Bisphenol Derivatives Research Articles

Removal of bisphenol derivatives through quinone oxidation by polyphenol oxidase and subsequent quinone adsorption on chitosan in the heterogeneous system

In this study, the combined use of a biopolymer chitosan and an oxidoreductase polyphenol oxidase (PPO) was systematically investigated for the removal of bisphenol derivatives from aqueous medium. The process parameters, such as the pH value, temperature, and PPO concentration, were estimated to conduct the enzymatic quinone oxidation of bisphenol derivatives by as little enzyme as possible. Bisphenol derivatives effectively underwent PPO-catalysed quinone oxidation without H2O2 unlike other oxidoreductases, such as peroxidase and tyrosinase, and the optimum conditions were determined to be pH 7.0 and 40°C for bisphenol B, bisphenol E, bisphenol O, and bisphenol Z; pH 7.0 and 30°C for bisphenol C and bisphenol F; and pH 8.0 and 40°C for bisphenol T. They were completely removed through adsorption of enzymatically generated quinone derivatives on chitosan beads or chitosan powders. Quinone adsorption on chitosan beads or chitosan powders in the heterogeneous system was found to be a more effective procedure than generation of aggregates in the homogeneous system with chitosan solution. The removal time was shortened by increasing the amount of chitosan beads or decreasing the size of the chitosan powders.

Adamantane-based oxacyclophanes containing pyrazines: synthesis, crystal structure, and self-assembly behavior.

Two adamantane-based oxacyclophanes were synthesized by the SNAr reaction of bis-phenol derivatives based on adamantane with 2,6-dichloropyrazine. Their crystal structures had distorted or twisted 1,3-alternate conformations. The oxacyclophanes indicated no formation of spherical aggregates in acetone. However, addition of water into the solution caused the generation of hollow spherical aggregates with a multilayer membrane. Over time, the hollow spheres were induced into fibrous and network assemblies, which were eventually transformed into single crystals.

Phase transition thermodynamics of bisphenols.

Herein we have studied, presented, and analyzed the phase equilibria thermodynamics of a bisphenols (BP-A, BP-E, BP-F, BP-AP, and BP-S) series. In particular, the heat capacities, melting temperatures, and vapor pressures at different temperatures as well as the standard enthalpies, entropies, and Gibbs energies of phase transition (fusion and sublimation) were experimentally determined. Also, we have presented the phase diagrams of each bisphenol derivative and investigated the key parameters related to the thermodynamic stability of the condensed phases. When all the bisphenol derivatives are compared at the same conditions, solids BP-AP and BP-S present lower volatilities (higher Gibbs energy of sublimation) and high melting temperatures due to the higher stability of their solid phases. Solids BP-A and BP-F present similar stabilities, whereas BP-E is more volatile. The introduction of -CH3 groups in BP-F (giving BP-E and BP-A) leads an entropic differentiation in the solid phase, whereas in the isotropic liquids the enthalpic and entropic differentiations are negligible.

Ionic liquid-initiated polymerization of epoxides: A useful strategy for the preparation of Pd-doped polyether catalysts

Palladium compounds (Pd(OAc)2 and Pd(acac)2) were dissolved in commercially available epoxy resins (glycidyl derivatives of bisphenol A and p-aminophenol) and the formulations were polymerized employing the ionic liquid 1-ethyl-2-methylimidazolium acetate (EMIM acetate) as polymerization initiator. Thus, palladium species could be incorporated in the network of the resulting polyether materials. Polymerization reactions were investigated by DSC and the curing behavior of different formulations was compared. High polymerization enthalpies were observed indicating high crosslinking in the materials. Accordingly, the materials exhibited high glass transition temperatures and thermogravimetric data revealed high thermal stability. Due to the good solubility of the palladium compounds in the epoxy resins, a widely homogeneous dispersion of palladium species in the polyether matrix could be realized. This was confirmed by SEM-EDX and TEM measurements. XPS measurements revealed that reduction of Pd(II) to Pd(0) species occurred during catalyst preparation and this was also proven by XRD. The materials were ground and successfully employed as catalysts for the hydrogenation of several alkenes under mild reaction conditions. High conversions and selectivities could be reached within a few hours at room temperature and moderate hydrogen pressure of 2.5bar. Palladium leaching from the catalysts to reaction solutions was investigated. To determine very low quantities, metal concentrations were enriched by removal of volatile components. Subsequent ICP-AES measurements revealed low palladium contents in the range of a few μg. These amounts correspond to values around 0.007% with respect to palladium originally loaded on the polymer. Catalyst recycling experiments were also carried out and it was shown that the catalysts can be employed in numerous consecutive reactions without any catalyst treatment and without loss of activity. Within a series of reactions, palladium leaching decreased while catalytic activity was not affected.

Examining the kinetics of the thermal polymerization of commercial aromatic bis‐benzoxazines

ABSTRACTThree commercial bis‐benzoxazine monomers based on the aniline derivatives of bisphenol A (BA‐a), bisphenol F (BF‐a), and 3,3′‐thiodiphenol (BT‐a) are examined using a variety of spectroscopic, chromatographic, and thermomechanical techniques. The kinetics of the polymerization of BA‐a were found to be well described using an autocatalytic model for which values of n = 1.39 and m = 2.49 were obtained for the early and later stages of reaction respectively (activation energy = 81–88 kJ/mol.). Following recrystallization the same monomer yielded values of n = 1.80, m = 0.92, and Ea = 94–97 kJ/mol. BF‐a and BT‐a were also found to be well described using an autocatalytic model for which values of n = m = 2.11 (BF‐a) and n = 2.10, m = 1.47 (BT‐a) were obtained for the early and later stages of reaction (activation energy = 80–84 kJ/mol. for BF‐a and 88–95 kJ/mol. for BT‐a). The kinetic data are compared with parallel studies involving chemically initiated benzoxazine monomers. Molecular simulation is used to examine the rotational freedom of the central bridging units and this is related to the degree of conversion achieved. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2068–2081

Estrogen-related receptor γ is an in vivo receptor of bisphenol A.

Bisphenol A (BPA) is an endocrine disruptor that displays estrogenic activity. Several reports suggest that BPA may have estrogen receptor-independent effects. In zebrafish, 50 μM BPA exposure induces otic vesicle abnormalities, including otolith aggregation. The purpose of this study was to test if BPA action was mediated in vivo during zebrafish development by the orphan nuclear estrogen related receptor (ERR) γ. Combining pharmacological and functional approaches, we demonstrate that the zebrafish ERRγ mediates BPA-induced malformations in otoliths. Using different bisphenol derivatives, we show that different compounds can induce a similar otolith phenotype than BPA and that the binding affinity of these derivatives to the zebrafish ERRγ correlates with their ability to induce otolith malformations. Morpholino knockdown of ERRγ function suppresses the BPA effect on otoliths whereas overexpression of ERRγ led to a BPA-like otolith phenotype. Moreover, a subphenotypical dose of BPA (1 μM) combined with ERRγ overexpression led to a full-dose (50 μM) BPA otolith phenotype. We therefore conclude that ERRγ mediates the otic vesicle phenotype generated by BPA. Our results suggest that the range of pathways perturbed by this compound and its potential harmful effect are larger than expected.-Tohmé, M., Prud'homme, S. M., Boulahtouf, A., Samarut, E., Brunet, F., Bernard, L., Bourguet, W., Gibert, Y., Balaguer, P., Laudet, V. Estrogen-related receptor γ is an in vivo receptor of bisphenol A.

Adsorption Properties of Modified Banana Fiber to Transition Metal Ions

Several syntheses of metal ion adsorbents using modified banana fibers having Schiff bases were investigated. In addition, adsorption properties of a metal ion adsorbent were also evaluated. Alkalitreated (BF)-g-(glycidyl methacrylate)(BF-GMA) were synthesized. The Schiff base, 2-2'{iminobis[ethane-2,1-diylnitrilo(E)methylidine]}bisphenol derivative was synthesized by the reaction of diethylenetriamine and salicylaldehyde derivatives in methanol. The metal ion adsorbents were synthesized by the reaction of 2,2'-{iminobis-[ethane-2,1-diylnitrilo(E)methylidine]}bisphenol derivative, and BF-GMA. Where, C1: R=H, C2: R=Cl, C3: R=Br. The concentration of metal ion was measured by an inductively coupled plasma atomic emission spectroscope. Metal ion adsorption percentage (%) of BFGMA(C3) was higher than those of BF-GMA(C1) and BF-GMA(C2). Especially, adsorption property to Co2+ was higher than that to the other metal ions. This result suggests that the acid dissociation constant of BF-GMA(C3) is larger than that of BF-GMA(C1). Therefore, BF-GMA(C3) can be chelated with metal ions more easily than BF-GMA(C1) can be. These results show a definite feasibility of the use of banana fibers for the metal ion adsorbent.

Aliphatic Substitution of <i>o</i>-Carboranyl Phenols Enhances Estrogen Receptor Beta Selectivity

The two subtypes of estrogen receptor (ER), ERα and ERβ, differ greatly in expression pattern and biological functions, and ERβ-selective ligands candidates to treat immune-related disorders. ERβ-selective ligands have mostly been designed based the idea of introducing a substituent that interferes sterically with the ligand's interaction with Met421 to selectively decrease the affinity for ERα (the equivalent residue in ERβ is Ile373). Therefore, we designed and synthesized a series of carboranyl phenol derivatives bearing an aliphatic substituent as candidate ERβ-selective ligands. Introduction of a longer aliphatic substituent into the carboranyl moiety enhanced the ERβ selectivity of o-carboranyl phenol derivatives 4, but not m-carboranyl bisphenol derivatives 5. Compound 4c showed 7.4-fold ERβ selectivity in ER-binding assay and exhibited moderate estrogenic activity in cell proliferation assay using MCF-7 cell line.

Examining the Initiation of the Polymerization Mechanism and Network Development in Aromatic Polybenzoxazines

Three bis-benzoxazine monomers based on the aniline derivatives of bisphenol A (BA-a), bisphenol F (BF-a), and 3,3′-thiodiphenol (BT-a) are examined using a variety of spectroscopic, chromatographic, and thermomechanical techniques. The effect on the polymerization of the monomers is compared using two common compounds, 3,3′-thiodiphenol (TDP) and 3,3′-thiodipropionic acid (TDA), at a variety of loadings. It is found that the diacid has a greater effect on reducing the onset of polymerization and increasing cross-link density and Tg for a given benzoxazine. However, the addition of >5 wt % of the diacid had a detrimental effect on the cross-link density, Tg, and thermal stability of the polymer. The kinetics of the polymerization of BA-a were found to be well described using an autocatalytic model for which values of n = 1.64 and m = 2.31 were obtained for the early and later stages of reaction (activation energy = 81 kJ/mol). Following recrystallization the same monomer yielded values n = 1.89, m = 0.89, and Ea = 94 kJ/mol (confirming the influence of higher oligomers on reactivity). The choice of additive (in particular the magnitude of its pKa) appears to influence the nature of the network formation from a linear toward a more clusterlike growth mechanism.

PTSA-catalyzed condensation of xylenols and aldehydes under solvent-free conditions: One-pot synthesis of 9H-xanthene or bisphenol derivatives

Abstract A simple and efficient procedure for the synthesis of 9H-xanthene or bisphenol derivatives has been developed by one-pot condensation of xylenols with aromatic aldehydes in the presence of p-toluenesulfonic acid (pTSA) as a catalyst under solvent-free conditions at 100 °C. It is noteworthy that the condensation reaction of 3,5-xylenol with aldehydes produces 9H-xanthene derivatives, while the reaction with other xylenols leads to the corresponding bisphenol derivatives. Different types of aromatic aldehydes are used in the reaction and in every case the products were obtained in good to excellent yields. The structures of these compounds were established on the basis of IR, 1H NMR, 13C NMR and CHN data.

Development of silicon-containing bis-phenol derivatives as androgen receptor antagonists: Selectivity switching by C/Si exchange

We previously reported that bis-phenol derivatives, including LG190178 (3a), possess not only vitamin D receptor (VDR) agonistic activity, but also androgen receptor (AR) antagonistic activity. Here, we describe the design, synthesis and evaluation of silicon-containing bis-phenol derivatives, with the objective of obtaining increased selectivity toward VDR or AR. We found that replacement of the quaternary carbon in the bis-phenol skeleton with silicon increased AR-antagonistic activity and reduced VDR-agonistic activity, that is, the AR selectivity of the silicon-containing compounds was higher than that of corresponding carbon compounds. To our knowledge, this is the first report of nuclear receptor (NR) selectivity switching by sila-substitution (C/Si exchange). Among the compounds synthesized, AR-selective ligand (S,R)-3b exhibited more potent anti-androgenic activity (IC50=0.072μM) than hydroxyflutamide, a well-known androgen antagonist (IC50=1.4μM), in SC-3 cell proliferation assay. These results suggest that sila-substitution is a useful approach for structural development of selective AR ligands.

Phytoremediation of 4,4′-thiodiphenol (TDP) and other bisphenol derivatives by Portulaca oleracea cv.

4,4'-Thiodiphenol (TDP) is a bisphenol derivative, and there has been no report on TDP removal by any plants or pure bacterial cultures. The removal of TDP by Portulaca oleracea cv., a floricultural herbal plant, was examined with a hydroculture system, and 97% of TDP was removed after 4 days culture.

Photolysis and thermal active polymerization of bis (benzylidene) based benzoxazine monomers

A new class of photopolymerizable benzoxazine monomers has been developed, using photoactive bisphenol derivatives such as bis (4-hydroxybenzylidene)-4-phenyl cyclopentanone and bis (4-hydroxybenzylidene)-4-phenyl cyclohexanone, p-toludine and formaldehyde (37%). The structure of the benzoxazine monomers has been confirmed by Fourier Transform Infra Red spectroscopy (FTIR) and 1H and 13C Nuclear Magnetic Resonance spectroscopy (NMR). Upon photolysis with radiation of 365nm, the monomers undergo photolysis via [2π+2π] cyclo-addition reaction, which was confirmed by UV spectroscopy. After photolysis, the benzoxazine monomers were subsequently cured at 200°C for 2h. The photo irradiated cured products possessed enhanced glass transition temperature and thermal stability, with an increase in the photodimerization time.

Total Synthesis of Bauhinoxepin J: A Biologically Active Dibenzo[b,f]oxepin Isolated from Bauhinia purpurea

AbstractBauhinoxepin J possessing antimycobacterial, antimalarial, and tumor growth inhibitory activities was efficiently synthesized. The method involves crucial steps, including a coupling reaction of two aromatic moieties to construct the desired carbon framework, chemoselective phenol oxidation of a bisphenol derivative to establish a key cyclization precursor, and construction of a characteristic seven‐membered dihydrooxepin ring by internal cyclization to yield the target bauhinoxepin J.

Inhibition of human carbonic anhydrase isozymes I, II and VI with a series of bisphenol, methoxy and bromophenol compounds

Carbonic anhydrase inhibitors (CAI) are valuable molecules as they have several therapeutic applications, including anti-glaucoma activity. In this study, inhibition of three human carbonic anhydrase (hCA, EC 4.2.1.1) isozymes I, II and VI with a series of bisphenol and bromophenol derivatives was investigated. Molecular docking studies of a set of such inhibitors within CA I and II were also performed. KI values of the molecules 2–9 were in the range of 10.025–892.109 μM for hCA I, 1.437–59.107 μM for hCA II and 11.143–919.182 μM for hCA VI, respectively. Reported inhibitory activities of molecules 2–9 will assist in better understanding of structure-activity relationship studies of CAI.

Supramolecular Organic Frameworks of Brominated Bisphenol Derivatives with Organoamines

Reactions of two brominated bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), with various organoamines resulted in six supramolecular organic frameworks (SOFs), formulated as (TBBPF2–)2·(HPZ+)2·(H2PZ2+) (1), (TBBPF–)2·(H2PZ2+)·2H2O·2MeOH (2), (TBBPF)·(TBBPF–)·(HDABCO+)·H2O (3), (TBBPF)·(HMTA) (4), (TBBPA)·(HMTA) (5), and (TBBPA)3·(HMTA)3·H2O (6) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine). Compounds 1–6 were characterized by single-crystal and powder X-ray diffractions. The predominant driving forces in 1–6 are hydrogen bonds (H-bonds), by which the compounds assemble into supramolecular organic frameworks with versatile topological structures. Compound 1 contains TBBPF/PZ in a 2:3 ratio and exhibits 2D (two-dimensional) H-bonded supramolecular 44-sql layer structure built by the four-connected {H2PZ2+} moieties and {TBBPF2–}. Compound 2 shows a 2-fold interpenetrated 3D (three-dimensional) H-bonded networks comprised by TBBPF/...

ChemInform Abstract: Facile Synthesis of Stereoisomers of the Non‐Secosteroidal Ligand LG190178 and Their Evaluation Using the Mutant Vitamin D Receptor.

AbstractAll four diastereomers of the non‐secosteroidal ligand LG190178 are prepared by asymmetric reduction of bisphenol derivative (I) with chiral oxazaborolidine reagents followed by treatment with the corresponding glycidol derivatives, e.g. (III).

Assessment of thyroid hormone activity of halogenated bisphenol A using a yeast two-hybrid assay

The thyroid hormone agonist/antagonist activities of halogenated derivatives of bisphenol A (BPA) were assessed using a yeast two-hybrid assay incorporating the human thyroid hormone α (TR α), both with and without possible metabolic activation by rat liver S9 preparation. In the absence of the rat liver S9 preparation, 3,3′,5,5′-tetrabromobisphenol A (TBBPA), 3,3′,5,5′-tetrachlorobisphenol A (TCBPA), and 3,3′,5-trichlorobisphenol A (3,3′,5-triClBPA) exhibited agonist activity, whereas 3-chlorobisphenol A (3-ClBPA), 3,5-dichlorobisphenol A (3,5-diClBPA), 3,3′-dichlorobisphenol A (3,3′-diClBPA), and BPA did not. The activities of TBBPA and TCBPA increased markedly (7.6-fold and 3.1-fold, respectively) after their metabolic activation with the rat liver S9 preparation. TBBPA, TCBPA, and 3,3′,5-triClBPA inhibited the binding of triiodothyronine (T3) to TR α at 2 × 10 −5 M without rat liver S9 treatment and 4 × 10 −6 M with rat liver S9 treatment, demonstrating their T3 antagonist activity. These results revealed that metabolic activation by rat liver S9 significantly increased the agonist/antagonist potential of some halogenated BPAs.

Soybean peroxidase‐catalyzed treatment and removal of BPA and bisphenol derivatives from aqueous solutions

AbstractThe systematic studies were carried out to determine the optimum process parameters, such as the hydrogen peroxide (H2O2) concentration, concentration and molar mass of poly(ethylene glycol) (PEG) as an additive, pH value, temperature, and enzyme dose for treatment of bisphenol A (BPA) with soybean peroxidase (SBP). The SBP‐catalyzed treatment of BPA was effectively enhanced by adding PEG in the presence of H2O2. BPA was completely treated by SBP of 0.50 U/cm3 and water‐insoluble oligomers were generated. The optimum conditions for SBP‐catalyzed treatment of BPA at 0.3 mM were determined to be 0.3 mM of H2O2 and 0.10 mg/cm3 of PEG with molar mass of 1.0 × 104 g/mol in a pH 7.0 buffer at 30°C. A variety of bisphenol derivatives were completely or effectively treated by SBP under the optimum conditions determined for treatment of BPA, although the SBP dose was further increased as necessary for some of them. The aggregation of water‐insoluble oligomers generated was enhanced by decreasing the pH values of the solutions to 4.0 with HCl after the enzymatic treatment, and BPA and bisphenol derivatives were removed from aqueous solutions by filtering off the oligomer precipitates. © 2010 American Institute of Chemical Engineers Environ Prog, 2011

Sensitive determination of bisphenol A and bisphenol F in canned food using a solid-phase microextraction fibre coated with single-walled carbon nanotubes before GC/MS

A reliable and sensitive method for simultaneous determination of bisphenol A (BPA) and bisphenol F (BPF) in canned food by gas chromatography-mass spectrometry (GC/MS) is described after extraction and pre-concentration by a new solid-phase microextraction (SPME) adsorbent. The potential of single-walled carbon nanotubes (SWCNTs) as SPME adsorbent for the pre-concentration of environmental contaminants has been investigated in recent years. This work was carried out to investigate the feasibility of SWCNTs as a headspace SPME adsorbent for the determination of bisphenol derivatives in canned food. Potential factors affecting the extraction efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. Calibration curves were linear (r 2≥ 0.994) over the concentration range from 0.30 to 60 µg kg−1. For both target analytes, the limit of detection (LOD) at signal-to-noise (S/N) ratio of 3 was 0.10 µg kg−1. In addition, a comparative study between the SWCNT and a commercial polydimethylsiloxane (PDMS) SPME fibre for the determination of bisphenol derivatives in canned food was conducted. SWCNT fibre showed higher extraction capacity, better thermal stability (over 350°C) and longer life span (over 150 times) than the commercial PDMS fibre. The method was successfully applied to determine BPA in canned food samples which were purchased from local markets. BPA was found in some of the samples within the concentration range from 0.5 to 5.2 µg kg−1.