Structural and Catalytic Studies of a Trimethyltin Vanadate Coordination Polymer

The organotin vanadate [Me₃SnVO₃] (1) has been prepared and characterised in the solid state by powder X-ray diffraction (XRD), thermogravimetric analysis, multinuclear magic-angle spinning (MAS) NMR, IR and Raman spectroscopy. The phase purity and structure of microcrystalline 1 were confirmed by carrying out a full Rietveld structural refinement at ambient temperature and from conventional powder XRD. ⁵¹V and ¹¹⁹Sn MAS NMR data for compound 1 were in agreement with the predicted structure, showing two equally-abundant, nonequivalent Me₃Sn groups and two equally-abundant, nonequivalent vanadium atoms. The compound was applied as a catalyst for the liquid-phase epoxidation of olefins at 55 °C using tert-butyl hydroperoxide (tBuOOH) as the oxidant. The reaction rate for the different substrates followed the order cis-cyclooctene > (R)-(+)-limonene ≅ trans-2-octene > cyclododecene > styrene > 1-octene; the corresponding epoxides were the only observed products. Leaching tests indicated that the catalytic epoxidation of cyclooctene was mainly heterogeneous in nature. This paper is dedicated to Professor Ian Manners and his scientific accomplishments.     

miR-218-5p/RUNX2 Axis Positively Regulates Proliferation and Is Associated with Poor Prognosis in Cervical Cancer

The overexpression of miR-218-5p in cervical cancer (CC) cell lines decreases migration, invasion and proliferation. The objective was to identify target genes of miR-218-5p and the signaling pathways and cellular processes that they regulate. The relationship between the expression of miR-218-5p and RUNX2 and overall survival in CC as well as the effect of the exogenous overexpression of miR-218-5p on the level of RUNX2 were analyzed. The target gene prediction of miR-218-5p was performed in TargetScan, miRTarBase and miRDB. Predicted target genes were subjected to gene ontology (GO) and pathway enrichment analysis using the Kyoto Encyclopaedia of Genes and Genomes (KEGG). The miR-218-5p mimetic was transfected into C-33A and CaSki cells, and the miR-218-5p and RUNX2 levels were determined by RT–qPCR. Of the 118 predicted targets for miR-218-5p, 86 are involved in protein binding, and 10, including RUNX2, are involved in the upregulation of proliferation. Low miR-218-5p expression and a high level of RUNX2 are related to poor prognosis in CC. miR-218-5p overexpression is related to decreased RUNX2 expression in C-33A and CaSki cells. miR-218-5p may regulate RUNX2, and both molecules may be prognostic markers in CC.     

Development of novel soy-protein-based superabsorbent matrixes through the addition of salts

The addition of salts, like sodium bicarbonate (SB) or carbonate (SC), into the formulation of bioplastic materials may alter their hydrophilic character to a significant extent. Soy protein isolate (SPI) is a byproduct of the soybean oil industry, which, when properly blended with glycerol (GL), can be further processed through a lab-scale injection molding device. A maximum in the water uptake around 2250 or 2500% is obtained for bioplastics obtained when either SB or SC content is around 1 wt %, respectively. Thus, they exceed the limit to be considered superabsorbent materials (SAMs). Regarding their mechanical properties, a higher presence of SB within the SPI/GL matrix provides materials with a higher extensibility and lower Young's modulus. A higher water uptake is observed after replacing SB for SC in the formulation, probably related to a higher alkalinization of the material as well as to the high hydrophilicity of the carbonate. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47012.     

Synthesis and characterization of cellulose acetate from royal palm tree agroindustrial waste

This study provides a novel value‐added utilization of the agroindustrial waste of royal palm tree leaf sheath to produce cellulose acetate. One of the motivations of this work was the fact that Brazil is one of the largest heart of palm producers in the world. However, as a result of extraction and processing, tons of waste are generated and discharged to the environment. Such waste is rich in lignocellulosic material, which could be reused to obtain derivatives of interest and commercial value. The synthesis of cellulose acetate was performed through a homogeneous acetylation reaction. Three different conditions were tested for delignification of the raw material, which resulted in a reduction in lignin content from 17.75 to 7.72%. The highest yield of cellulose acetate reached 99.5%, with degree of substitutions ranging between 2.08 and 2.82, which indicates satisfactory conversion. The Fourier transform infrared spectrum showed that practically all hydroxyl groups were replaced by acetate groups; this was also confirmed by nuclear magnetic resonance analysis. X‐ray diffraction analysis showed that the cellulose acetate crystallinity index was 8.9%. This demonstrates the viable potential of cellulose acetate production with low cost and use of highly available agroindustrial waste. POLYM. ENG. SCI., 59:891–898, 2019. © 2018 Society of Plastics Engineers     

A Mitochondrial Membrane Exopolyphosphatase Is Modulated by, and Plays a Role in, the Energy Metabolism of Hard Tick Rhipicephalus (Boophilus) microplus Embryos

The physiological roles of polyphosphates (polyP) recently found in arthropod mitochondria remain obscure. Here, the relationship between the mitochondrial membrane exopolyphosphatase (PPX) and the energy metabolism of hard tick Rhipicephalus microplus embryos are investigated. Mitochondrial respiration was activated by adenosine diphosphate using polyP as the only source of inorganic phosphate (P(i)) and this activation was much greater using polyP(3) than polyP(15). After mitochondrial subfractionation, most of the PPX activity was recovered in the membrane fraction and its kinetic analysis revealed that the affinity for polyP(3) was 10 times stronger than that for polyP(15). Membrane PPX activity was also increased in the presence of the respiratory substrate pyruvic acid and after addition of the protonophore carbonyl cyanide-p-trifluoromethoxyphenylhydrazone. Furthermore, these stimulatory effects disappeared upon addition of the cytochrome oxidase inhibitor potassium cyanide and the activity was completely inhibited by 20 μg/mL heparin. The activity was either increased or decreased by 50% upon addition of dithiothreitol or hydrogen peroxide, respectively, suggesting redox regulation. These results indicate a PPX activity that is regulated during mitochondrial respiration and that plays a role in adenosine-5'-triphosphate synthesis in hard tick embryos.     

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.     

Comparative study using different infrared zones of the solventless activation of organic reactions

In this work, the results of a study comparing the use of irradiation from different regions of the infrared spectrum for the promotion of several organic reactions, are presented and discussed. This use of eco-conditions provides a green approach to chemical synthesis. A set of ten different organic reactions were evaluated, including the Knoevenagel, Hantzsch, Biginelli and Meldrum reactions. It is important to highlight the use of a commercial device that produces infrared irradiation in the near infrared region and its distribution by convection providing heating uniformity, significantly reducing reaction times, achieving good yields and proceeding in the absence of solvent. It is also worth noting that a variety of different reactions may be performed at the same time. Finally, the products obtained were identified using TLC, together with corresponding MS-data, complementarily in comparison of NMR (1)H and (13)C data with literature information.     

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.     

Control of fluidized bed coating particles using Gaussian spectral pressure distribution

Fluidization has been used extensively in many industrial processes in chemical, food and pharmaceutical branches. However, the operational conditions of these processes frequently lead to the defluidization phenomenon or to the total collapse of the particles in the bed. The maintenance of stable conditions in the fluidization regime during fluidized bed coating processes is very important, because the moisture content excess can cause the defluidization of the bed. The objective of this work was to apply a new methodology, known as Gaussian spectral pressure distribution, to monitor and control the defluidization phenomenon in a fluidized bed coating process using microcrystalline cellulose as fluidizing particles. The work was performed in two stages: 1) monitoring of the fluidization regimes during the development of the coating process without control and 2) control of the airflow rate and of the coating suspension flow rate using PI controllers. The experiments were carried out varying solid particle mass, coating suspension flow rate and excess air velocity in relation to the minimum fluidization velocity working with a temperature of 70 °C. The Gaussian mean frequency evolution showed the fluidization regime transitions and it allowed to define a band of stable regime (6.0 Hz to 7.0 Hz), which was used as a set-point range of the controllers to manipulate the signal of command for frequency converter and for the peristaltic pump. The application of Åström and Hägglund [29] method allowed obtaining the PI controller parameters for the converter and the reaction curve method provided an initial guess of the PI controller parameters for the pump. The experiments of microcrystalline cellulose coating in closed-loop showed that the use of a control system allowed obtaining better fluid-dynamic conditions of the bed in relation to the process without control.     

The influence of chromate quenching and chloride contamination level on the performance of the painted hot-dipped galvanized steel (duplex system)

The influences of the chromate quenching step and the surface chloride contamination levels of galvanized steel on the performance of duplex systems were studied. Steel panels were galvanized in a commercial steel bath adopting three different postdipping procedures. A comparative study of the galvanized steel, both painted and nonpainted, was performed by electrochemical techniques. It was verified that the chloride contamination level of the galvanized steel surfaces is the main cause of duplex system failures. An explanation for the influence of the chromate quenching on the performance of duplex systems was presented.