Flexible oligomeric silicon-containing poly(ether-azomethine)s obtained from epoxide derivatives. Synthesis and characterization

Three new diamines derived from epoxide compounds were synthesized. The preparation of diamine monomers implied the reaction between a phenoxyalkyloxirane (alkyl: H, methyl, isopropyl) and bisphenol A, obtaining the respective aliphatic diols, which produced the corresponding dinitro derivatives. Finally, these derivatives were reduced by using palladium/carbon activated as catalyst and hydrazine as a hydrogen source. Then, six oligomeric poly(ether-azomethine)s (PEAzMs) were obtained from a polycondensation reaction between the new diamines and bis(4-formylbiphenyl-4-yl)dialkylsilane (alkyl: methyl, phenyl) with 84–93% yields. The structural characterization of the diamines and PEAzMs was performed by elemental analysis, infrared spectroscopy, and nuclear magnetic resonance spectroscopy (¹H, ¹³C, and ²⁹Si). Furthermore, polymers were analyzed by solubility tests, gel permeation chromatography, ultraviolet–visible (UV–vis) spectroscopy, thermogravimetry, and differential scanning calorimetry analysis. The results showed PEAzMs with 2–11 repetitive units, where the design of the monomers allowed to obtain improved solution processability in comparison with previously reported silylated poly(azomethine)s and good thermal stability. Additionally, all samples showed high transparency in the UV–vis region. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48055.     

Electrical properties of biomorphic SiC ceramics and SiC/Si composites fabricated from medium density fiberboard

A study has been made of the dependences of the electrical resistivity and the Hall coefficient on the temperature in the range 1.8-1300 K and on magnetic fields of up to 28 kOe for the biomorphic SiC/Si (MDF-SiC/Si) composite and biomorphic porous SiC (MDF-SiC) based upon artificial cellulosic precursor (MDF - medium density fiberboards). It has been shown that electric transport in MDF-SiC is effected by carriers of n-type with a high concentration of ∼10²⁰ cm⁻³ and a low mobility of ∼0.4 cm² V⁻¹ s⁻¹. The specific features in the conductivity of MDF-SiC are explained by quantum effects arising in disordered systems and requiring quantum corrections to conductivity. The TEM studies confirmed the presence of disordering structural features (nanocrystalline regions) in MDF-SiC. The conductivity of MDF-SiC/Si composite originates primarily from Si component in the temperature range 1.8-500 K and since ∼500 to 600 K the contribution of MDF-SiC matrix becomes dominant.     

Behavior of phenols and phenoxyacids on a bisphenol-a imprinted polymer. Application for selective solid-phase extraction from water and urine samples

A molecularly imprinted polymer (MIP), obtained by precipitation polymerisation with 4-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate as cross-linker, and bisphenol-A (BPA) as template, was prepared. The binding site configuration of the BPA-MIP was examined using Scatchard analysis. Moreover, the behaviour of the BPA-MIP for the extraction of several phenolic compounds (bisphenol-A, bisphenol-F, 4-nitrophenol, 3-methyl-4-nitrophenol) and phenoxyacid herbicides such as 2,4-D, 2,4,5-T and 2,4,5-TP has been studied in organic and aqueous media in the presence of other pesticides in common use. It was possible to carry out the selective preconcentration of the target analytes from the organic medium with recoveries of higher than 70%. In an aqueous medium, hydrophobic interactions were found to exert a remarkably non-specific contribution to the overall binding process. Several parameters affecting the extraction efficiency of the BPA-MIP were evaluated to achieve the selective preconcentration of phenols and phenoxyacids from aqueous samples. The possibility of using the BPA-MIP as a selective sorbent to preconcentrate these compounds from other samples such as urine and river water was also explored.     

Comparison of a pair of synthetic tea-catechin-derived epimers: synthesis, antifolate activity, and tyrosinase-mediated activation in melanoma

Despite bioavailability issues, tea catechins have emerged as promising chemopreventive agents because of their efficacy in various animal models. We synthesized two catechin-derived compounds, 3-O-(3,4,5-trimethoxybenzoyl)-(-)-catechin (TMCG) and 3-O-(3,4,5-trimethoxybenzoyl)-(-)-epicatechin (TMECG), in an attempt to improve the stability and cellular absorption of tea polyphenols. The antiproliferative and pro-apoptotic activities of both compounds were analyzed with various cancer cell systems, and TMCG, which was easily synthesized in excellent yield, was more active than TMECG in both melanoma and non-melanoma cell lines. TMCG was also a better inhibitor of dihydrofolate reductase and was more efficiently oxidized by tyrosinase, potentially explaining the difference in activity between these epimers.     

Process Optimisation of In Situ H2 Generation From Ammonia Using Ni on Alumina Coated Cordierite Monoliths

A catalyst of Ni supported on alumina coated monolith has been prepared, characterized and tested in NH₃ decomposition. The characterization of the catalyst by XPS and TPR showed that there is no formation of aluminates after catalyst use. It is studied the effect of the space velocity, by varying the feed flow rate and the catalyst??s length. Some evidences are shown about the reaction inhibition by produced H₂ and about the reasons for the better performance of the monolith than packed bed catalyst.     

gef Gene Expression in MCF-7 Breast Cancer Cells is Associated with a Better Prognosis and Induction of Apoptosis by p53-Mediated Signaling Pathway

Breast cancer research has developed rapidly in the past few decades, leading to longer survival times for patients and opening up the possibility of developing curative treatments for advanced breast cancer. Our increasing knowledge of the biological pathways associated with the progression and development of breast cancer, alongside the failure of conventional treatments, has prompted us to explore gene therapy as an alternative therapeutic strategy. We previously reported that gef gene from E. coli has shown considerable cytotoxic effects in breast cancer cells. However, its action mechanism has not been elucidated. Indirect immunofluorescence technique using flow cytometry and immunocytochemical analysis were used to detect breast cancer markers: estrogen (ER) and progesterone (PR) hormonal receptors, human epidermal growth factor receptor-2 proto-oncogene (c-erbB-2), ki-67 antigen and p53 protein. gef gene induces an increase in ER and PR expressions and a decrease in ki-67 and c-erbB-2 gene expressions, indicating a better prognosis and response to treatment and a longer disease-free interval and survival. It also increased p53 expression, suggesting that gef-induced apoptosis is regulated by a p53-mediated signaling pathway. These findings support the hypothesis that the gef gene offers a new approach to gene therapy in breast cancer.     

High-Stable Mesoporous Ni-Ce/Clay Catalysts for Syngas Production

Abstract  

A mesoporous-type catalytic support was synthesized through the modification of a smectite with polyvinyl alcohol (PVA) and microwaves. Texture and micro-morphology of the support was determined. Several techniques were employed in order to describe the chemical environment of active species on the surface. Ni⁰ particle sizes were dependent on the structural site of reducible species. High stable Ni-Ce catalysts (calcined at 800 °C) were evaluated in the CO₂ reforming of methane reaction at 700 °C (WHSV = 96 L g⁻¹ h⁻¹, without dilution gas and pre-reduction). The catalysts have presented CH₄ conversions between 40 and 65%, CO₂ conversion between 35 and 65% and H₂/CO ratios between 0.2 and 0.4.     

Evaluation of emu oil extraction methods and their effects on physical and rheological behavior

In this study we evaluated the efficiency of six extraction methods for emu fat based on the quantification of yield, color, density, refraction index, and rheological behavior. Both physical methods (Bain Marie, rotary evaporator, fusion, ultrasound, and microwave) and chemical methods (solvents) were evaluated. Oil properties were compared with commercial emu oil as a reference. Solvent‐based extraction produced the greatest yield (72.8%). Among the physical methods, the greatest yield was produced by the ultrasound method (42.8%). In general, properties were similar to those reported for vegetable oils. The rotary evaporator method showed the greatest difference in total color (ΔE) in comparison with a commercially‐produced reference, while the fusion method showed the smallest ΔE. No statistically significant differences were found between the density and refraction index of the treated samples and those of the reference. Kinematic viscosity increased significantly in samples extracted via microwave method. All samples displayed pseudoplastic behavior. The data showed a good fit to the power law model (R² > 0.90). The consistency coefficient and flow behavior index were determined for all methods. Practical applications: Therapeutic applications for oil have been posited for emu oil. In pharmaceutical products, oils are used as emollients and as carriers for medicinal substances. The practical importance of an oil depends on its physical properties, thus a thorough understanding of those physical properties is very important for identifying potential applications. These properties are affected by the extraction method employed; the present paper evaluates the effects of a range of extraction methods on yield efficiency, as well as physical and rheological properties. Novel extraction methods such as ultrasound and microwave are also evaluated in this study.     

Laser transmission welding of poly(lactic acid) and polyamide66/sepiolite nanocomposites

Influence of sepiolite nanoclay on the properties of the resulting join between poly(lactic acid) (PLA) and different Polyamide66 (PA66)/nanoclay nanocomposites was studied in this work. Six different polymer nanocomposites based on PA66 were manufactured through a melt compounding process by adding a fixed 1.64 wt % of a commercial IR absorber additive and the respective weight percentages of sepiolite to the polymer matrix. Several nanocomposite/PLA joints were finally performed by means of the transmission laser welding technology and the resulting weldings were characterized in terms of mechanical properties by performing peeling and shearing tests. Furthermore, both welded and mechanically tested samples were also analyzed by scanning electron microscopy in order to study the morphology of the weld seam. The results of the performed tests show that the addition of sepiolite to the PA66 improves the welding performance only in those cases in which the percentage of sepiolite of the nanocomposites is higher than 5 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46638.