased after ferrate treatment, whilst the toxicity of ferric chloride treated samples was all increased. © 2020 Society of Chemical Industry

This research is an application of fiber-in-tube solid-phase microextraction followed by high-performance liquid chromatography with UV detection for the extraction and determination of trace amounts of bisphenol A. Nanomagnetic Fe3 O4 was formed on the surface of polypropylene porous hollow fibers to increase the surface area and then it was coated with polystyrene. The introduction of polystyrene improves the surface hydrophobicity and is an appropriate extractive phase because it is highly stable in aquatic media. The extraction was carried out in a short capillary packed longitudinally with the fine fibers as the extraction medium. Extraction conditions, including extraction and desorption flow rates, extraction time, pH, and ionic strength of the sample solution, were investigated and optimized. Under optimal conditions, the limit of detection was 0.01 µg/L. This method showed good linearity for bisphenol A in the range of 0.033-1000 µg/L, with the coefficient of determination of 0.9984. The inter- and intraday precisions (RSD%, n = 3) were 7.9 and 6.3%, respectively. Finally, the method was applied to analysis of the analyte in thermal papers, disposable plastic cups, and soft drink bottles.

Bisphenol A (BPA) has been widely reported to exert endocrine disrupting effects, including the induction of adipogenesis in cultured preadipocytes and intact animals. Because of the potential harm to human health, BPA is being substituted by structurally related bisphenols. Whether or not such BPA analogues are safe substitutes, however, remains largely unknown. Here, we investigated the potential of bisphenol B (BPB), bisphenol E (BPE), bisphenol F (BPF), bisphenol S (BPS), and 4-cumylphenol (4-CP) to affect lipid and hormone levels in 3 T3-L1 cells. We found that BPB, BPE, BPF, BPS, and 4-CP all affected lipid accumulation and leptin levels to the same extent and potencies as BPA. Based on these and other results, we conclude that these BPA analogues and 4-CP most likely will elicit similar effects on adipocytes as BPA. Using them to substitute BPA in products should be done with caution.

A novel approach is presented to determine four bisphenols in water and urine samples, employing magnetic dispersive solid‐phase extraction combined with liquid chromatography and diode array detection. A modified zeolite‐based magnetic composite was used as an efficient sorbent, combining the advantages of magnetic materials with the remarkable properties of zeolites. A multivariate optimization design was employed to optimize some experimental factors affecting magnetic dispersive solid‐phase extraction. The method was evaluated under optimized conditions (i.e., amount of sorbent, 50 mg; sample pH, unadjusted; NaCl concentration, 1.25%; extraction and elution time, 2 min; eluent solvent, ethanol; eluent solvent volume, 400 µL), obtaining good linearity with correlation coefficients ranging between 0.995 and 0.999 (N = 5) (from 2 to 250 µg/L for bisphenol A, bisphenol AP, and bisphenol P and from 5 to 250 µg/L for bisphenol AF). Method repeatability was assessed obtaining coefficients of variation between 3 and 11% (n = 6). Finally, the method was applied to spiked real samples, obtaining for water samples relative recoveries between 83 and 105%, and for urine samples between 81 and 108% for bisphenol A, bisphenol AP, and bisphenol AF, and between 47 and 59% for bisphenol P. The authors would like to thank the Spanish Ministry of Economy and Competitiveness and European Union (FEDER funds) (project no. CTQ2016-79991-R) and Generalitat Valenciana (Spain) (project no. PROMETEO/2018/087) for the financial support. P. Baile also thanks Ministry of Education, Culture and Sports for her FPU grant (FPU14/04589).

Background Bisphenol A is widely used in the manufacture of polycarbonate plastics and has caused increasing concern over its potential adverse impacts on spermatogenesis. However, the effect of bisphenol A on spermiogenesis is yet to be explored. Objectives To evaluate whether bisphenol A has adverse effects on DNA integrity and protamination of spermatogenic cell. Materials and methods Newborn male mice were subcutaneously injected with bisphenol A (0.1, 5 mg/kg body weight, n = 15) or coin oil (control group, n = 20) daily from post-natal day 1 until 35. At post-natal day 70, epididymis caudal spermatozoa and testes were collected. Sperm count, sperm motility, and sperm morphology were analyzed. The sperm chromatin structure assay was performed to examine the sperm DNA fragmentation. Terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) method was used to assess apoptosis of spermatogenic cells. The ultrastructural features of testicular sections were examined under a transmission electron microscope. Western blot and RT-PCR were used to detect the expression levels of transition protein (Tnp) 1 and Tnp2, protamine (Prm) 1 and Prm2 protein, and mRNA in mice testes. Results Bisphenol A significantly reduced sperm counts, impaired sperm motility, and increased the percentage of malformed spermatozoa. Poor sperm chromatin integrity and increased TUNEL-positive spermatogenic cells were also observed in mice exposed to bisphenol A. Ultrastructural analysis of testes showed that bisphenol A exposure caused incomplete chromatin condensation, retention of residual cytoplasm, and abnormal acrosome formation. In addition, the relative expression levels of Tnp2 and Prm2 in mice testes decreased significantly in bisphenol A groups. Discussion and conclusion Our findings identified that neonatal bisphenol A exposure may negatively contribute to the sperm quality in adult mice. Mechanistically, we showed that bisphenol A reduced sperm chromatin integrity along with increased DNA damage, which may be due to poor protamination of spermatozoa.

Aim To study the molecular mechanism of G protein-coupled receptor 30-epidermal growth factor receptor (GPR30-EGFR) signaling pathway on the proliferation of leiomyoma cells exposed with bisphenol A. Methods Primary cultures and subcultures of human uterine leiomyoma (UL) cells. The expressions of messenger RNA and proteins of GPR30 and EGFR in 15 leiomyoma tissue specimens and all groups were detected by real-time quantitative polymerase chain reaction assay and Western blot assay. The protein of mitogen-activated protein kinases (MAPK)/extracellular signal-regulated kinases (ERK)/c-fos signaling pathway members was detected by Western blot assay. Results Bisphenol A promoted the growth of UL cells and the expressions of GPR30, EGFR, c-fos and p-ERK1/2. Conclusion Bisphenol A was found to be a promoter specifically to proliferate the human UL cells by activating the transcription and translation of GPR30-EGFR and MAPK/ERK/c-fos signaling pathway members.

As an important branch of halogenated bisphenol compounds, the halogenated bisphenol monosubstituted-ether compounds have received a lot of attention in environmental health science because of their toxicity and variability. In this study, a synthetic method for bisphenol monosubstituted-ether byproduct libraries was developed. By using the versatile and efficient method, tetrachlorobisphenol A, tetrabromobisphenol A, and tetrabromobisphenol S monosubstituted alkyl-ether compounds were accessed in 39-82 % yield. Subsequently, the cytotoxicity of 27 compounds were screened using three different cell lines (HepG2, mouse primary astrocytes and Chang liver cells). Compound 2,6-dibromo-4-[3,5-dibromo-4-(2-hydroxyethoxy)benzene-1-sulfonyl]phenol was more toxic than other compounds in various cells, and the sensitivity of this compound to the normal hepatocytes and cancer cells was inconsistent. The compounds 2,6-dichloro-4-(2-{3,5-dichloro-4-[(prop-2-en-1-yl)oxy]phenyl}propan-2-yl)phenol and 2,6-dibromo-4-(2-{3,5-dibromo-4-[(prop-2-en-1-yl)oxy]phenyl}propan-2-yl)phenol were the most toxic to HepG2 cells, and most of the other compounds inhibited cell proliferation. Moreover, typical compounds were also reproductive and developmental toxic to zebrafish embryos at different concentrations. The synthetic byproduct libraries could be used as pure standard compounds and applied in research on environmental behavior and the transformation of halogenated flame retardants.

Human exposure to bisphenol compounds (BPs) has been implicated in the development of several chronic diseases. Instead of exploiting the traditional methods for determination of BPs, this work confirms that the human estrogen receptor α ligand binding domain (hERα-LBD) is a powerful recognition element that can be used to monitor multi-residue of BPs in urine samples by fluorescence polarization (FP) assay. Test parameters were optimized for the best performance. Under the optimal conditions, the IC50 values of BPs are in the range of 0.04-1.61 μg mL-1 . Recovery experiments were then performed to assess the accuracy and precision of the established method. The results detected by FP assay show good agreements with that of liquid chromatography-tandem mass spectrometry method with a fit of R2 = 0.9372 and 0.9640 for BPE and BPAP, respectively. A computational methodology, ligand-based pharmacophore model, was also employed to further explore the broad-specific of tested compounds. It was found that the two hydrogen bond acceptor features and one hydrophobic aliphatic feature were essential for the corresponding cross-reactivity results from the FP assay. All these results suggest that the established method can be successfully applied to monitor the occurrence of BPs in urine.

Because of increasing concerns about its toxic effects, bisphenol A (BPA) has been gradually replaced in industrial applications by analogs such as bisphenol S (BPS). Few comparative toxicity evaluations of bisphenol analogs have been done. In the present study, 72-h exposure in L1 larvae of the model animal Caenorhabditis elegans was used to evaluate low-concentration BPS toxicity. Multiple indicators at the physiological, biochemical, and molecular levels were tested. At the physiological level, BPS exposure resulted in significantly negative effects at treatments >1 µM, with head thrash being the most sensitive endpoint. At the biochemical level, BPS exposure induced no significant oxidative stress, but significantly increased apoptosis at 1 µM. At the molecular level, BPS exposure induced small but significant variations in most stress-related gene expressions at all doses. In addition, the transgenic nematode TJ375 cell line with the green fluorescent protein-based reporter hsp-16.2 was used to determine stress responses; it was found that TJ375 was not sensitive to BPS exposure. Compared with the effects of BPA shown in our previous 2016 study, the overall results showed that BPS was less noxious to C. elegans than BPA. These toxicity data for BPS could provide a foundation to evaluate the comparative toxicity of BPA alternatives. Environ Toxicol Chem 2018;37:2560-2565. © 2018 SETAC.

In this study, new bio-based magnetic molecularly imprinted polymer nanoparticles (∼23 nm) were synthesized from keratin extracted from chicken feathers and methacrylate-functionalized Fe3 O4 nanoparticles for its potential application in separation and removal of bisphenol A from water. The prepared magnetic molecularly imprinted polymer was characterized by Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy, thermogravimetric analysis, alternative gradient field magnetometry, and energy-dispersive X-ray spectroscopy. The sorption of bisphenol A was investigated by changing the influencing factors such as pH, immersion time, Fe3 O4 nanoparticles dosage, and the initial concentration of bisphenol A. Results illustrated that sorption was very fast and efficient (Qm = 600 mg/g) having a removal efficiency of ∼98% in 40 min of immersion. The adsorption process showed better conformity with the Weber-Morris kinetics and the Freundlich isotherm model. The selectivity of bisphenol A by adsorbent was checked in the presence of hydroquinone, phenol, tetrabromobisphenol, and 4,4'-biphenol as interferences.

Microwave- and ultrasound-assisted methods based on a quick, easy, cheap, effective, rugged, and safe sample preparation approach followed by high-performance liquid chromatography with tandem mass spectrometry were developed for the simultaneous determination of eight bisphenol analogues in serum and sediment. The developed methods provided satisfactory extraction efficiency for the energy provided by microwaves and ultrasound. Compositions of commercial sorbents (primary secondary amine, MgSO4 , octadecyl-modified silica, and graphitized carbon black) were evaluated. The ultrasound-assisted method was suited for serum using primary secondary amine, MgSO4 , and octadecyl-modified silica as sorbents and a mixture of hexane and ethyl acetate as extraction solvent. The microwave-assisted method worked better for sediment with tetrahydrofuran and methanol as solvents and primary secondary amine, MgSO4 , octadecyl-modified silica, and graphitized carbon black as sorbents. Other experimental parameters, such as extraction temperature and time, were also optimized. The inter- and intraday relative standard deviations ranged from 2.7 to 5.5%. The limits of detection were between 0.1 and 1.0 ng/mL for serum and between 0.1 and 0.5 ng/g dry weight for sediment. The proposed methods were successfully applied to seven sediment and 20 human serum samples. The results showed that the developed methods were practical for the analysis and biomonitoring of bisphenols in sera and sediment.

Two new polybenzoxazine copolymers were synthesized by polymerizing conventional benzoxazine monomer with varying weight percentage of tetraphenylimidazole and diphenylquinoline. The tetrasubstituted imidazole was synthesized through Debus-Radziszewski imidazole synthesis method, and quinoline derivative was synthesized through Friedlander quinoline synthesis, and their structure was confirmed through FTIR, 1HNMR, and MASS spectral analysis. New polybenzoxazine copolymers were synthesized by polymerizing conventional benzoxazine monomer with varying weight percentage of (10, 20, and 30%) of phenolic tetraphenylimidazole and diphenylquinoline. The polybenzoxazines cocured with 10, 20, and 30 wt% of imidazole derivative showed a band gap of 2.27, 2.08, and 2.2 eV, respectively, and the quinoline derivative incorporated at 10, 20, and 30 wt% in to polybenzoxazines exhibited a band gap of 2.26, 2.3, and 2.03 eV, respectively. The polybenzoxazines cocured with phenolic imidazoles and quinolines have high glass transition and thermal degradation stability in addition to significant improvement in optical and electrochemical properties than that of conventional bisphenol-based polybenzoxazines.

In this work, we describe the SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph3P=N-PPh3]+[HF2]− as the catalyst. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, we were able to achieve a remarkable diversity of monomeric building blocks by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of side chain functionalities in >99% conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry based post-polymerization modification.

A renewable bisepoxide, SYR-EPO, was prepared from syringaresinol, a naturally occurring bisphenol deriving from sinapic acid, by using a chemo-enzymatic synthetic pathway. Estrogenic activity tests revealed no endocrine disruption for syringaresinol. Its glycidylation afforded SYR-EPO with excellent yield and purity. This biobased, safe epoxy precursor was then cured with conventional and renewable diamines for the preparation of epoxy-amine resins. The resulting thermosets were thermally and mechanically characterized. Thermal analyses of these new resins showed excellent thermal stabilities (T-d5%=279-309 degrees C) and T-g ranging from 73 to 126 degrees C, almost reaching the properties of those obtained with the diglycidylether of bisphenol A (DGEBA), extensively used in the polymer industry (T-d5%= 319 degrees C and T-g = 150 degrees C for DGEBA/isophorone diamine resins). Degradation studies in NaOH and HCl aqueous solutions also highlighted the robustness of the syringaresinol-based resins, similar to bisphenol A (BPA). All these results undoubtedly confirmed the potential of syringaresinol as a greener and safer substitute for BPA

A novel nanocomposite of molecularly imprinted polymers and graphene sheets was fabricated and used to obtain a highly conductive acetylene black paste electrode with high conductivity for the detection of bisphenol A. The two-dimensional structure and the chemical functionality of graphene provide an excellent surface for the enhancement of the sensitivity of the electrochemical sensor and the specificity of molecularly imprinted polymers to improve detection of bisphenol A. The synergistic effect between graphene and molecularly imprinted polymers confers the nanocomposite with superior conductivity, broadened effective surface area and outstanding electrochemical performance. Factors affecting the performance of the imprinted sensor such as molecularly imprinted polymers concentration, foster time and scan rate are discussed. The sensor successfully detects bisphenol A with a wide linear range of 3.21 × 10-10 to 2.8 × 10-1 g/L (R = 0.995) and a detection limit of 9.63 × 10-11 g/L. The fabricated sensor also possessed high selectivity and stability and exhibits potential for environmental detection of contaminants and food safety inspection.

In the current study, we investigated poly-2-oxazolidones containing one of four different diglycidyl ethers carrying different bulky bisphenol centers. With increasing steric hindrance of the bisphenol-based diepoxide from bisphenol F to bisphenol A, Z and TMC, the glass transition temperature (Tg) increased markedly from 156 to 211 °C, whereas the plateau modulus of the polymer, i.e. the chain flexibility as determined from rheological characterization, remained almost unchanged. This study demonstrates the general feasibility of the chemical design of poly-2-oxazolidones as an amorphous high-performance thermoplastic. © 2016 Society of Chemical Industry

Nanocavity structures provide important functions of ion or molecular inclusions for chemical sensing, molecular recognition, and selective chemical extraction. Architecture of surface nanocavity structures of organic compounds on inorganic semiconductor surfaces is an interesting subject for exploring novel functional nanostructures. In this communication, we demonstrate the formation of a surface nanocavity structure of bisphenol P on a wide-band-gap semiconductor titanium dioxide (TiO2). The coordination of the two phenol moieties in bisphenol P with surfaces Ti atoms on TiO2 leads to the formation of the organic-semiconductor nanocavity structure. In addition, the nanocavity structure shows interfacial charge-transfer (ICT) transitions in the visible region. The ICT transitions change the electric-field distribution inside the nanocavity, suggesting the possibility of optically responsive inclusion functions. Our work reveals a way toward a novel type of functional nanocavity structures.

The objective of this work was to propose a novel low migration additive (i.e. a phosphine) to overcome the oxygen inhibition in a camphorquinone (CQ) base photoinitiating system for the polymerization of methacrylates (e.g. a bisphenol A-glycidyl methacrylate (Bis-GMA)/triethyleneglycol dimethacrylate (TEGDMA) blend (70%/30% w/w)) upon exposure to a commercial blue light emitting diode centred at 477 nm. CQ/amine/phosphine derivative or CQ/amine/iodonium salt/phosphine derivative combinations were studied. Real-time Fourier transform IR and photo-DSC experiments were used to monitor the polymerization profiles. Remarkably, it was found that the addition of the new phosphine derivative to CQ/amine or CQ/amine/iodonium salt noticeably improved the rate of polymerization and the final conversion in air. A low migration was found for this additive as shown by HPLC experiments in agreement with a copolymerizable behaviour. No additional yellowing of the film was observed. Electron spin resonance spectrometry was used to detect the produced radicals. The overall chemical mechanisms are investigated and discussed. © 2016 Society of Chemical Industry

Rationale Bisphenol A and its alternatives are widely used in common consumer products and are known as environmental endocrine disrupting chemicals. Five bisphenol analogues, namely, tetrabromobisphenol A (TBBPA), tetrachlorobisphenol A (TCBPA), 4,4′-sulfonyldiphenol (BPS), bisphenol A (BPA) and 4,4′-hexafluoroisopropylidenediphenol (BPAF), were selected to study their interactions with serum albumins, aiming at a better understanding of the toxicological mechanisms of bisphenol compounds. Methods The interactions between human and bovine serum albumins (HSA and BSA) with these five compounds were investigated by electrospray ionization mass spectrometry (ESI-MS). Fluorescence spectroscopy and molecular docking confirmed the ESI-MS observations and provided complementary information with respect to thermodynamic properties and binding modes. Results TBBPA showed the highest binding ability with HSA and BSA, followed by TBBPA and BPS, whereas BPA and BPAF exhibited little or no binding with these serum albumins. The calculated thermodynamic parameters suggested that hydrogen bonds and electrostatic forces played important roles for these interactions. Binding energies of TBBPA, TCBPA, and BPS calculated by molecular docking were −35.18, −34.39, and −25.89 kJ mol−1, respectively, in good agreement with ESI-MS measurements. Conclusions The results of this study showed that halogenated substituents on the phenolic rings of bisphenol could enhance the binding ability with serum albumins. This work could provide useful information for further research on the relationship between molecular structures and toxicities of bisphenols. Copyright © 2016 John Wiley & Sons, Ltd.

The developing brain is remarkably malleable as neural circuits are formed and these circuits are strongly dependent on hormones for their development. For those reasons, the brain is very vulnerable to the effects of endocrine-disrupting chemicals (EDCs) during critical periods of development. This review focuses on three ubiquitous endocrine disruptors that are known to disrupt the thyroid function and are associated with neurobehavioral deficits: polychlorinated biphenyls, polybrominated diphenyl ethers, and bisphenol A. The human and rodent data suggesting effects of those EDCs on memory, cognition, and social behavior are discussed. Their mechanisms of action go beyond relative hypothyroidism with effects on neurotransmitter release and calcium signaling.

The dummy molecularly imprinted polymers were prepared by Pickering emulsion polymerization. 4,4'-(1-Phenylethylidene) bisphenol was selected as the dummy template to avoid the leakage of the target bisphenols. The microsphere particles were characterized by scanning electron microscopy and nitrogen adsorption-desorption measurements, demonstrating that the regular-shaped and medium-sized particles (40-70 μm) were obtained with a specific surface area of 355.759 m(2) /g and a total pore volume of 0.561 cm(3) /g. The molecular imprinting properties of the particles were evaluated by static adsorption and chromatographic evaluation experiments. The association constant and maximum adsorption amount of bisphenol A were 0.115 mmol/L and 3.327 μmol/g using Scatchard analysis. The microsphere particles were then used as a solid-phase extraction sorbent for selective extraction of seven bisphenols. The method of dummy molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography and diode array detection was successfully established for the extraction and determination of seven bisphenols from environmental sediment samples with method detection limits of 0.6-1.1 ng/g. Good recoveries (75.5-105.2%) for sediment samples at two spiking levels (500 and 250 ng/g) and reproducibility (RSDs < 7.7%, n = 3) were obtained.

Polyether polyols based on bisphenol-S were prepared by alkoxylation and compared with analogs based on bisphenol-A, as well as standard aromatic polyester, and polyether polyols for viscosity and temperature stability. Thermo-oxidative stability was determined by thermo-gravimetric analysis, pyrolysis gas chromatography/mass spectroscopy, and evolved gas analysis mass spectroscopy. Incorporation of the sulfone moiety was found to dramatically improve the thermo-oxidative stability of the neat polyol. Significant char formation was observed with gas phase evolution of flame retardant SO2 and aromatic sulfone only apparent at about 600 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2102–2108

The potentially adverse health implications of bisphenol A (BPA) have led to increasing use of alternative bisphenols (BPs). However, little is known about the toxicity of alternative BPs. In this study, the cytotoxicity, genotoxicity, intracellular ROS formation, and Ca2+ fluctuation effects of BPs on MCF-7 cells were evaluated. At the same time, the estrogenic and thyroidal hormone effect potentials of six BPs were also evaluated using two-hybrid yeast bioassay. The results showed that most BPs at 0.01-1 μM significantly increased cell viability in MCF-7 cells and at higher exposure concentrations of 25-100 μM, they caused a significant decrease of cell viability. At the same time, these BPs also at 25-100 μM significantly increased LDH release of MCF-7 cells. In addition, several BPs at 10-50 μM resulted in a significantly concentration-depended increase in DNA-damaging effect on MCF-7 cells and elevated ROS production. Most BPs at 0.0001-10 μM significantly increased intracellular Ca2+ level. These results showed that bisphenol AF (BPAF) and thiodiphenol (TDP) exerted cell biological effect, estrogenic, and thyroidal effect potentials greater than those of BPA. The cytotoxicity and endocrine disrupting effects of other BPs are similar to or slightly lower than those of BPA. Therefore, as potential alternatives to BPA, endocrine disrupting effects and potential health harm of alternative BPs to human can also not be ignored. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 278-289, 2017.

K-Ras4B is a small GTPase that belongs to the Ras superfamily of guanine nucleotide-binding proteins. GTPases function as molecular switches in cells and are key players in intracellular signalling. Ras has been identified as an oncogene and is mutated in more than 20% of human cancers. Here, we report that Bisphenol S binds into a binding pocket of K-Ras4B previously identified for various low molecular weight compounds. Our results advocate for more comprehensive safety studies on the toxicity of Bisphenol S, as it is frequently used for Bisphenol A-free food containers.

A series of acrylate-based shape-memory materials are synthesized from bisphenol A diacrylate monomers as crosslinking agents. Networks are synthesized by keeping constant the content of bisphenol A-based crosslinking agent and systematically varying the content ratio of different monofunctional chain builder monomers. The implications of the structure of bisphenol A-based monomers and the chemical structure and content of monofunctional monomers on thermomechanical properties are discussed. Thermomechanical properties are analyzed using dynamic mechanical analyses and mechanical properties are studied at room temperature and at the onset of the glass transition temperature. Shape-memory performances under isothermal and transient temperature conditions are also carried out. Tensile tests show excellent values of stress at break up to 45 and 15 MPa at room and high temperature, respectively. The measurements show excellent shape recovery and shape fixity ratios, ˜95% and 97%, respectively. These materials also show very high recovery velocities under transient temperature conditions, up to 24% min-1, and very short recovery times, up to 1.5 s, under isothermal conditions in a water bath. The results confirm that networks synthesized from bisphenol A crosslinkers are promising shape-memory materials.

Tamoxifen is a widely used anticancer drug with both an estrogen agonist and antagonist effect. This study focused on its endocrine disrupting effect, and overall environmental significance. Zebrafish embryos were exposed to different concentrations (0.5, 5, 50 and 500 µg l(-1) ) of tamoxifen for 96 h. The results showed a complex effect of tamoxifen on zebrafish embryo development. For the 500 µg l(-1) exposure group, the heart rate was decreased by 20% and mild defects in caudal fin and skin were observed. Expressions of a series of genes related to endocrine and morphological changes were subsequently tested through quantitative real-time polymerase chain reaction. Bisphenol A as a known estrogen was also tested as an endocrine-related comparison. Among the expression of endocrine-related genes, esr1, ar, cyp19a1b, hsd3b1 and ugt1a1 were all increased by tamoxifen exposure, similar to bisphenol A. The cyp19a1b is a key gene that controls estrogen synthesis. Exposure to 0.5, 5, 50 and 500 µg l(-1) of tamoxifen caused upregulation of cyp19a1b expression to 152%, 568%, 953% and 2024% compared to controls, higher than the effects from the same concentrations of bisphenol A treatment, yet vtg1 was suppressed by 24% from exposure to 500 µg l(-1) tamoxifen. The expression of metabolic-related genes such as cyp1a, cyp1c2, cyp3a65, gpx1a, gstp1, gsr and genes related to observed morphological changes such as krt17 were also found to be upregulated by high concentrations of tamoxifen. These findings indicated the potential environmental effect of tamoxifen on teleost early development. Copyright © 2015 John Wiley & Sons, Ltd.

Random copolycyanurates with a low number of amide units in the main chain have been developed as a candidate of dismantlable adhesives based on the rapid decrease of the molecular weights during the rearrangement to polyisocyanurates by a thermal treatment. The random copolycyanurates were prepared by the phase-transfer-catalyzed polycondensation of 2,4-dichloro-6-methoxy-1,3,5-triazine with bisphenol A and a new bisphenol containing an amide unit in the presence of tetrabutylammonium bromide. They exhibited an excellent adhesive property for the silicon and copper deposited on the silicon substrate after the high thermal treatment of 240 °C under 0.6 MPa compression, and the die shear strengths of these polymers dramatically decreased at 260 °C for 1 h. Random copolycyanurates containing the amide unit are shown to be promising materials for dismantlable adhesion. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1153–1158

Molecularly imprinted polymers are important tools for the design of sensors and other molecular recognition based analytical systems. In this paper the development of a photoelectrochemical sensor for selective bisphenol determination is reported. The sensor is based on a glass/ZnO/MIP‐Ppy structure consisting of glass modified by a ZnO layer (glass/ZnO), which is functionalized by molecularly imprinted conducting polymer polypyrrole (MIP‐Ppy). The sensitivity of the sensor to bisphenol is in the range of 0.7–12.5 µm. Selectivity tests to other bisphenolic compounds are performed. Some aspects of a photoinduced response mechanism in glass/ZnO/MIP‐Ppy nanostructures are predicted and discussed.

A new hyperbranched polymer (HBP) with a flexible aromatic skeleton and terminal epoxy groups was synthesized to improve the toughness of diglycidyl ether of bisphenol A. The HBP was characterized using nuclear magnetic resonance, Fourier transfer infrared spectroscopy and gel permeation chromatography. The effect of HBP on the thermomechanical and mechanical properties of modified epoxy systems was studied. For evaluating the efficiency of the modified epoxy systems, composite samples using glass fiber cloth were molded and tested. Using dynamic mechanical analysis, a slight reduction in glass transition temperature (Tg) with increasing HBP content was observed. Analysis of fracture surfaces revealed a possible effect of HBP as a toughener and showed no phase separation in the modified resin systems. The results showed that the addition of 15 phr HBP maximized the toughness of the modified resin systems with 215 and 40% increases in impact and flexural strengths, respectively. Tg and heat resistance of cured modified resin systems decreased slightly with an increase in HBP content and, at 15 phr HBP, only a 2.6% decrease in thermomechanical properties was observed. Meanwhile, a molded composite with HBP showed improved mechanical properties and retention rate at 150 °C as compared to that made with neat resin. © 2015 Society of Chemical Industry

Lignosulfonic acid, a byproduct of the paper industry, was demonstrated to be an efficient and green catalyst in water for the stoichiometric condensation of creosol with formaldehyde to synthesize lignin-derived renewable bisphenols. the distribution and structures of the products were confirmed by (hnmr)-h-1, (cnmr)-c-13, and ftir spectroscopy and x-ray analysis; furthermore, a possible reaction mechanism was proposed. a polycarbonate was prepared from the bisphenol product and characterized as a model application, and thermogravimetric analysis (tga) showed that decomposition occurred in a single stage with the maximum rate of degradation at approximately 420 degrees c. differential scanning calorimetry (dsc) analysis showed that the glass transition temperature and melting peak of the polycarbonate were approximately 122 and 314 degrees c, respectively. the environmentally friendly characteristics of this study are featured by the integrated utilization of a biorenewable feedstock, a green biomacromolecule catalyst, and a green solvent for the preparation of valuable biochemicals and materials.

A diallyl-containing bisphenol, 1,1-bis(3-allyl-4-hydroxyphenyl)-1-(6-oxido-6H -dibenzo [c,e][1,2] oxaphosphorin-6-yl) ethane (1), was prepared by a two-step procedure. Then, a diallyl-containing diamine, 1,1-bis(3-allyl-4-(4-aminophenoxy)-phenyl)-1-(6-oxido-6H-dibenzo [c,e][1,2] oxaphosphorin-6-yl)ethane (3), was prepared from the nucleophilic substitution of (1) with 4-fluoronitrobenzene, followed by the reduction by Fe/HCl. A flexible polyimide (4) with curable diallyl linkages was prepared from the condensation of (3) and 4,4′-oxydiphthalic anhydride in m-cresol in the presence of isoquinoline. Curing polyimide (4) at 300 °C leads to thermosetting polyimide (5). We discussed the amounts of allyl group on Tg, coefficient of thermal expansion, and thermal stability of thermosetting polyimides, and found that thermal properties and dimensional stability of thermosetting polyimides increase with the amounts of cured allyl moieties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 513–520

A simple ultrahigh-performance liquid chromatography (UHPLC) tandem mass spectrometric method for the identification and quantification of two photoinitiators 4-methylbenzophenone and 2-ethylhexyl-4-dimethylaminobenzoate; nine plasticizers including di(2-ethylhexyl) adipate and diisobutyl adipate; three primary aromatic amines 4-aminobiphenyl, 4-amino-2′,3-dimethylazobenzene and bis-(4-aminophenyl) methane and six bisphenols bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A (BPA), bisphenol B (BPB), bisphenol E (BPE) and bisphenol F (BPF) in food contact materials has been developed. The chromatographic conditions, pre-treatment methods and matrix effects were studied and optimized. For the determination of the four bisphenols, BPA, BPB, BPE and BPF, the UHPLC method employed a mobile phase of aqueous ammonia and methanol in binary gradient mode, and measurement was based on a triple quadrupole mass spectrometer equipped with an electrospray ionization (ESI) source operating in negative ion mode. The remaining chemicals were determined using the ESI source in positive ion mode and using the [M + NH4]+ or [M + H]+ adducts as precursor ions for tandem mass spectrometry. The calibration graphs were linear with correlation coefficients of above 0.995. Detection limits for the method were in the range of 1–16 µg/kg. Analyte recovery values were in the range of 70–114%, and relative standard deviations were 1–14%. Under optimized conditions, the chromatographic separation was performed in 12 min. The validation data indicated that the method was effective for the determination of the four classes of hazardous chemicals in plastic packaging materials or in can lacquers. The optimized method was successfully applied to trace analysis of commercially available food contact materials. Copyright © 2014 John Wiley & Sons, Ltd.

A method for the rapid pretreatment and determination of bisphenol A in water samples based on vortex-assisted liquid-liquid microextraction followed by high-performance liquid chromatography with fluorescence detection was proposed in this paper. A simple apparatus consisting of a test tube and a cut-glass dropper was designed and applied to collect the floating extraction drop in liquid-liquid microextraction when low-density organic solvent was used as the extraction solvent. Solidification and melting steps that were tedious but necessary once the low-density organic solvent used as extraction solvent could be avoided by using this apparatus. Bisphenol A was selected as model pollutant and vortex-assisted liquid-liquid microextraction was employed to investigate the usefulness of the apparatus. High-performance liquid chromatography with fluorescence detection was selected as the analytical tool for the detection of bisphenol A. The linear dynamic range was from 0.10 to 100 μg/L for bisphenol A, with good squared regression coefficient (r(2) = 0.9990). The relative standard deviation (n = 7) was 4.7% and the limit of detection was 0.02 μg/L. The proposed method had been applied to the determination of bisphenol A in natural water samples and was shown to be economical, fast, and convenient.

Background and Purpose Triphenylethylene (TPE)-like compounds were the first agents to be used in the treatment of metastatic breast cancer in postmenopausal women. Although structurally related to the anti-oestrogen, 4-hydroxytamoxifen, TPEs possess oestrogenic properties in fully oestrogenized breast cancer cells but do not induce apoptosis with short-term treatment in long-term oestrogen-deprived breast cancer cells. This study determined the differential effects of bisphenol, a TPE, on growth and apoptosis based on the modulation of the shape of the ligand–oestrogen receptor complex. Experimental Approach Apoptotic flow cytometric studies were used to evaluate apoptosis over time. Proliferation of the breast cancer cells was assessed using DNA quantification and cell cycle analysis. Real-time PCR was performed to quantify mRNA levels of apoptotic genes. Regulation of cell cycle and apoptotic genes was determined using PCR-based arrays. Key Results Bisphenol induced an up-regulation of cell cycle genes similar to those induced by 17β oestradiol (E2). Unlike the changes induced by E2 that occur after 24 h, the apoptosis evoked by bisphenol occurred after 4 days, with quantifiable apoptotic changes noted at 6 days. A prolonged up-regulation of endoplasmic reticulum stress and inflammatory stress response genes was observed with subsequent activation of apoptosis-related genes in the second week of treatment with bisphenol. Conclusions and Implications The bisphenol: ERα complex induces delayed biological effects on the growth and apoptosis of breast cancer cells. Both the shape of the complex and the duration of treatment control the initiation of apoptosis.

We report the thermal, mechanical, and diffusion properties of bisphenol E based polycyanurate nanocomposites with three forms of graphene derived from sequential processing of the same carbon nanostructure. Edge-functionalized graphene nanoplatelets (GNP) were converted to graphene oxide (GO), then heated to produce thermally reduced graphene oxide (TRGO). All three reinforcements were individually mixed with the dicyanate ester of bisphenol E (LECy) at low loading levels and cured to form polycyanurate nanocomposites. GNP, with very low oxygen functionality, was incompatible with the cyanate ester, while the highly oxidized GO formed well-dispersed (though not exfoliated) nanocomposites, with the TRGO forming a good dispersion on mixing but phase separating during cure. The addition of GO, and, to a lesser extent, TRGO, resulted in improved mechanical properties, particularly fracture toughness, with the addition of TRGO having a modestly negative effect on the glass transition temperature. Surprisingly, neither GO nor TRGO addition was effective at slowing down the diffusion of water in the polycyanurate, with the addition of both resulting in increased equilibrium moisture uptake. It thus appears that the trade-off between dispersion and the required level of oxygen functionality acts in a manner to frustrate attempts at minimizing the permeation of water by addition of graphene-based reinforcements.

In silico–based model predictions, originating from structural and mechanistic (e.g., transport, bioavailability, reactivity, and binding potential) profiling, were compared against laboratory-derived data to estimate the bioaccumulation potential in earthworms of 2 organic substances (1 neutral, 1 ionogenic) known to primarily partition to soil. Two compounds representative of specific classes of chemicals were evaluated: a nonchlorinated bisphenol containing an –OH group (4,4′-methylenebis[2,6-di-tert-butylphenol] [Binox]), and an ionogenic xanthene dye (2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxy-, disodium salt [Phloxine B]). Soil bioaccumulation studies were conducted using Eisenia andrei and 2 field-collected soils (a clay loam and a sandy soil). In general, the in silico structural and mechanistic profiling was consistent with the observed soil bioaccumulation tests. Binox did not bioaccumulate to a significant extent in E. andrei in either soil type; however, Phloxine B not only accumulated within tissue, but was not depurated from the earthworms during the course of the elimination phase. Structural and mechanistic profiling demonstrated the binding and reactivity potential of Phloxine B; this would not be accounted for using traditional bioaccumulation metrics, which are founded on passive-based diffusion mechanisms. This illustrates the importance of profiling for reactive ionogenic substances; even limited bioavailability combined with reactivity can result in exposures to a hazardous substance not predictable by traditional in silico modeling methods. Environ Toxicol Chem 2014;33:308–316. © 2013 SETAC

A carbene-catalyzed desymmetrization of prochiral bisphenol compounds bearing remote P-stereogenic centers is disclosed. The catalytic reactions can be performed on gram scales with 1 mol % N-heterocyclic carbene (NHC) catalyst, providing efficient access to enantiomerically enriched P-stereogenic phosphinates. The chiral phosphinates prepared with our method can find widespread applications as asymmetric organic catalysts and ligands.

Sulfur-containing allyl ester, which reacts with diallyl phthalate (DAP) resin to have allyl groups, was synthesized by the reaction of allyl phthalic acid with bisphenol having sulfur atoms. The sulfur-containing allyl ester compound was blended with DAP resin to improve the adhesive properties to copper. By modification with sulfur-containing allyl ester compound, the T-peel adhesive strength and the lap shear adhesive strength to copper was improved. In particular, the adhesive strength was greatly improved when the resin was modified with the allyl ester compound having a disulfide bond (−S−S−) (DADS). It is concluded that this result is due to the improvement of the interfacial adhesive strength because the sulfur atom was found to be located in the surface of the copper by Fourier transform infrared (FTIR) analysis. The glass transition temperature (Tg) and the thermal decomposition temperature (Td) of the cured DAP resin modified with DADS slightly decreased with increasing concentration of DADS. The lowering of Tg is because the crosslinking density of the DAP resin modified with DADS is smaller than that of DAP resin. Moreover, from thermogravimetric analysis, the lowering of Td of the DAP resin modified with DADS is because DADS is likely to pyrolyze. © 2013 Society of Chemical Industry