Synthesis, characterization and crystal structure of a novel thiocyanate–ruthenium(II) complex

The cis-[Ru(dppb)(Me-bipy)(NCS)₂], dppb = 1,4-bis (diphenylphosphino)butane, Me-bipy = 4,4′-dimethyl-2,2′-bipyridine, and NCS = thiocyanate, was synthesized and characterized by spectroscopic and electrochemical techniques and its structure was determined by crystal X-ray analysis. The crystal structure reveals that the coordination geometry around the Ru(II) center is distorted octahedron where two molecules of thiocyanate are bonded to the ruthenium through nitrogen atom in cis orientation. The half-wave formal potential value E_1/2 = 0.8 V (versus Ag/AgCl) observed is considerable higher than that for the cis-[RuCl₂(dppb)(Me-bipy)] complex, E_1/2 = 0.6 V (versus Ag/AgCl), well illustrating the strong π-acceptor effect the NCS ligand toward the backbonding interaction with the Ru(II) metal center. The MLCT absorption bands of the thiocyanate complex present a higher molar absorptivity (about 12%) compared with the cis-[RuCl₂(dppb)(Me-bipy)] complex, in the same experimental conditions. These properties make the complex potentially promising for the photosensitization process.     

Miscibility and morphology of poly(vinylidene fluoride)/poly[(vinylidene fluoride)‐ran‐trifluorethylene] blends

This study presents an investigation of the effect of the different crystalline phases of each blend component on miscibility when blending poly(vinylidene fluoride) (PVDF) and its copolymer poly[(vinylidene fluoride)‐ran‐trifluorethylene] [P(VDF–TrFE)] containing 72 mol % of VDF. It was found that, when both components crystallized in their ferroelectric phase, the PVDF showed a strong effect on the crystallinity and phase‐transition temperature of the copolymer, indicating partial miscibility in the crystalline state. On the other hand, immiscibility was observed when both components, after melting, were crystallized in their paraelectric phase. In this case, however, a decrease in crystallization temperatures suggested a strong interaction between monomers in the liquid state. Blend morphologies indicated that, in spite of the lack of miscibility in the crystalline state, there is at least miscibility between PVDF and P(VDF–TrFE) in the liquid state, and that a very intimate mixture of the two phases on the lamellar level can be maintained upon crystallization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1362–1369, 2002     

Off-line optimization and control for real time integration of a three-phase hydrogenation catalytic reactor

In order to develop and test the integration procedure, in this paper a real time process integration involving the optimization and control of the process is presented, in this case, with the two-layer approach. The used optimization algorithms were Levenberg–Marquardt and SQP that solve a non-linear least square problem subject to bounds on the variables. The two-layer approach is a hierarchical control structure where an optimization layer calculates the set points and manipulated variables to the advanced controller, which is based on the dynamic matrix control with constraints (QDMC). The non-isothermal dynamic model of the three-phase slurry catalytic reactor with appropriate solution procedure was utilized in this work (Vasco de Toledo, E. C., Santana, P. L., Maciel, M. R. W., & Maciel Filho, R. (2001). Dynamic modeling of a three-phase catalytic slurry reactor. Chemical Engineering Science, 56, 6055–6061). The model consists on mass and heat balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. The model was used to describe the dynamic behavior of hydrogenation reaction of o-cresol to obtain 2-methil-cyclohexanol, in the presence of a catalyst Ni/SiO₂.     

Update on the pharmacology of Spirulina (Arthrospira), an unconventional food

Spirulina (Arthrospira), a filamentous, unicellular alga, is a cyanobacterium grown in certain countries as food for human and animal consumption. It is also used to derive additives in pharmaceuticals and foods. This alga is a rich source of proteins, vitamins, amino acids, minerals, and other nutrients. Its main use, therefore, is as a food supplement. Over the last few years, however, it has been found to have many additional pharmacological properties. Thus, it has been experimentally proven, in vivo and in vitro that it is effective to treat certain allergies, anemia, cancer, hepatotoxicity, viral and cardiovascular diseases, hyperglycemia, hyperlipidemia, immunodeficiency, and inflammatory processes, among others. Several of these activities are attributed to Spirulina itself or to some of its components including fatty acids omega-3 or omega-6, beta-carotene, alpha-tocopherol, phycocyanin, phenol compounds, and a recently isolated complex, Ca-Spirulan (Ca-SP). This paper aims to update and critically review the results published over the last few years with regards to these properties. The conclusion is that even if this cyanobacterium has been one of the most extensively studied from the chemical, pharmacological and toxicological points of view, it is still necessary to expand the research in order to have more consistent data for its possible use in human beings.     

Electrochemical behaviour of heat-treated AlZnMg alloys in chloride solutions containing sulphate

The electrochemical corrosion and passivation of Al5Zn1.7Mg0.23Cu0.053Nb alloys, submitted to different heat treatments (cold-rolled, annealed, quenched and aged, and quenched in two steps and aged), in sulphate-containing chloride solutions, has been studied by means of cyclic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The cyclic polarization curves showed that sulphate addition to the chloride solution produced a poor reproducible shift of the breakdown potential to more positive potentials. The repassivation potentials, much more reproducible, and practically separating the passive from the pitting potential region, were slightly displaced in the negative direction with that addition. When the alloys were potentiodynamically polarized in the passive potential region, sulphate was incorporated in the oxide film, thus precluding chloride ingress. In addition, Zn depletion was favoured, whereas Mg losses were avoided. Different equivalent circuits corresponding to different alloys and potentials in the passive and pitting regions were employed to account for the electrochemical processes taking place in each condition. This work shows that sulphate makes these alloys more sensitive to corrosion, increasing the fracture properties of the surface layer and favouring the pitting attack over greater areas than chloride alone.     

Effect of the addition of Cr and Nb on the microstructure and electrochemical corrosion of heat-treatable Al-Zn-Mg alloys

The effect of the addition of Cr and Nb on the microstructure and the electrochemical corrosion of the weldable, high-strength and stress corrosion cracking (SCC) resistant Al-5%Zn–1.67%Mg–0.23%Cu alloy (H) has been studied. Combined additions of the alloying elements, J (with Nb), L (with Cr) and O (with Cr and Nb) and different heat treatments, ST (cold-rolled), A (annealed), F (quenched), B (quenched and aged) and C (quenched in two steps and aged), to obtain different microstructures and hardness have been performed. To correlate the electrochemical corrosion with the microstructure of the specimens, corrosion potential (E _cor) measurements in different chloride solutions were performed and optical microscopy, SEM, TEM and EDX were applied. In chloride solutions containing dissolved O₂ or H₂O₂, the present alloys were polarized up to the pitting attack. It was shown that theE _cor measurements were very sensitive to the alloy composition and heat treatment, increasing in the order H < J < L < O < Al (for a given heat treatment) and F < A ST < B < C (for a given alloy). The MgZn₂ precipitates of the annealed (A) and cold-rolled (ST) specimens were dissolved in chloride solutions containing oxidizing agents and pitting attack was shown to develop in the cavities where the precipitates were present. In the specimens B and C, the compositions of the precipitate free zones was found to be equal to that of the matrix solid solution and preferential intergranular attack was not evident, this being in agreement with their SCC resistance. The addition of Cr and Nb increased the pitting corrosion resistance. The effects of Cr and Nb were additive, that of Cr being predominant, either, in theE _cor shift or in the increase in the pitting corrosion resistance.     

The role of the Tm3+ concentration on CaMoO4 properties processed by microwave hydrothermal under stirring condition

The compounds based on calcium molybdate (CaMoO₄) are the subject of extensive research due to their excellent optical properties and a broad range of potential technological applications. In this work, we report a systematic study of CaMoO₄:Tm³⁺ phosphors synthesized by coprecipitation and processed in a microwave-hydrothermal system at low temperature (100°C) and stirring. The effect of the Tm³⁺ doping content (0%–12%) is studied in full detail to understand their role in the CaMoO₄:Tm³⁺ morphological, structural, and luminescent properties. The X-ray diffraction, Raman, and Fourier Transform Infrared spectroscopic techniques revealed that all the prepared powders have a tetragonal crystal structure with a distinct density of cation vacancies and structural disorders. The band gap remains almost constant for doping levels lower than 8%, but it narrows strongly for powders doped with 12% Tm³⁺ ions. The designed phosphors have shown two emission bands in which intensity depends on the Tm³⁺ ions doping level. For doping levels lower than 2%, the photoluminescence profile displays a broad emission band peaking at 543 nm (green). For concentrations higher than 4%, the band centered at 543 nm decreases in intensity and the near-infrared emission band at around 800 nm, assigned to ³F₃, ³H₄ → ³H₆ transitions from Tm³⁺ ion, become more intense. The outcomes of this work reveal that appropriated Tm³⁺ ions doping levels can be applied to suppress the PL emission in the visible range and improve that in the near-infrared region in CaMoO₄-based materials.     

Fabrication of hybrid proton-exchange membranes using a brandnew high temperature ionic liquid as charge transporting and clay modifier

The search for more compatibility between ionic liquids (ILs) and polymer matrices in proton-exchange membrane fuel cells (PEMFCs) is one of the ways in which IL leaking from proton-exchange membranes could be minimized. In this work, it is presented the synthesis of an aromatic high temperature ionic liquid (HTIL), which, incorporated into an aromatic matrix such as sulfonated polyether ether ketone (sPEEK), is expected to diminish the IL leaking that normally affects PEMFC. Phenylethylammonium trifluoromethane sulfonate (PhetaTfO) was successfully synthesized and characterized. Its melting point of 88°C makes it to classify as a HTIL and it was employed as modifier of natural Montmorillonite, forming the phenylethylammonium intercalated montmorillonite (MmtPheta) and thus, ternary membranes containing PhetaTfO, MmtPheta, and sPEEK were prepared and characterized. Immersion tests demonstrated a higher compatibility of PhetaTfO with matrix when compared to the reference DemaTfO, which was reflected in up to 30% lower IL loss by the synthesized IL than the DemaTfO; X-rays diffraction (XRD) patterns demonstrated that the modified clay was properly dispersed inside the membranes, while dynamic mechanical analyses (DMA) results indicated a strong plasticizer effect along the increase of PhetaTfO content inside the membrane, while at the same time, the conductivity increased in an exponential manner, which permitted to identify an empiric exponential equation to evaluate the effect of concentration on ionic conductivity. The maximum conductivity obtained at IL concentrations of around 38 wt% was 0.2 mS/cm. It could expect high ionic conductivities of 10 mS/cm when the concentration of this IL is 60%; nevertheless, in order to achieve that, crosslinking treatments should be done to give the membranes enough mechanical resistance.     

Poly(vinylidene fluoride) with zinc oxide and carbon nanotubes applied to pressure sheath layers in oil and gas pipelines

In this work, PVDF composites containing 0.2% (m/m) of carbon nanotubes (MWCNTs), PVDF with 5.0% (m/m) of zinc oxide (ZnO), and composites containing both particles in the same contents in the matrix were melt processed in a mini-extruder machine with double screws, using the counter-rotation mode. Composites were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic-mechanical analysis (DMA), and contact angle tests (CA). The samples presented the predominance of the α phase, with an increased degree of crystallinity as well as an increase in dimensional stability by incorporating both fillers, showing a synergistic effect between these particles, as shown on FTIR, DSC, and XRD results. SEM images showed a good dispersion of high aspect ratio particles. In general, DMA and TGA analysis showed that composites had not decreased their thermal and mechanical performance when compared to neat PVDF. Results of CA analysis showed an increase in the hydrophobicity of the sample containing MWCNTs. Permeability tests were also performed using a differential pressure system, combining high temperature and pressure, obtaining permeability measures and time lag. This work presents an alternative of composite materials, suggesting its application in the internal pressure sheath layers of oil and gas flexible pipes.     

Simple approach for the plasma treatment of polymeric membranes and investigation of the aging effect

The modification of the surface characteristics after treatment with plasma in polymeric materials, such as the aging phenomenon, calls the attention of research in the area of nonthermal plasma technology. In this work, a direct treatment with dielectric-barrier discharge plasma was used on the surfaces of ultrafiltration membranes. The measurements of the contact angle with water, attenuated total reflectance accessory, zeta potential, atomic force microscopy and scanning electron microscopy-MEV were performed on the surfaces to verify changes after plasma treatment and to understand the occurrence and timing of the plasma aging effect. In the analysis of the membrane performance, hydraulic permeation and protein retention tests were performed. The results showed an improvement in wettability and hydrophilic properties in the post-treated membranes. The study of reversibility/aging of the post-plasma surface is important for research that deals with the modification of polymeric membranes. Changes in surface morphology, topography and wettability of the membranes were observed up to seven days after treatment, with a tendency to return to the initial characteristics of the membranes.