Catalytic Reduction of 4-Nitrobenzoic Acid by cis-[Rh(CO)2(Amine)2](PF6) Complexes Under Water–Gas Shift Reaction Conditions: Kinetics Study

Rhodium(I) complexes of the type, cis-[Rh(CO)₂(amine)₂](PF₆) where (amine = 3-picoline, 2-picoline, pyridine, 2,6-lutidina or 3,5-lutidine) dissolved in 80% aqueous amine solutions catalyzed the selective reduction of 4-nitrobenzoic acid to 4-aminobenzoic acid under CO atmosphere. The importance of these catalytic systems is their high chemo selectivity for the aromatic nitro group of the 4-nitrobenzoic acid with respect to the carboxylic group, allowing the production of the desired aromatic amine in high yields. The 4-aminobenzoic acid production depends on the nature of the coordinated amine. The Rh/3,5-lutidine system, the most active catalyst among tested, displays turnover frequencies for 4-aminobenzoic acid production of about 173 moles per mole Rh per day for [Rh] = 1 × 10^?4 mol, [4-nitrobenzoic acid] = 3.82 × 10^?3mol, 10 mL of 80% aqueous 3,5-lutidine, P(CO) = 0.9 atm at 100 °C. Analyses of kinetic results for the Rh/3,5-lutidine system show a first order dependence on 4-nitrobenzoic acid concentration, a non-linear dependence on CO pressure, a segmented Arrhenius plot and dependence on the nature of the reducing gas agent. These data are discussed in terms of a possible mechanism.     

Mechanical and dynamical mechanical properties of chloroprene rubber and cellulose II composites

Vulcanized composites of chloroprene rubber (CR) with cellulose II (Cel II) as a filler were investigated. Cel II, obtained by the coagulation of cellulose xanthate, was incorporated in the rubber by the traditional method. The filler content varied from 0 to 30 phr. For comparison purposes, carbon black (CB)–CR composites were also studied. The CB amount varied from 0 to 45 phr. The mechanical and dynamic mechanical properties were determined, and the CR composite containing 20 phr of Cel II showed the best set of properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2425–2430, 2004     

Characterisation of surface oxidation of nickel-titanium alloy by ion-beam and electrochemical techniques

The passivating effects produced on Ni₄₉Ti₅₁ (at.%) shape memory alloy by electropolishing in methanol-sulphuric acid electrolyte or thermal treatment in air are investigated with ion-beam techniques (secondary ion mass spectrometry (SIMS) and mass resolved ion scattering spectrometry (MARISS)) and electrochemical techniques (polarisation curves, photocurrent spectroscopy and impedance). Electropolishing produces a limited passivation due to formation of a thin layer of amorphous TiO₂, which causes only a slight hindrance to the oxygen evolution reaction. Thermal treatment in air at 450 °C causes a more substantial passivation due to formation of a thick oxide layer, estimated at about 80 nm for a 16 h treatment on the basis of weight increase, disregarding roughness. Data indicate that the film produced by thermal oxidation has probably a duplex structure, with a porous outer layer with inclusions of Ni species and a compact inner layer, in contact with the substrate, consisting of (essentially) nickel free TiO₂ rutile.     

Accelerated Aging in 3-mol%-Yttria-Stabilized Tetragonal Zirconia Ceramics Sintered in Reducing Conditions

The aging behavior of 3-mol%-yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics sintered in air and in reducing conditions was investigated at 140°C in water vapor. It was observed by X-ray diffraction (XRD) that 3Y-TZP samples sintered in reducing conditions exhibited significantly higher tetragonal-to-monoclinic transformation than samples with similar density and average grain size values but obtained by sintering in air. This fact is explained by the increase of the oxygen vacancy concentration and by the presence at the grain boundary region of a new aggregate phase formed because of the exolution of Fe²⁺ ions observed by X-ray photoelectron spectroscopy.     

On the steady‐state drop size distribution in stirred vessels. Part I: Effect of dispersed phase viscosity

Previous studies on emulsification have used the maximum drop size (d_max) or Sauter mean diameter ( ) to investigate the effect of viscosity on the drop size distribution (DSD), however, these parameters fall short for highly polydispersed emulsions. In this investigation (Part I), the steady‐state DSD of dilute emulsions is studied using of silicon oils with viscosities varying across six orders of magnitude at different stirring speeds. Different emulsification regimes were identified; our modeling and analysis is centered on the intermediate viscosity range where interfacial cohesive stresses can be considered negligible and drop size increases with viscosity. The bimodal frequency distributions by volume were well described using two log‐normal density functions. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3293–3302, 2018     

Structural Determinants of the Selectivity of 3‐Benzyluracil‐1‐acetic Acids toward Human Enzymes Aldose Reductase and AKR1B10

The human enzymes aldose reductase (AR) and AKR1B10 have been thoroughly explored in terms of their roles in diabetes, inflammatory disorders, and cancer. In this study we identified two new lead compounds, 2‐(3‐(4‐chloro‐3‐nitrobenzyl)‐2,4‐dioxo‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0048, 3 ) and 2‐(2,4‐dioxo‐3‐(2,3,4,5‐tetrabromo‐6‐methoxybenzyl)‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0049, 4 ), which selectively target these enzymes. Although 3 and 4 share the 3‐benzyluracil‐1‐acetic acid scaffold, they have different substituents in their aryl moieties. Inhibition studies along with thermodynamic and structural characterizations of both enzymes revealed that the chloronitrobenzyl moiety of compound 3 can open the AR specificity pocket but not that of the AKR1B10 cognate. In contrast, the larger atoms at the ortho and/or meta positions of compound 4 prevent the AR specificity pocket from opening due to steric hindrance and provide a tighter fit to the AKR1B10 inhibitor binding pocket, probably enhanced by the displacement of a disordered water molecule trapped in a hydrophobic subpocket, creating an enthalpic signature. Furthermore, this selectivity also occurs in the cell, which enables the development of a more efficient drug design strategy: compound 3 prevents sorbitol accumulation in human retinal ARPE‐19 cells, whereas 4 stops proliferation in human lung cancer NCI‐H460 cells.     

Synthesis and characterization of the polyols by air oxidation of soybean oil and its effect on the morphology and dynamic mechanical properties of poly(vinyl chloride) blends

The use of natural additives, with low toxicity and good compatibility, for PVC is becoming increasingly attractive. In this study, soybean oil additives were prepared by air oxidation reactions and blending with PVC. The oxidation reaction produced a significant increase in the number of hydroxyl groups in soybean oil; however, this kind of reaction results in the formation of a heterogeneous structure due to free radical reactions in the medium. The oxidized soybean oil improved the compatibility with PVC due to an increase in the number of polar groups, such as hydroxyls, and thus a reduction in the amount of atactic polymer was observed. Furthermore, an increase in the molecular weight of the oxidized oil, as well as large amounts of polar groups contributes to reducing the migration of oil in the PVC. Regarding the crystallinity of PVC, the use of pure and oxidized soybean oil causes small changes in the crystalline phase of the polymer. Oxidized soybean oil has great potential for usage as a secondary plasticizer for PVC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42102.     

The Anti-Inflammatory Effects of the Methanolic Extract and Fractions from Davilla elliptica St. Hil. (Dilleniaceae) on Bothrops jararaca Envenomation

Inflammation and haemorrhage are the main characteristics of tissue injury in botropic envenomation. Although some studies have shown that anti-venom prevents systemic reactions, it is not efficient in preventing tissue injury at the site of the bite. Therefore, this work was undertaken to investigate the anti-inflammatory effects of the methanolic extract and fractions from D. elliptica and to evaluate the role of matrix metalloproteinases (MMPs) in this process. Effects of the extract and fractions from D. elliptica were evaluated using a carrageenan-induced paw oedema model in rats, and leukocyte rolling was visualized by intravital. The quantification of MMPs activities (MMP-2 and MMP-9) extracted from the dermis of mice treated with extract and fractions alone or incubated with venom was determined by zymographic analyses. Our results show that intraperitoneal (i.p.) injection of fractions significantly reduced paw oedema after the carrageenan challenge. Treatment with the tannins fraction also resulted in considerable inhibition of the rolling of leukocytes and this fraction was able to decrease the activation of MMP-9. These results confirmed the anti-inflammatory activity of the methanolic extract and tannins fraction of D. elliptica and showed that the dermonecrosis properties of B. jararaca venom might be mediated through the inhibition of MMP-9 activity.     

Promising curaua fiber‐reinforced polyester composite for high‐impact ballistic multilayered armor

A typical multilayered armor system (MAS) is composed of a harder front ceramic tile, which is able to erode heavy ammunition, such as the 7.62 mm bullet, followed by a second layer to further reduce the impact energy. Aramid fabric is a common choice for the second layer. In the present work, polyester matrix composites reinforced with 10 to 30 vol% of curaua fibers, despite having much lower strength and stiffness than aramid fabric, displayed similar trauma indentation in a standard clay witness simulating the human body. Impedance matching and scanning electron microscopy analyses suggest effective energy absorption through ceramic fragment capture by curaua composites. Additionally, because of the high cost of aramid fabric, a full MAS with curaua fiber composite is much cheaper than a MAS composed of aramid fabric. Taking into consideration, both the economical and environmental advantages of natural fibers, it is concluded that curaua fiber‐reinforced polyester composite could replace aramid fabric as the second layer in MASs for personal ballistic protection. POLYM. ENG. SCI., 57:947–954, 2017. © 2016 Society of Plastics Engineers