Phosphonic acid‐containing polysulfones as anticorrosive layers

As a part of research work to elaborate polymeric materials for metal corrosion protection, we have developed a new family of phosphonic acid‐containing polymers. The synthesis and the characterization of polysulfones bearing alkyl phosphonate ester side groups are first described. These polymers are synthesized by direct polycondensation of a phosphonate ester‐containing bisphenol by aromatic nucleophilic substitution. The physicochemical properties of the resulting polymers are described. Acidic hydrolysis of phosphonate esters results in the formation of phosphonic acid groups. A series of phosphonic acid‐containing polysulfones is therefore obtained and characterized. A preliminary evaluation of the anticorrosive properties of these polymers is described. In 0.25M Na₂SO₄ solution, the corrosion rate of a polymer‐coated mild steel sample is much lower than of the free metal substrate. These results suggest that phosphonic acid‐containing polysulfones might be interesting as anticorrosive coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41890.     

El Sur Global: Future Resilient City

Shifting the focus from futuristic visions, Alfredo Brillembourg and Hubert Klumpner with Alexis Kalagas of interdisciplinary design practice Urban-Think Tank urge us to ‘forget about utopia’, for in the most part the urban environment of 2050 is already built. Architects’ sights need to be set on the sometimes grim and unfolding reality of favelas and the world's informal cities.     

Theoretical and empirical assessment of evaluation methods of the electric charge transference in welding with covered electrodes

The present work is based on an assessment of experimentally obtained results from the application of different methods of evaluation, reported in the specialised literature, of the electrical charge transference stability in the arc. A simple factorial design, taking the welding current as independent variable, was applied to the process with an AWS A5.1 E6013 electrode. The welds were carried out in the flat position by a gravity device. It was possible to obtain criteria to classify the electrical charge transference stability of the process by digital signal processing and a statistical technique. The outcome was based on visual inspection and morphologic studies. It was concluded that amongst the considered parameters, the average value of the arc conductivity during reignition peaks and the quantity of reignition peaks are the more representative indices, both from statistics and from phenomenological points of view. This finding is validated by the fact that the bead morphology and the stability analysis of the electrical charge transference process coincides with the fact that the 160 A (for 4 mm-diameter electrodes) is the most stable regime.     

Control of the permeability of a porous media using a thermally sensitive polymer

Experiments explore the reduction in permeability of a porous bead pack when a suspension of thermally responsive polymer is injected and the temperature then increased above the thermal activation temperature. The change in permeability is greater with higher polymer concentration, provided that the ionic concentration of the solution is sufficient for floc formation. The time for activation of the blocking effect is within tens of seconds to minutes of when the polymer solution is heated. This is consistent with the timescale for diffusion‐limited aggregation, although the detailed value depends on the geometry and polymer concentration. Dynamical experiments demonstrate that once the porous media is blocked, adding additional polymer has no effect. The mechanism for permeability reduction may be modeled in the context of a pore‐network model, and we build a simple model to illustrate the permeability reduction as a function of the fraction of pores links which are blocked. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1193–1201, 2014     

Copper‐Catalyzed Trifluoromethylation of Aliphatic N‐Arylhydrazones: A Concise Synthetic Entry to 2‐Trifluoromethylindoles from Simple Aldehydes

The copper‐catalyzed C(sp²) H trifluoromethylation of N,N‐disubstituted hydrazones using the Togni reagent is demonstrated to proceed efficiently for aliphatic aldehyde‐derived substrates. The success of the reactions relied on the choice of the N,N‐diphenylamino group as the terminal hydrazone amino group where N,N‐dialkylamino groups were preferred for (hetero)aromatic aldehyde‐derived substrates. In addition, the trifluoromethylated N‐arylhydrazones are shown to be ideal substrates for Fischer indole synthesis allowing a straightforward, three‐step access to 2‐trifluoromethylindole derivatives from simple aldehydes.

     

Replication-Deficient Lymphocytic Choriomeningitis Virus-Vectored Vaccine Candidate for the Induction of T Cell Immunity against Mycobacterium tuberculosis

Mycobacterium tuberculosis (Mtb) represents a major burden to global health, and refined vaccines are needed. Replication-deficient lymphocytic choriomeningitis virus (rLCMV)-based vaccine vectors against cytomegalovirus have proven safe for human use and elicited robust T cell responses in a large proportion of vaccine recipients. Here, we developed an rLCMV vaccine expressing the Mtb antigens TB10.4 and Ag85B. In mice, rLCMV elicited high frequencies of polyfunctional Mtb-specific CD8 and CD4 T cell responses. CD8 but not CD4 T cells were efficiently boosted upon vector re-vaccination. High-frequency responses were also observed in neonatally vaccinated mice, and co-administration of rLCMV with Expanded Program of Immunization (EPI) vaccines did not result in substantial reciprocal interference. Importantly, rLCMV immunization significantly reduced the lung Mtb burden upon aerosol challenge, resulting in improved lung ventilation. Protection was associated with increased CD8 T cell recruitment but reduced CD4 T cell infiltration upon Mtb challenge. When combining rLCMV with BCG vaccination in a heterologous prime-boost regimen, responses to the rLCMV-encoded Mtb antigens were further augmented, but protection was not significantly different from rLCMV or BCG vaccination alone. This work suggests that rLCMV may show utility for neonatal and/or adult vaccination efforts against pulmonary tuberculosis.     

Quantification of Mixtures of C2 and C3 Hydroxy Acids and Products of Glycerol Oxidation by High-Performance Liquid Chromatography and Quantitative 13C NMR

The aim of this study was to develop an improved general method for detecting and quantifying mixtures of hydroxy acids and other products of glycerol oxidation in aqueous media, to prevent the confusions that can occur due to similarities and interactions between these compounds depending on media conditions. Standard potential products of glycerol oxidation—glycerol, glyceraldehyde, dihydroxyacetone, glyceric acid, lactic acid, glycolic acid, glyoxylic acid, oxalic acid, tartronic acid, and mesoxalic acid—were analyzed by high-performance liquid chromatography (HPLC) and quantitative ¹³C nuclear magnetic resonance (NMR), in mixtures of known composition. The results obtained were concordant with the known compositions tested. HPLC was more accurate than quantitative ¹³C NMR for simple mixtures, but ¹³C NMR was required for complex mixtures containing dihydroxyacetone and glycerol, oxalic acid and mesoxalic acid, or glyoxylic acid and tartronic acid, pairs of compounds not well separated or detected by HPLC. As proof-of-concept, an unknown mixture generated by glycerol oxidation was analyzed by HPLC and quantitative ¹³C NMR. The results obtained were concordant and allowed accurate determination of the composition of the sample, which contained mesoxalic acid as the major product, with oxalic acid, tartronic acid, and glyceric acid as by-products.     

Discovery of Ubonodin,an Antimicrobial Lasso Peptide Active against Members of the Burkholderia cepacia Complex

We report the heterologous expression, structure, and antimicrobial activity of a lasso peptide, ubonodin, encoded in the genome of Burkholderia ubonensis. The topology of ubonodin is unprecedented amongst lasso peptides, with 18 of its 28 amino acids found in the mechanically bonded loop segment. Ubonodin inhibits RNA polymerase in vitro and has potent antimicrobial activity against several pathogenic members of the Burkholderia genus, most notably B. cepacia and B. multivorans, causative agents of lung infections in cystic fibrosis patients.     

Influence of titania on zirconia promoted Cu/SiO2 catalysts for methanol synthesis from CO/H2 and CO2/H2

The effects of adding mixtures of titania and zirconia on the methanol synthesis activity and selectivity of Cu/SiO₂ were investigated. The synthesis of methanol from both CO/H₂ and CO₂/H₂ mixtures was examined at 0.65 MPa and temperatures between 448 and 573 K. For CO hydrogenation, the addition of ZrO₂ alone increased the methanol synthesis activity of Cu/SiO₂ by up to three-fold. Substitution of a portion of the ZrO₂ by TiO₂ decreased the methanol synthesis activity of the catalyst relative to that observed when only ZrO₂ is added. ZrO₂ addition also enhanced the methane synthesis activity by as much as seven fold. In the case of CO₂ hydrogenation, the maximum methanol synthesis activity is achieved when a 50/50 wt% mixture of ZrO₂ and TiO₂ is added to Cu/SiO₂. Neither the presence of the oxide additive nor its composition had any effect on the activity of the reverse water–gas-shift reaction, which suggests that this reaction proceeds only on Cu. The observed effects of ZrO₂ and TiO₂ on the catalytic activity of methanol synthesis from CO and CO₂, and methane synthesis from CO, are interpreted in terms of the strength and concentration of acidic and basic groups on the surface of the dispersed oxide.