Bisphenol Derivatives Research Articles

A brief review of bisphenol derivatives and their electrochemical detection methods

A brief review of bisphenol derivatives and their electrochemical detection methods

Optical characteristics of brown carbon in the atmospheric particulate matter of Dhaka, Bangladesh: Analysis of solvent effects and chromophore identification

The prevalence of brown carbon (BrC) in the atmosphere has experienced a notable upsurge owing to human activities of anthropogenic origin. This study aims to examine the optical characteristics of BrC in both deionized (DI) water and organic solvents (OS), alongside the identification of BrC chromophores within the ambient atmosphere of Dhaka, Bangladesh. Particulate matter (PM) samples were collected on quartz filters using a low-volume sampler from December 2021 to May 2022 at Mukarram Hussain Khundker Bhaban, University of Dhaka. The concentration of BrC was measured using soot analyzer, optical properties of BrC were determined using UV–Vis spectrometer, and BrC chromophores were identified with GC-MS. Average concentration of BrC was 19.13 ± 5.71 μgm−3. The average of absorption coefficient (babs_365), mass absorption efficiency (MAE), absorption angstrom exponent (AAE), and refractive index (kabs_365) of BrC_DI have been observed to be 38.75 ± 21.90 Mm−1, 2.16 ± 1.42 m2 g-1, 1.51 ± 0.08, 0.06 ± 0.04, respectively. The absorption coefficient and MAE of BrC_OS are 1.3 and 1.36 times, respectively higher than that of BrC_DI. Thirty chromophores of BrC have been identified, predominantly consisting of oxygenated compounds. Derivatives of Bisphenol A (C27H44O2Si2) were detected in all samples of oxygenated compounds, primarily originating from the combustion of plastic and the incineration of e-waste. Additionally, compounds containing nitrogen and sulfur, such as C14H26N2O, C31H55N, and C31H49NO3S, were identified, largely attributed to biomass combustion and traffic emissions. These chromophores play a significant role in the absorption of solar radiation, thus influencing atmospheric photochemistry.

Comparative in silico and in vitro evaluation of possible toxic effects of bisphenol derivatives in HepG2 cells.

Bisphenols are widely used in the production of polycarbonate plastics and resin coatings. Bisphenol A (BPA) is suggested to cause a wide range of unwanted effects and "low dose toxicity". With the search for alternative substances to BPA, the use of other bisphenol derivatives namely bisphenol F (BPF) and bisphenol S (BPS) has increased. In the current study, we aimed to evaluate the in silico predicted inhibitory concentration 50s (pIC50s) of bisphenol derivatives on immune and apoptotic markers and DNA damage on HepG2 cells. Moreover, apoptotic, genotoxic and immunotoxic effects of BPA, BPF and BPS were determined comparatively. Effects of bisphenols on apoptosis were evaluated by detecting different caspase activities. The genotoxic effects of bisphenols were evaluated by measuring the levels of 8-hydroxy-2'-deoxyguanosine (8-OHdG) and 8-oxoguanine glycosylase (OGG1). To determine the immunotoxic effect of bisphenol derivatives, the levels of interleukin 4 (IL-4) and interleukin 10 (IL-10), transforming growth factor beta (TGF-β) and tumor necrosis factor-alpha (TNF-α), which are known to be expressed by HepG2 cells, were measured. Results: In silico data indicate that all of the bisphenols may cause alterations in immune and apoptotic markers as well as DNA damage at low doses. İn vitro data revealed that all bisphenol derivatives could affect immune markers at inhibitory concentration 30s (IC30s). In addition, BPF and BPS may also have apoptotic immunotoxic effects. Both in silico and in vivo research are needed further to examine the toxic effects of alternative bisphenol derivatives.

Development of novel bisphenol derivatives with a membrane-targeting mechanism as potent gram-positive antibacterial agents

Antibiotic resistance is becoming increasingly severe. The development of small molecular antimicrobial peptides is regarded as a promising design strategy for antibiotics. Here, a series of bisphenol derivatives with amphiphilic structures were designed and synthesized as antibacterial agents by imitating the design strategy of antimicrobial peptides. After a series of structural optimizations, lead compound 43 was identified, which exhibited excellent antibacterial activity against Gram-positive bacterial strains (MICs = 0.78–1.56 μg/mL), poor hemolytic activity (HC50 > 200 μg/mL), and low cytotoxicity (CC50 > 100 μg/mL). Further biological evaluation results indicated that 43 exerted antibacterial effects by directly destroying bacterial cell membranes and displayed rapid bactericidal properties (within 0.5–1 h), leading to a very low probability of drug resistance. Moreover, in a murine model of corneal infection, 43 exhibited a strong in vivo antibacterial efficacy. These findings indicate that 43 is a promising candidate compound for the treatment of bacterial infections.

Sulfonic acid functionalized SBA−15 catalyst and mercaptopropionic acid promotor for the selective synthesis of p,p′−bisphenol A: Replacement to mineral acid−based process

The significance of selective catalysis in producing plastic monomers is crucial to meet sustainability and economic requirements. It is essential to develop a selective solid acid catalyst to replace irrecoverable corrosive mineral acids and thermolabile sulfonated resins for the production of p,p′−bisphenol A (BPA) isomer, a key intermediate in polycarbonate production. However, limited success has been achieved due to low activity and selectivity towards the desired p,p′−BPA isomer. Herein, a mild and selective route is presented for producing p,p′−BPA using SBA-15 functionalized sulfonic acid catalysts. Sulfonic acid-based catalysts with and without alkyl chain linkers, supported on SBA−15, were synthesized to evaluate the effect of acidity, and textual properties on the catalytic efficiency, and product selectivity. Among all the synthesized catalysts, SBA−15−Pr−SO3H exhibited the highest product selectivity. The addition of mercaptopropionic acid (as a promoter) enhanced the catalytic efficiency and afforded ∼99% acetone conversion, with 97.3% p,p′−BPA selectivity. A detailed mechanism with and without the promoter is proposed. The study also highlights the potential of mesoporous SBA−15−supported sulfonic acid catalysts as a selective and efficient catalyst for synthesizing bisphenol derivatives from the lignocellulose biomass−derived platform molecules, addressing challenges posed by fossil resources.

Impact of bisphenol A and analogues eluted from resin-based dental materials on cellular and molecular processes: An insight on underlying toxicity mechanisms.

Dental resin systems, used for artificial replacement of teeth and their surrounding structures, have gained popularity due to the Food and Drug Administration's (FDA) recommendation to reduce dental amalgam use in high-risk populations and medical circumstances. Bisphenol A (BPA), an endocrine-disrupting chemical, is an essential monomer within dental resin in the form of various analogues and derivatives. Leaching of monomers from resins results in toxicity, affecting hormone metabolism and causing long-term health risks. Understanding cellular-level toxicity profiles of bisphenol derivatives is crucial for conducting toxicity studies in in vivo models. This review provides insights into the unique expression patterns of BPA and its analogues among different cell types and their underlying toxicity mechanisms. Lack of a consistent cell line for toxic effects necessitates exploring various cell lines. Among the individual monomers, BisGMA was found to be the most toxic; however, BisDMA and BADGE generates BPA endogenously and found to elicit severe adverse reactions. In correlating in vitro data with in vivo findings, further research is necessary to classify the elutes as human carcinogens or xenoestrogens. Though the basic mechanisms underlying toxicity were believed to be the production of intracellular reactive oxygen species and a corresponding decline in glutathione levels, several underlying mechanisms were identified to stimulate cellular responses at low concentrations. The review calls for further research to assess the synergistic interactions of co-monomers and other components in dental resins. The review emphasizes the clinical relevance of these findings, highlighting the necessity for safer dental materials and underscoring the potential health risks associated with current dental resin systems.

DETERMINATION OF DNA DAMAGE INDUCED BY BISPHENOL A AND BISPHENOL S IN MCF7 CELL LINE

Objective: This study aimed to determine the DNA damage induced by Bisphenol A (BPA) and Bisphenol S (BPS) on MCF7 cell line. Material and Method: DNA damage was determined by COMET assay in MCF7 cell line at 0.1, 0.5, 1, 5, 10 and 50 μM concentrations of BPA and BPS. Result and Discussion: All BPA and BPS concentrations studied (0.1, 0.5, 1, 5, 10 and 50 μM) significantly induced DNA damage on MCF7 cell line compared with control (p<0.05). BPS significantly induced DNA damage more than BPA at the 3 highest concentrations studied (5, 10 and 50 μM) (p<0.05). This study shows that bisphenol derivatives can also cause DNA damage like BPA.

Gas and Liquid Chromatography Mass Spectrometry as a Tool for Elucidating Volatile Organic Compounds (VOCs) and Metabolites in Maternal Milk: A Perspective on Infants’ Health Risk Assessment

Maternal milk is pivotal for infants’ nutrition. It also portrays the chemical burden to which the mother has been exposed. One of the chemical families that is prevalent and related to potential toxic effects are volatile organic compounds (VOCs). In the present study, motivated by the scarcity of works dealing with concomitant VOC and metabolite determination in maternal milk, two new gas/liquid chromatography tandem mass spectrometry (GC-MS/MS, LC-MS/MS) methods for the simultaneous measurement of 25 VOCs and 9 of their metabolites, respectively, in maternal milk were developed and applied to 20 maternal milk samples collected from mothers in Greece. In parallel, a headspace solid-phase microextraction (HS-SPME)–GC-MS method was employed for the untargeted screening of chemicals. Low detection rates for benzene, toluene, styrene and p,m-xylenes, and three of their metabolites, namely N-acetyl-S-(benzyl)-L-cysteine (BMA, metabolite of toluene), 3-methylhippuric (3-MHA, metabolite of xylenes) and mandelic acid (MA as DL and R isomers, metabolites of styrene and ethylbenzene), were evidenced in concentrations varying from <lower limit of quantification (LLOQ) to 0.79 ng mL−1. HS-SPME–GC-MS disclosed the presence of common maternal milk constituents such as fatty acids. Nevertheless, bisphenol-A, bisphenol derivatives and phthalates were also detected. The infants’ health risk assessment demonstrated a low risk and negligible carcinogenic risk, yet the detection of these compounds should not be underestimated.

Occurrence of Chlorinated Derivatives of Bisphenol S in Paper Products and Their Potential Health Risks through Dermal Exposure.

The occurrence of chlorinated derivatives of bisphenol S (Clx-BPS) and BPS was investigated in nine types of paper products (n = 125), including thermal paper, corrugated boxes, mail envelopes, newspapers, flyers, magazines, food contact paper, household paper, and business cards. BPS was found in all paper product samples, while Clx-BPS were mainly found in thermal paper (from below the limit of detection (<LOD) to 3.76 μg g-1), corrugated box (<LOD to 30.2 ng g-1), mailing envelope (<LOD to 31.0 ng g-1), and newspaper (<LOD to 98.5 ng g-1) samples. All samples with detectable Clx-BPS concentrations contained a high concentration of BPS. Cl1-BPS was the most frequently detected analyte, followed by Cl2-BPS-2 (2-chloro-4-(3-chloro-4-hydroxyphenyl)sulfonylphenol), Cl2-BPS-1 (2,6-dichloro-4-(4-hydroxyphenyl)sulfonylphenol), Cl3-BPS, and Cl4-BPS. The estimated daily intake of Clx-BPS via dermal transfer upon handling of paper products was 0.546 and 16.4 ng per day for generally and occupationally exposed individuals, at the maximum concentration of 3.76 μg g-1. Additionally, the potential toxicity of Clx-BPS was predicted using an in silico tool, showing toxicity gradually increased with an increasing degree of chlorination of BPS. Thus, human exposure to Clx-BPS through paper products should be given due attention as a health risk.

Synthesis and Characterization of DOPO-Containing Poly(2,6-dimethyl-1,4-phenylene oxide)s by Oxidative Coupling Polymerization.

A set of polyphenylene oxides incorporating DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) functionality, denoted as DOPO-R-PPO, was synthesized by copolymerization of 2,6-dimethylphenol (2,6-DMP) with various DOPO-substituted tetramethyl bisphenol monomers. In the initial step, a Friedel-Crafts acylation reaction was employed to react 2,6-DMP with different acyl chlorides, leading to the formation of ketone derivatives substituted with 2,6-dimethylphenyl groups. Subsequently, the ketones, along with DOPO and 2,6-DMP, underwent a condensation reaction to yield a series of DOPO-substituted bisphenol derivatives. Finally, polymerizations of 2,6-dimethylphenol with these DOPO-substituted bisphenols were carried out in organic solvents using copper(I) bromide/N-butyldimethylamine catalysts (CuBr/DMBA) under a continuous flow of oxygen, yielding telechelic PPO oligomers with DOPO moieties incorporated into the polymer backbone. The chemical structures of the synthesized compounds were characterized using various analytical techniques, including Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H NMR), phosphorus nuclear magnetic resonance (31P NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). When compared to conventional poly(2,6-dimethyl-1,4-phenylene oxide)s with a similar molecular weight range, all DOPO-PPOs exhibited higher glass transition temperatures, enhanced thermal degradability, and increased char yield formation at 800 °C without compromising solubility in organic solvents.

Bisphenol A and chlorinated derivatives of bisphenol A assessment in end stage renal disease patients: Impact of dialysis therapy

Patients with end stage kidney disease treated by dialysis (ESKDD) process dialysis sessions to remove molecules usually excreted by kidneys. However, dialysis therapy could also contribute to endocrine disruptors (ED) burden. Indeed, materials like dialyzer filters, ultrapure dialysate and replacement fluid could exposed ESKDD patients to Bisphenol A (BPA) and chlorinated derivatives of BPA (ClxBPAs). Thus, our aim was to compare BPA and ClxBPAs exposure between ESKDD patients, patients with stage 5 chronic kidney disease (CKD5) not dialyzed and healthy volunteers. Then we describe the impact of a single dialysis session, according to dialysis modalities (hemodialysis therapy (HD) versus online hemodiafiltration therapy (HDF)) and materials used with pre-post BPA and ClxBPAs concentrations. The plasma levels of BPA and four ClxBPAs, were assessed for 64 ESKDD patients in pre and post dialysis samples (32 treated by HD and 32 treated by HDF) in 36 CKD5 patients and in 24 healthy volunteers. BPA plasma concentrations were 22.5 times higher for ESKDD patients in pre-dialysis samples versus healthy volunteers (2.208 ± 5.525 ng/mL versus 0.098 ± 0.169 ng/mL) (p < 0.001). BPA plasma concentrations were 16 times higher for CKD5 patients versus healthy volunteers, but it was not significant (1.606 ± 3.230 ng/mL versus 0.098 ± 0.169 ng/mL) (p > 0.05). BPA plasma concentrations for ESKDD patients in pre-dialysis samples were 1.4 times higher versus CKD5 patients (2.208 ± 5.525 ng/mL versus 1.606 ± 3.230 ng/mL) (p < 0.001). For healthy volunteers, ClxBPAs were never detected, or quantified while for CKD5 and ESKDD patients one ClxBPAs at least has been detected or quantified in 14 patients (38.8%) and 24 patients (37.5%), respectively. Dialysis therapy was inefficient to remove BPA either for HD (1.983 ± 6.042 ng/mL in pre-dialysis versus 3.675 ± 8.445 ng/mL in post-dialysis) or HDF (2.434 ± 5.042 ng/mL in pre-dialysis versus 7.462 ± 15.960 ng/mL in post dialysis) regarding pre-post BPA concentrations (p > 0.05). The same result was observed regarding ClxBPA analysis. Presence of polysulfone in dialyzer fibers overexposed ESKDD patients to BPA in pre-dialysis samples with 3.054 ± 6.770 for ESKDD patients treated with a polysulfone dialyzer versus 0.708 ± 0.638 (p = 0.040) for ESKDD patients treated without a polysulfone dialyzer and to BPA in post-dialysis samples with 6.629 ± 13.932 for ESKDD patients treated with a polysulfone dialyzer versus 3.982 ± 11.004 (p = 0.018) for ESKDD patients treated without a polysulfone dialyzer. This work is to our knowledge the first to investigate, the impact of a dialysis session and materials used on BPA and ClxBPAs plasma concentrations and to compare these concentrations to those found in CKD5 patients and in healthy volunteers.

Towards an in-Depth Understanding of Single-Ion Conducting Polymer Electrolytes for Lithium-Metal Batteries

Recently, we have reported a new polyarylene-based single-ion conducting multi-block copolymer electrolyte providing very high ionic conductivities of about 1 mS cm-1 at ambient temperature and excellent cycling stability of LiNMC811 (LiNi0.8Mn0.1Co0.1O2) cells – even at 0 °C.1–3 Further improvement of this new electrolyte system, however, requires an in-depth understanding of ideally each single functional unit in the polymer.Herein, we present some of our latest results on the experimental and theoretical investigation of stepwise modified copolymers in order to decipher the impact of the different functional groups on the eventual mechanical, thermal, chemical, and electrochemical behavior. This stepwise modification includes, amongst others, the replacement of the biphenyl unit by a series of bisphenol derivatives and the variation of the ionophobic and ionophilic block. The former approach provides the unique opportunity to investigate the influence of the monomer substitution pattern, while the latter unveils some rather unexpected findings concerning the impact of the lithium concentration in the electrolyte. References H.-D. Nguyen et al., Energy Environ. Sci., 11, 3298–3309 (2018).D. Steinle et al., J. Solid State Electrochem., 26, 97–102 (2022).Z. Chen et al., Nano Energy, 77, 105129 (2020).

Bisphenol derivatives in cord blood and association between thyroid hormones and potential exposure sources

ABSTRACT Endocrine-disrupting environmental chemicals are a public health concern, particularly fetal exposure to Bisphenol derivatives. This study aimed to assess fetal exposure to Bisphenol derivatives (BPA, BPF, and BPS) by measuring their levels in cord blood and investigating their association with plastic material used in daily life as well as cord blood TSH and free L-thyroxine (fT4) levels. In this descriptive study, a questionnaire with a face-to-face interview was administered before birth, and cord blood samples were taken immediately after delivery. The mean levels of BPA, BPF, TSH, and fT4 were measured as 10.69 ± 2.39 ng/ml, 3.80 ± 0.58 ng/ml; 2.36 ± 0.23 µIU/ml, and 14.18 ± 0.53 pg/ml, respectively, in a total of 104 cord blood samples. All BPS levels remained below the detection limit. Linear regression analysis revealed a positive association between birth weight and cord blood BPA concentration (β = 0.26; p = 0.02). Further research on maternal exposure during the fetal and neonatal period is critical for public health.

Synthesis and properties of an amide- and Meldrum's acid-functionalized mainchain-type polybenzoxazine and the corresponding crosslinked resin

Mainchain-type polybenzoxazines (PBz) are self-crosslinkable polymers possessing high flexibility of molecular designs and property adjustments. The corresponding crosslinked PBz in different forms, such as films, porous membranes, electrospun fiber mats, have been prepared for various applications. This work aims on functionalization of PBz with amide groups and Meldrum's acid moieties, to bring hydrogen bonding interaction and additional covalent crosslinks to the crosslinked PBz. A bisphenol derivative possessing both MA and amide groups (MA/Am-BP) is synthesized from a biomass-based precursor of 3,4-dihydrocoumarine. MA/Am-BP is utilized as a monomer, together with 4,4′-oxydianiline and formaldehyde, for preparation of amide- and Meldrum's acid-functionalized polybenzoxazine (MA/Am-PBz) and the corresponding crosslinked polybenzoxazine (CR_MA/Am-PBz). The benzoxazine- and Meldrum's acid-involved crosslinking reactions have been investigated with temperature-dependent Fourier transform infrared spectroscopy. CR_MA/Am-PBz has demonstrated film formability and flexibility. In addition to the attractive thermal properties, including a thermal stability of 340 °C, a char yield of 52 wt% at 800 °C, a storage modulus of 1.44 GPa at 50 °C, and a Tg of 295 °C, CR_MA/Am-PBz also exhibits a high tensile strength of 97 MPa, which is superior over the data reported to crosslinked polybenzoxazine films.

Halogenated bisphenol A derivatives potently inhibit human, rat, and mouse gonadal 3β-hydroxysteroid dehydrogenases: Structure-activity relationship and in silico molecular docking analysis

Bisphenol A (BPA) is a widely used plastic material, and halogenated BPA derivatives are formed either by synthesis or environmental processes. However, the effect of halogenated bisphenols on steroidogenesis remains unclear. The aim of this study was to compare inhibition of 6 BPA derivatives on gonadal 3β-hydroxysteroid dehydrogenases (3β-HSDs) in three species (human, rat, and mouse). The inhibition on human 3β-HSD2 was tetrabromo BPA (TBBPA, IC50, 1.01 μM)>trichloro BPA (TrCBPA, 3.95 μM)>tetrachloro BPA (TCBPA, 4.14 μM)>monochloro BPA (MCBPA, 4.74 μM)>others with TrCBPA of competitive, TBBPA of noncompetitive and MCBPA/TCBPA of mixed inhibition. The inhibition on rat 3β-HSD1 was TCBPA (1.68 μM)>TrCBPA (1.72 μM)>MCBPA (2.80 μM)>BPA>others with mixed inhibition. The inhibition on mouse 3β-HSD6 was TrCBPA (1.59 μM) >MCBPA (3.36 μM)>TCBPA (3.72 μM)>others with mixed inhibition. Molecular docking analysis showed that TBBPA, TrCBPA, and TCBPA bind to steroid active sites, contacting with catalytic residue Tyr154 of human 3β-HSD2. MCBPA, TrCBPA, and TCBPA bind to steroid active site of rat 3β-HSD1. MCBPA and TrCBPA bind to active site of mouse 3β-HSD6. Regression of lowest binding energy values with Ki values revealed a significant negative linear regression (P < 0.05). In conclusion, halogenated BPA derivatives are more potent inhibitors of three 3β-HSDs than BPA and there is structure-dependent inhibition. SynopsisChlorinated bisphenol derivatives after water chlorination process and other halogenated bisphenols effectively inhibit human and rat 3β-HSD activity, thereby leading to steroid hormone deficiency.

Assessment of Endocrine Disruptor Exposure in Hospital Professionals Using Hair and Urine Analyses: An Awareness Campaign.

In 2021, French public authorities initiated the fourth National Environmental Health Plan to prevent environment-related health risks. This plan primarily focuses on the sensitization of health professionals and health care institutions. Endocrine disruptors (EDs) are environmental factors associated with several adverse health effects, such as reproductive disorders, obesity, and cancer. This study aimed to conduct an awareness campaign among professionals at a general hospital center on the risks related to EDs. Hospital professionals were directly involved in this study, and urine and hair samples were collected to determine bisphenol and paraben exposure levels. Analyses were performed using validated liquid chromatography-tandem mass spectrometry methods, enabling the simultaneous determination of bisphenols and parabens. A questionnaire on lifestyle habits was distributed to assess its relationship with the exposure profiles. Nineteen professionals were recruited for the study. Bisphenol A was detected in 95% of the urine samples, and the chlorinated derivatives of bisphenol A were between 16% and 63%. parabens showed detection frequencies between 37% and 100%, and methylparaben was quantified at an average concentration of 0.45 ± 0.46 ng/mL. In hair samples, bisphenols A, F, and S were detected at 95%-100%, chlorinated derivatives of bisphenol A were detected at 37%-68%, and parabens were detected at 100%. This awareness campaign may encourage health care institutions to adopt a policy of reducing endocrine disruptor exposure among their patients and professionals, who could be educated regarding the risks associated with EDs. Conducting a multicenter study to refine the results herein and establish a dynamic to prevent endocrine disruptor and environmental risks in health care systems would be valuable.

Fate of five bisphenol derivatives in Chlamydomonas mexicana: Toxicity, removal, biotransformation and microalgal metabolism

Bisphenols (BPs) are recognized as emerging contaminants because of their estrogenic properties and frequent occurrence in environmental matrices. Here, we evaluated the toxic effects of five common BPs on freshwater microalga Chlamydomonas mexicana and removal of the BPs by the alga. Bisphenols -AF (BPAF), -B (BPB), and -Z (BPZ) (96 h, EC50 1.78–12.09 mg·L−1) exhibited higher toxicity to C. mexicana compared to bisphenol -S (BPS) and -F (BPF) (96 h, EC50 30.53–85.48 mg·L−1). In contrast, the mixture of BPs exhibited acute toxicity (96 h, EC50 8.07 mg·L−1). After 14 days, C. mexicana had effectively removed 61%, 99%, 55%, 87%, and 89% of BPS, BPF, BPAF, BPB, and BPZ, respectively, at 1 mg L−1. The biotransformed products of all five BPs were analyzed using UHPLC QTOF, and their toxicity was predicted. All biotransformed products were observed to be less toxic than the parent compounds. The fatty acid composition of C. mexicana after exposure to the BP mixture was predominantly palmitic acid (34.14%), followed by oleic acid (18.9%), and γ-linolenic acid (10.79%). The results provide crucial information on the ecotoxicity of these five BPs and their removal by C. mexicana; the resulting biomass is a potential feedstock for producing biodiesel.

Fully bio-based furan/maleic anhydride epoxy resin with enhanced adhesive properties

Epoxy resins are widely used in a variety of application fields, thanks to their good mechanical strength, chemical resistance and adhesion to several substrates. Nowadays, the quite majority of epoxy resins are based on derivatives of bisphenol A (BPA), which poses serious health concerns. This issue is pushing the research towards suitable bio-based alternatives to this product, being furan-based epoxies very promising in this respect. In a previous work, 2,5-bis[(oxiran-2-ylmethoxy)methyl]furan (BOMF) was cured with methyl nadic anhydride (MNA), and successfully used as tinplate coating. Herein, in a view of increasing the sustainability of these epoxy resins, we have replaced MNA with maleic anhydride (MA), which can be derived from vegetable feedstocks, thus obtaining a fully bio-based epoxy resin. This latter has then been used as adhesive for carbon fiber-reinforced thermosetting plastics (CFRP). The curing process of the resin was monitored by differential scanning calorimetry (DSC) and chemo-rheological analysis. The results highlighted the significantly higher reactivity of BOMF towards MA compared to the diglycidyl ether of BPA (DGEBA). The crosslinked samples were characterized in their thermal, mechanical and adhesive properties. In comparison to DGEBA/MA and BOMF/MNA, BOMF/MA showed higher ultimate strain and slightly lower glass transition temperature, tensile modulus and ultimate strength. Interestingly, BOMF/MA displayed outstanding adhesive strength on CFRP joints, outperforming the DGEBA-based counterpart by three times. Indeed, by properly selecting the anhydride curing agent, a highly ductile fully bio-based material was developed for high performance adhesive applications. The overall results demonstrate that the properties of BOMF-based epoxy resins can be tailored to meet technical and safety requirements of downstream applications, representing a sustainable alternative to traditional systems containing DGEBA.

Broadening the lens on bisphenols in coastal waters: Occurrence, partitioning, and input fluxes of multiple novel bisphenol S derivatives along with BPA and BPA analogues in the Pearl River Delta, China

Bisphenol S derivatives (BDs) are being widely used as novel substitutes for BPA and BPA analogues (BPAs), causing pollution in various environmental compartments. However, the occurrence and fate of BDs in coastal waters are currently unknown. To broaden the lens on bisphenols in coastal waters, this study measured a broad suite of 23 bisphenols, including 12 BDs along with BPA and 10 BPAs, in water, suspended particulate matter (SPM), and sediment from eight major outlets of the Pearl River Delta, China (PRD). In addition to BPA and BPAs, all the 12 BDs were detected in the collected samples. The total concentration of 12 BDs ranged from 1.2 to 25 ng/L (median of 4.3 ng/L) in water samples, 0.80–13 ng/g dw (median of 3.0 ng/g dw) in SPM samples and 0.48–3.7 ng/g dw (median of 0.64 ng/g dw) in sediment samples. For most individual BDs, they had comparable concentrations to individual BPAs. In addition, logKd values of the frequently detected bisphenols, including BPA, BPS, BPF, 4-((4-Isopropoxyphenyl)sulfonyl)phenol (BPSIP), 2,4-bis(phenylsulfonyl)phenol (DBSP), and other 9 bisphenols, were significantly correlated with their logKow values (R2 = 0.38, p < 0.05), indicating that the partitioning of bisphenols between the aqueous and SPM phases were strongly influenced by hydrophobic interaction. Based on bisphenols’ concentrations in water from the eight outlets of PRD, the estimated input fluxes of novel BDs (1900 kg/y) were found to be even higher than that of BPAs (550 kg/y). This indicates that the riverine input of BDs into the coastal environment is gradually increasing, which should be taken seriously in the future.

Expression of selected nuclear receptors in human epithelial ovarian cell line Caov3 exposed to bisphenol derivatives.

Objectives. Bisphenol A (BPA) is an indispensable industrial chemical. However, as a proven endocrine disruptor, it may be associated with several health disturbances, including the reproductive functions impairment and cancer. Due to the restriction of BPA usage, many bisphenol derivatives gradually substitute BPA. However, studies have reported adverse biological effects of BPA analogs, but the specific sites of their action remain largely unknown. Nuclear receptors (NRs) appear to play significant roles in various types of cancer. In addition, they are considered relevant targets of bisphenols. In the present study, we investigated the effects of BPA and its analogs bisphenol S (BPS), bisphenol F (BPF), and bisphenol AF (BPAF) on mRNA expression of selected NRs in the human ovarian epithelial cell line Caov3. The NRs examined included retinoic acid receptor α (RARA), retinoid X receptor α (RXRA), peroxisome proliferator activating receptor β/δ (PPARD), chicken ovalbumin upstream promoter-transcription factor 2 (COUPTFII), and nuclear receptor-related protein 1 (NURR1). Methods. Caov3 cells were treated with the bisphenols at the concentrations of 1 nM, 100 nM, 10 µM and 100 µM. After 24 h and 72 h of incubation, cell viability was determined by the MTS assay, and the selected genes expression was analyzed using RT-qPCR. Results. Bisphenol treatment did not affect Caov3 cell viability, except the significant impairment after exposure to the highest BPAF dose (100 µM). At lower doses, neither bisphenol analog altered the expression of the NRs. However, at the highest concentration (100 µM), BPAF and BPA altered the mRNA levels of PPARD, COUPTFII, and NURR1 in a time- and receptor-specific manner. Conclusions. The effects of bisphenols on the specific NRs in the epithelial ovarian cancer cells were addressed for the first time by the present study. Although generally we did not find that bisphenols may provoke significant alterations in the expression of the selected NRs in Caov3 cells, they may alter mRNA expression of certain NRs at high concentrations.