Electrochemical treatment of bisphenol-A using response surface methodology

The decomposition of bisphenol-A (BPA) in synthetic solution and in municipal effluent was investigated using an electro-oxidation process. Electrolysis was conducted using a cylindrical electrolytic cell containing two circular anodes (expanded metal) and two circular cathodes (stainless steel) alternated in the electrode pack. Different anode materials (Ti/SnO₂, Ti/IrO₂ and Ti/PbO₂) were tested, and Ti/PbO₂ was found to be the most effective electrode for BPA degradation. An experimental design methodology (2³ Box–Behnken design) was applied to determine the optimal experimental conditions in terms of cost effectiveness. The BPA concentration (C ₀ = 1.0 mg l⁻¹) could be optimally diminished by up to 90% by applying a current intensity of 2.0 A for a 100-min reaction period in the presence of 250 mg Na₂SO₄ l⁻¹ (used as a supporting electrolyte). Then, the optimal conditions were applied on a municipal wastewater effluent (sampled after secondary treatment) artificially contaminated with 1 mg BPA l⁻¹ without the addition of a supporting electrolyte. The treatment was more effective with the municipal effluent due to the presence of a high concentration of chloride ions that could easily be transformed into active chlorine. BPA could be oxidized by both direct anodic electrochemical oxidation (by means of OH·) and indirect electrochemical oxidation via mediators, such as hypochlorous acid generated by chloride oxidation. Both actions (direct and indirect effects) lead to the formation of powerful oxidizing agents capable of rapidly oxidizing BPA.     

Graded evolution of anisotropic microstructure during sintering from crystal-oriented powder compact

Anisotropic sintering, including shrinkage and grain growth, was examined for c-axis-oriented (Sr,Ca)₂NaNb₅O₁₅ (SCNN) ceramics, which were prepared by colloidal processing under a magnetic field. In the c-axis-oriented SCNN powder compact, shrinkage and grain growth along the c-axis were higher than those along the a-axis. The anisotropic microstructural development was clearly associated with anisotropic sintering shrinkage. X-ray diffraction, scanning electron microscopy, and energy back scattering diffraction showed that the grain growth of oriented particles by including random grains contribute to the development of the oriented microstructure. Finally, the highly crystal-oriented SCNN ceramics with a densified microstructure were obtained through anisotropic sintering. These results clearly showed the potential to develop a well-defined anisotropic microstructure during sintering by designing and controlling the particle packing structure in a powder compact.     

Tamoxifen derivatives for delivery of the antitumoral (DACH)Pt group: selective synthesis by McMurry coupling,and biochemical behaviour

The goal of our study was to potentiate the effects of the ((R,R)-trans-1,2-diaminocyclohexane)-platinum(II) fragment [(DACH)Pt], known for its cytotoxic properties, either with tamoxifen (Tam), the most widely used antiestrogen in the treatment of hormone-dependent breast cancers, or with its active metabolite hydroxytamoxifen (hydroxy-Tam). We coupled Tam or hydroxy-Tam derivatives bearing a malonato group at the para position of the beta aromatic ring with the (DACH)Pt fragment. The malonato-Tam and malonato-hydroxy-Tam compounds were prepared through McMurry coupling of the appropriate ketones. The presence of the malonate group resulted in a pronounced stereospecificity in the reaction, since malonato-Tam was obtained only as the Z isomer, while malonato-hydroxy-Tam was obtained as an 80/20 E/Z mixture. Attribution of the isomeric structures was achieved by 2D NMR spectroscopy. The platinum complexes (DACH)Pt-malonato-Tam and (DACH)Pt-malonato-hydroxy-Tam were then prepared by coupling the barium salts derived from the malonato-Tam and malonato-hydroxy-Tam with the nitrate derived from (DACH)PtCl(2). Study of the biochemical properties of these two platinum complexes showed that, while the hydroxy-Tam complex is satisfactorily recognized by the estrogen receptor (relative binding affinity, RBA=6.4 %), the Tam complex is less well recognized (RBA=0.5 %). The effects of these complexes on two hormone-dependent breast cancer cell lines (MCF7 and MVLN) were studied in vitro. Both complexes showed an antiproliferative effect on MCF7 cells, and an antiestrogenic effect on MVLN cells. The observed effects appear to be essentially antihormonal, since incorporation of the (DACH)Pt fragment into the tamoxifen skeleton did not cause an increase in the cytotoxicity of the complexes.     

Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. II. Network‐forming DGEBA + MDA

Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (T_g) rises above the cure temperature (T_cure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of T_cure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E_1OH = 44 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and T_cure. The relation between x, r, and T_g, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in C_p in the glassy region with x and T_cure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004     

Evaluation of structural similarity based on reduced dimensionality representations of protein structure

Protein similarity estimations can be achieved using reduced dimensional representations and we describe a new application for the generation of two-dimensional maps from the three-dimensional structure. The code for the dimensionality reduction is based on the concept of pseudo-random generation of two-dimensional coordinates and Monte Carlo-like acceptance criteria for the generated coordinates. A new method for calculating protein similarity is developed by introducing a distance-dependent similarity field. Similarity of two proteins is derived from similarity field indices between amino acids based on various criteria such as hydrophobicity, residue replacement factors and conformational similarity, each showing a one factor Gaussian dependence. Results on comparisons of misfolded protein models with data sets of correctly folded structures show that discrimination between correctly folded and misfolded structures is possible. Tests were carried out on five different proteins, comparing a misfolded protein structure with members of the same topology, architecture, family and domain according to the CATH classification.     

Accepting its random coil nature allows a partial NMR assignment of the neuronal Tau protein

A combined strategy to obtain a partial NMR assignment of the neuronal Tau protein is presented. Confronted with the extreme spectral degeneracy that the spectrum of this 441 amino acid long unstructured protein presents, we have introduced a graphical procedure based on residue type-specific product planes. Combining this strategy with the search for pairwise motifs, and combining the spectra of different Tau isoforms and even of peptides derived from the native sequence, we arrive at a partial assignment that is sufficient to map the interactions of Tau with its molecular partners. The obtained assignments equally confirm the absence of regular secondary structure in the isolated protein.     

On the mechanisms of secondary flows in a gas vortex unit

The hydrodynamics of secondary flow phenomena in a disc‐shaped gas vortex unit (GVU) is investigated using experimentally validated numerical simulations. The simulation using ANSYS FLUENT^® v.14a reveals the development of a backflow region along the core of the central gas exhaust, and of a counterflow multivortex region in the bulk of the disc part of the unit. Under the tested conditions, the GVU flow is found to be highly spiraling in nature. Secondary flow phenomena develop as swirl becomes stronger. The backflow region develops first via the swirl‐decay mechanism in the exhaust line. Near‐wall jet formation in the boundary layers near the GVU end‐walls eventually results in flow reversal in the bulk of the unit. When the jets grow stronger the counterflow becomes multivortex. The simulation results are validated with experimental data obtained from Stereoscopic Particle Image Velocimetry and surface oil visualization measurements. © 2018 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 64: 1859–1873, 2018     

Oxidative catabolism of α-tocopherol in rat liver microsomes

The goal of this study was to clarify the mechanism responsible for the catabolism of α-tocopherol. The vitamin, bound to albumin, was incubated with rat liver microsomes and appeared to be broken down. Optimal production of the metabolite was obtained when 1 mg of microsomal protein was incubated with 36 μM of α-tocopherol in the presence of 1.5 mM of NADPH. Chromatographic and mass spectrometric analyses of the metabolite led to the conclusion that it consists of an ω-acid with an opened chroman ring, although we could not perform nuclear magnetic resonance analysis to confirm this. Our data show that α-tocopherol is ω-oxidized to a carboxylic acid and that this process can occur in rat liver microsomes in the presence of NADPH and O₂. The oxidation to the quinone structure appears to be a subsequent event that may be artifactual and/or catalyzed by a microsomal enzyme(s).     

Model of a polymer chain twisted inside a statistical segment. Poly(3‐hexylthiophene) in chloroform solutions

A set of hydrodynamic methods in extremely dilute solutions (determination of intrinsic viscosity [η ], translational diffusion D and flotation in a centrifugal field s ) was used in the studies of conformational properties, dimensions and equilibrium rigidity of individual molecules of a series of samples of poly(3‐hexylthiophene). Absolute molecular masses M _sD were determined. The Mark–Kuhn–Houwink equations for the range of M _sD from 2240 to 15 300 g mol^?1 are given. For the first time, an analysis of conformational properties and equilibrium flexibility of poly(3‐hexylthiophene) molecules was carried out using the model of a statistical segment containing a twisted polymer chain. © 2017 Society of Chemical Industry