To enhance the electron-hole separation and boost the practical performance of commercial titania (Degussa P25) under natural solar light, in this work, P25 was modified with Co(II) species (CoP25) through post-treatment with decomposition of Co-EDTA precursors in a wet chemical anchoring process. With appropriate Co(II) loading amount as molecular cocatalyst, the resulted CoP25-4 showed significantly improved photocatalytic performance for Cr(VI) reduction and bisphenol A (BPA) oxidation under UV-light irradiation. The co-existence of Cr(VI) and BPA promoted mutually the degradation of both pollutants. Under simulated solar light (AM 1.5G) illumination, the Cr(VI) reduction rate over CoP25-4 was 8.5 times enhanced compared with that over P25, while the simultaneous degradation rate of BPA over CoP25-4 was 8 times higher than that over P25. Further investigations indicated that the covalent atomic Co(II) anchoring on P25 significantly promoted the photogenerated electron-hole separation and facilitated Cr(VI) reduction via the formation of Co(I) intermediate and simultaneously boosted BPA oxidation. Our results demonstrated a facile strategy to modify P25 with remarkably improved performance for the practical application in environmental pollution management under natural light excitation.

Here we report a vertically integrated in vitro - in silico study that aims to elucidate the molecular initiating events involved in the induction of oxidative stress (OS) by seven diverse chemicals (cumene hydroperoxide, t-butyl hydroperoxide, hydroquinone, t-butyl hydroquinone, bisphenol A, Dinoseb, and perflourooctanoic acid). To that end, we probe the relationship between chemical properties, cell viability, glutathione (GSH) depletion and antioxidant gene expression. Concentration-dependent effects on cell viability were assessed by MTT assay in two Hepa-1 derived mouse liver cell lines: a control plasmid vector transfected cell line (Hepa-V), and a cell line with increased glutamate-cysteine ligase (GCL) activity and GSH content (CR17). Changes to intracellular GSH content and mRNA expression levels for the Nrf2-driven antioxidant genes Gclc, Gclm, heme oxygenase-1 (Hmox1), and NADPH quinone oxidoreductase-1 (Nqo1) were monitored after sub-lethal exposure to the chemicals. In silico models of covalent and redox reactivity were used to rationalize differences in activity of quinones and peroxides. Our findings show CR17 cells were generally more resistant to chemical toxicity and showed markedly attenuated induction of OS biomarkers; however, differences in viability effects between the two cell lines were not the same for all chemicals. The results highlight the vital role of GSH in protecting against oxidative stress-inducing chemicals, as well as the importance of probing molecular initiating events in order to identify chemicals with lower potential to cause oxidative stress.

As amalgam is partly composed of mercury, a known toxic substance,there are concerns about the safety of this filling material for human health, and for the environmental impact of mercury released from amalgam waste generated by dental offices. Resin-based composite is the most common alternative dental filling material to amalgam. However, concerns have also been raised about the potential for toxicity to human health from composite resin compounds, such as bisphenol A. With an increasing reliance on resin-based composite restorations, there is a need to understand the potential implications for Canadian dental care access, practice, and affordability.

The use of nanosheets of layered calcium phenylphosphonate as a filler in a polymeric matrix was investigated. Layered calcium phenylphosphonate (CaPhP), with chemical formula CaC6H5PO3∙2H2O, is a hybrid organic-inorganic material that exhibits a hydrophobic character due to the presence of phenyl groups on the surface of the layers. In this paper, various CaPhP synthesis methods were studied with the aim of obtaining a product most suitable for its subsequent exfoliation. The liquid-based approach was used for the exfoliation. It was found that the most promising technique for the exfoliation of CaPhP in an amount sufficient for incorporation into polymers involved using propan-2-ol with a strong shear force generated in a high-shear disperser. The filler was tested both in its unexfoliated and exfoliated forms for the preparation of polymer composites, for which a low molecular weight epoxy resin based on bisphenol A was used as a polymer matrix. The prepared samples were characterized by powder X-ray diffraction, atomic force microscopy, optical and scanning electron microscopy, and dynamic mechanical analysis. Flammability and gas permeation tests were also performed. The addition of the nanofiller was found to influence the composite properties - the exfoliated particles were found to have a higher impact on the properties of the prepared composites than the unexfoliated particles of the same loading.

Bioactive dimethacrylate composites filled with silver nanoparticles (AgNP) might be used in medical applications, such as dental restorations and bone cements. The composition of bisphenol A glycerolate dimethacrylate (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA) mixed in a 60/40 wt% ratio was filled from 25 to 5000 ppm of AgNP. An exponential increase in resin viscosity was observed with an increase in AgNP concentration. Curing was performed by way of photopolymerization, room temperature polymerization, and thermal polymerization. The results showed that the polymerization mode determines the degree of conversion (DC), which governs the ultimate mechanical properties of nanocomposites. Thermal polymerization resulted in a higher DC than photo- and room temperature polymerizations. The DC always decreased as AgNP content increased. Flexural strength, flexural modulus, hardness, and impact strength initially increased, as AgNP concentration increased, and then decreased at higher AgNP loadings. This turning point usually occurred when the DC dropped below 65% and moved toward higher AgNP concentrations, according to the following order of polymerization methods: photopolymerization < room temperature polymerization < thermal polymerization. Water sorption (WS) was also determined. Nanocomposites revealed an average decrease of 16% in WS with respect to the neat polymer. AgNP concentration did not significantly affect WS.

Epoxy resin monomers (ERMs) are used as building blocks for thermosetting polymers in applications where strong, flexible, and light-weight materials are required. Most epoxy resins are polymers of diglycidyl ether of bisphenol A (DGEBA). It is highly allergenic and causes occupational allergic contact dermatitis and contact allergy in the general population. Thus, measures to prevent exposure by protective clothing and education are not enough. The work describes a continuation of our research aiming at reducing the skin sensitizing potency of ERMs while maintaining the ability to form polymers. Alternative ERMs were designed and synthesized whereafter the sensitizing potency was determined using the murine local lymph node assay (LLNA). The reactivity of the diepoxides towards a nucleophilic peptide was investigated and the differences in reactivity explained using computational studies. The diepoxides were reacted with triethylenetetramine and the formed polymers were tested for technical applicability using thermogravimetric analysis. We had previously shown that the absence of an oxygen atom in the side chains or removal of aromaticity reduced the sensitizing potency compared to that of DGEBA. Thus, a cycloaliphatic analogue 1 of DGEBA without ether oxygen in the side chains was considered promising and was synthesized. As predicted the sensitizing potency was considerably reduced (10 times) compared to that of DGEBA. However, the technical properties of the polymer of this compound were not considered sufficient. More polar aromatic analogues were investigated, but they could not compete with our previously described ERMs regarding polymerization properties and with 1 regarding low skin sensitization properties. Development of alternative epoxy materials is a delicate balance between allergenic activity and polymerization properties. Tuning of structural properties together with investigation of polymerization conditions combined with skin sensitization studies should be used in industrial research and development. ERM 1 could be used as a lead compound for further studies of aliphatic ERMs.

Bisphenol A (BPA) is an endocrine disrupting compound commonly found in natural waters at concentrations that are considered harmful for aquatic life. Manganese(iii/iv) oxides are strong oxidants capable of oxidizing organic and inorganic contaminants, including BPA. Here we use δ-MnO2 in stirred flow reactors to determine if higher influent BPA concentrations, or introduction rates, lead to increased polymer production. A major BPA oxidation product, 4-hydroxycumyl alcohol (HCA), is formed through radical coupling, and was therefore used as a metric for polymer production in this study. The influent BPA concentration in stirred flow reactors did not affect HCA yield, suggesting that polymeric production is not strongly dependent on influent concentrations. However, changes in influent BPA concentration affected BPA oxidation rates and the rate of δ-MnO2 reduction. Lower aqueous Mn(ii) production was observed in reactors at higher BPA introduction rates, suggesting that single-electron transfer and polymer production are favored under these conditions. However, an examination of Mn(ii) sorption during these reactions indicated that the length of the reaction, rather than BPA introduction rate, caused enhanced aqueous Mn(ii) production in reactors with low introduction rates and longer reaction times due to increased opportunity for disproportionation and comproportionation. This study demonstrates the importance of investigating both the organic and inorganic reactants in the aqueous and solid phases in this complex reaction.

Bisphenol A (BPA) is an endocrine disruptor of xenobiotic type, mainly used for the production of polycarbonate plastic, epoxy resins and non-polymer additives. Because of its wide usages in the environment, the toxic effects of BPA have proved to be harmful to human health. However, its effects on human haemoglobin remain unclear. The affinity between BPA and haemoglobin, as well as erythrocytes, is an important factor in understanding the mechanism of the toxicity of BPA. Flavonoids are strong antioxidants that prevent oxidative stress and Quercetin is a flavonoid found in numerous vegetables and fruits. Therefore, the present investigation was undertaken to investigate whether Quercetin can be used to alleviate the toxic effects of BPA in vitro in human red blood cells (RBC). Venous blood samples were collected from healthy, well-nourished adult volunteers (25-30 years old) by phlebotomy. In a RBC suspension with a cell density of 2 × 104 cell per mL, the concentration of BPA (25-150 µg mL-1) was found to cause an increase in the lipid peroxidation (LPO) and a decrease in the activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX) in human RBC. However, the concurrent addition of BPA (150 µg mL-1) and quercetin (10-50 µg mL-1) lead to significant amelioration. In silico studies gave structural insight into BPA and quercetin to decipher the plausible binding mechanism and molecular level recognition.

Phoenixin (PNX) is a newly identified reproductive peptide required for the estrous cycle. It is most highly expressed in the hypothalamus, where it is a positive regulator of gonadotropin-releasing hormone (GnRH) and kisspeptin. However, it is unknown what signals lie upstream of Pnx to coordinate its effects on GnRH and kisspeptin. We investigated the effects of the hormones, estrogen and leptin; the fatty acids, palmitate, docosahexaenoic acid (DHA), oleate and palmitoleate; and the endocrine disrupting chemical BPA on Pnx mRNA levels. We also examined whether the signaling pathways of nitric oxide, lipopolysaccharide, cAMP and protein kinase C could alter Pnx expression. Immortalized hypothalamic neurons were treated from 2 to 24 h with these compounds and Pnx mRNA levels were measured with RT-qPCR. Unexpectedly, only BPA as well as the fatty acids, palmitate, DHA and oleate, could alter Pnx expression; therefore suggesting that Pnx may fulfill a nutrient-sensing role in the hypothalamus. Our study is the first to delineate potential regulators of this novel neuropeptide, and our findings provide some insight into the functional role of PNX in the hypothalamus.