N‐Benzyl‐4‐((heteroaryl)methyl)benzamides: A New Class of Direct NADH‐Dependent 2‐trans Enoyl–Acyl Carrier Protein Reductase (InhA) Inhibitors with Antitubercular Activity

Isoniazid (INH) remains one of the cornerstones of antitubercular chemotherapy for drug‐sensitive strains of M. tuberculosis bacteria. However, the increasing prevalence of multidrug‐resistant (MDR) and extensively drug‐resistant (XDR) strains containing mutations in the KatG enzyme, which is responsible for the activation of INH into its antitubercular form, have rendered this drug of little or no use in many cases of drug‐resistant tuberculosis. Presented herein is a novel family of antitubercular direct NADH‐dependent 2‐trans enoyl–acyl carrier protein reductase (InhA) inhibitors based on an N‐benzyl‐4‐((heteroaryl)methyl)benzamide template; unlike INH, these do not require prior activation by KatG. Given their direct InhA target engagement, these compounds should be able to circumvent KatG‐related resistance in the clinic. The lead molecules were shown to be potent inhibitors of InhA and showed activity against M. tuberculosis bacteria. This new family of inhibitors was found to be chemically tractable, as exemplified by the facile synthesis of analogues and the establishment of structure–activity relationships. Furthermore, a co‐crystal structure of the initial hit with the enzyme is disclosed, providing valuable information toward the design of new InhA inhibitors for the treatment of MDR/XDR tuberculosis.     

Effect of the annealing procedure and the molecular weight on the crystalline phase morphology and thermal properties of polylactide

The thermomechanical properties of poly(lactide) (PLA) are strongly related to its semicrystalline microstructure and morphology. Thermal annealing is a strategy to improve the crystallinity of PLA. However, the different techniques and specimen types needed for each kind of characterization could lead to misleading conclusions. In this work, annealed samples of three PLA grades with different molecular weights were studied by DSC, wide angle X‐ray scattering and polarized optical microscopy (POM) and the results are related to their thermomechanical and impact properties. Special focus is put on the POM results obtained by different approaches and the suitability of each of them to be related to the thermomechanical properties. By annealing medium molecular weight PLA specimens at 140 °C an important increase of the heat distortion temperature was obtained, which was not related to the spherulite size but to the combination of high crystallinity degree together with high α/α′ crystal type ratio. However, the impact properties of annealed PLA decreased with increase in the annealing temperature according to an increment in crystallinity and in the α/α′ crystal ratio. © 2019 Society of Chemical Industry     

Experimental Design Applied for Cost and Efficiency of Antioxidants in Biodiesel

Oxidation stability is a parameter of great importance for biodiesel quality control to both producers and subsequent consumers. To maintain the quality of biodiesel, currently the most effective and economical method is the addition of antioxidants that prevent or retard the biofuel oxidation reaction. In this study, efficiency and cost of synthetic antioxidants added to B100 biodiesel from soybean oil and pork fat were evaluated, using butylhydroxyanisole (BHA), butylhydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ), in pure form or in mixtures, according to a simplex-centroid mixture experimental design. Results demonstrate an increased induction period (IP) in all trials when compared to the control sample, and TBHQ was the only antioxidant alone that met all the specification standards, while BHT and BHA alone met only the American standard specifications. The antioxidant mixture that presented the highest synergistic effect was that of TBHQ and BHA. Multi-response optimization indicated an optimum formulation containing 75 % TBHQ and 25 % BHA with an IP of 7.27 h at 110 °C and the antioxidant mixture cost of 31.31 USD, to be added for a ton of biodiesel. This simplex-centroid mixture experimental design shows an ability to be applied in the biodiesel, oils and fats industry to evaluate the oxidation stability and the occurrence of synergism between different mixtures of synthetic or natural antioxidants and their costs.     

Synthetic fayalite Fe2SiO4 by kinetically controlled reaction between hematite and silicon carbide

The present work explores the preparation of fayalite α-Fe₂SiO₄, the iron-rich end-member of the olivine solid-solution series, as a tar removal catalyst for biomass gasification. The synthetic procedure was developed starting from the stoichiometric mixture of hematite and micrometer size silicon carbide and employing thermal treatments in controlled atmospheres at 1000-1100°C supported by thermodynamic modeling to assess the required redox conditions. The treatments in dry and humidified inert gas yielded phase mixtures containing metallic Fe as one of the main phases, thus emphasizing a shortage of oxygen supply. XRD and TGA studies of precursor mixtures on heating in dry CO₂ demonstrated a multistep mechanism of the overall reaction including (a) fast reactivity between silicon carbide and hematite at ~920°C with formation of metallic Fe and amorphous silica followed by (b) formation of fayalite involving oxygen supplied in the form of CO₂ and competing with (c) over-oxidation to thermodynamically favorable Fe₃O₄+SiO₂ mixture. Comparative studies of reactivity in powdered and pelletized samples emphasized the importance of the kinetic factor in the formation of Fe₂SiO₄ while preventing further oxidation. The preferential formation of fayalite in the CO₂ atmosphere is shown to be favored by shorter treatments of compacted samples at higher temperatures. The procedure was designed (2-step heating to 1100°C in CO₂ followed by fast cooling) for the preparation of pelletized fayalite α-Fe₂SiO₄ catalyst with only minor traces of surface over-oxidation which can be suppressed by adding 10 vol.% of forming gas to CO₂ flow.     

The Irritant Effects of Pharmaceutically Applied Surfactants

Dermal or transdermal medication may lead to irritant contact dermatitis. However, little information is available on the irritant effect of surfactants which are applied in topical formulations. Our aim was to examine the irritant effect of the most frequent compounds in topical products. A murine model was applied. The following compounds were examined: sodium lauryl sulphate (SLS), polyethoxylated (40EO) hydrogenated castor oil and sucrose laurate. SLS led to severe erythema, increase in transepidermal water loss (TEWL) and induced necrosis and accumulation of neutrophylic granulocytes and lymphocytes. Exposure to sucrose laurate resulted in an elevation of TEWL, but histology did not reveal impairment of the skin structure. Application of polyethoxylated (40EO) hydrogenated castor oil was not accompanied by tissue damage. Special attention should be paid to the irritant effect of SLS. Polyethoxylated (40EO) hydrogenated castor oil seems to be a non-irritant agent and sucrose laurate is also a promising candidate for application in topical preparations.     

Effect of the nanoparticles in the stability of hydrolyzed polyacrylamide/resorcinol/formaldehyde gel systems for water shut-off/conformance control applications

The main objective of this work is to evaluate the inclusion of nanoparticles to partially hydrolyzed polyacrylamide/resorcinol/formaldehyde gel systems to improve the stability under static and dynamic conditions. Oxide nanoparticles (<100 mg·L⁻¹) of SiO₂, Al₂O₃, MgO, and Cr₂O₃ were employed and characterized by their physicochemical properties. Gels were prepared and subsequently placed at 70 °C for evaluating the nanoparticles influence in gel strength through rheological properties and syneresis measurements. Al₂O₃ nanoparticles showed the highest potential for the reduction of the syneresis phenomena, followed by MgO and Cr₂O₃. The SiO₂ nanoparticles lead to a higher degradation of the gel. As the zeta potential increases, the syneresis of the gel system decreases. The nanoparticles did not significantly affect the storage modulus, describing similar gel strength than the original gel. Also, displacement tests showed an incremental of 64% of oil recovery regarding the system in the absence of Al₂O₃ nanoparticles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47568.     

CALIBRATION OF THE METHOD TO MEASURE BUBBLE PROPERTIES IN 2D FLUIDIZED BEDS

The purpose of the present work is to demonstrate the reliability of a digital image processing technique. A CCD (Charge Coupled Device) is used to perform an investigation on the bubble properties of a 2D gas-solid fluidized bed, and the aim of this study is to establish a criterion in order to reject all images that could not be interpreted as bubbles. This may lead to an alteration of the information obtained. The two-dimensional fluidized bed is 20 cm wide and at least 20 cm high, and the field of view of the camera is 12.54 cm wide and 12.99 cm high. In this way, bubbles could be totally or partially placed into this field of view so that a partial image of a bubble could be analyzed as a whole bubble. With this calibration, a geometric decision criterion for the rejection of nonbubble images was developed.