Synthesis and ex-situ evaluation of quaternized polysulfone as an anion exchange ionomer for AEM technologies

Anion exchange ionomer (AEI) is a critical component used on anion exchange membrane fuel cell (AEMFC) and alkaline water electrolyzer (AWE). In this work, quaternized polysulfone with different functionalization degree were used as an ionomer to evaluate the performance in the oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR), both implied in the operation of AEMFC and AWE. The synthesized ionomer exhibited a better performance in both reactions in comparison to the commercial AEI Aemion®. PSf-130 exhibited better performance, since IEC and surface area increases twice regarding the same parameters in the PSf-60. The PSf-130 conductivity increases three times regarding the value exhibited by PSf-60. Finally, the J_lim and J_k increases 67% and 100% for ORR. On the other hand, the same catalytic parameter increased 44% and 35% for HOR comparing both polysulfone-based ionomers. The Tafel slope values do not showed drastically changes for different ionomers indicating the same rate determining step (RDS) and the same mechanism in both reactions for all the ionomers.     

Investigation of Polyimidesiloxanes for Use as Adhesives by Electron Spectroscopy for Chemical Analysis

Angle-dependent electron spectroscopy for chemical analysis (ESCA) was used to examine the air facing surface (20–100 Å thick) composition of polyimidesiloxanes with different processing variations, and of varying polydimethylsiloxane (PDMS) content and block length (number of PDMS repeat unit varies from 1 to 9). Polyimide was clearly detected (due to the nitrogen content) in the 20–100 Å surface regions. This shows that a small amount of PDMS and short PDMS segment lengths in polyimidesiloxanes give a surface region with both PDMS and polyimide present. The surface composition, particularly that in the ca. 100 Å region, was correlated to the peel strength of polyimidesiloxane melt pressed to a metal substrate. Our results suggest that both PDMS and polyimide are essential components to rendering a needed peel strength. PDMS, having a good diffusive ability, readily reaches the substrate upon being pressed, achieving intimate contact, while imide groups interact with the substrate, presumably through chemical bonding; these two factors act synergistically to result in a high peel strength. In addition, the interaction mechanism and the failure mechanism involved in bonding polyimidesiloxane and metal substrate were also elucidated based on the ESCA results.     

High-Area Ti/Pt Electrodes for the Electrochemically Catalyzed Transesterification of Soybean Oil with Methanol

Biodiesel fuel is a renewable energy source normally produced in industry by using an alkaline homogeneous catalyst to promote the transesterification of oil and methanol to fatty acid methyl ester (FAME). Undesirable side reactions occur when poorly refined oils are used, leading to serious problems of product separation and low FAME yield. Therefore, about 85% of the cost of biodiesel is determined by the cost of the feedstock. Here, we describe the development of high-area Pt films deposited on Ti substrates for the electrolytic synthesis of biodiesel from soybean oil containing water, without the addition of catalyst. The higher both the calcination temperature and the number of layers deposited on the Ti surface, the higher the electrochemically active area of Pt exposed to surface. Conversion into esters in electrolysis is proportional to the increase in the superficial area of the Ti/Pt electrodes. Thus, it is possible to synthesize biodiesel using electrodes containing very low amounts of Pt (<0.441 mg cm^?2), an important parameter in the industrial production of biodiesel.     

Sintering of porous alumina obtained by biotemplate fibers for low thermal conductivity applications

In this research report, a sintering process of porous ceramic materials based on Al₂O₃ was employed using a method where a cation precursor solution is embedded in an organic fibrous cotton matrix. For porous green bodies, the precursor solution and cotton were annealed at temperatures in the range of 100–1600 °C using scanning electron microscopy (SEM) and thermogravimetric (TG) analysis to obtain a porous body formation and disposal process containing organic fibers and precursor solution. In a structure consisting of open pores and interconnected nanometric grains, despite the low porosity of around 40% (calculated geometrically), nitrogen physisorption determined a specific surface area of 14 m²/g, which shows much sintering of porous bodies. Energy dispersive X-ray (EDX) and X-ray diffraction (XRD) analytical methods revealed a predominant amount of α-Al₂O₃ in the sintered samples. Thermal properties of the sintered Al₂O₃ fibers were obtained by using the Laser Flash which resulted in the lower thermal conductivity obtained by α-Al₂O₃ and therefore improved its potential use as an insulating material.     

Effect of temperature on hot-air drying rate and on retention of antioxidant capacity in apple leathers

Fruit leathers are pectic gels, eaten as snack or dessert, obtained by dehydrating fruit purees. In this work, apple leathers were prepared by a hot-air drying process which allows the formation of a gel, following the “saccharide–acid–high methoxyl pectin” gelation mechanism. Leathers were produced at 50, 60 and 70 °C, from two formulations: control and added with potassium metabisulphite (KM) as antioxidant. The drying process was studied applying a diffusive model, while antioxidant capacity (AC) losses were represented by a first-order model. Activation energy for drying (20.6 kJ/mol) was lower than those estimated for AC losses in control (31.5 kJ/mol) and KM-added (37.9 kJ/mol) leathers. Therefore, the drying time reduction achieved by increasing air temperature is not sufficient to decrease AC losses in the range covered. AC retention decreased in both formulations at increasing air temperature. KM-added samples showed higher AC retention than the controls, except for those dried at 70 °C. Kinetic constants were lower for KM-added samples, suggesting a protective effect of the additive, especially at moderate air temperatures. In the most favorable situation, AC retention was of only 16%. Therefore, the functional character of these products may not be preserved if dried with hot air and the research on economically viable, less-severe drying technologies should be intensified.     

The role of lanthana loading on the catalytic properties of Pd/Al2O3-La2O3 in the NO reduction with H2

The role of La₂O₃ loading in Pd/Al₂O₃-La₂O₃ prepared by sol–gel on the catalytic properties in the NO reduction with H₂ was studied. The catalysts were characterized by N₂ physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.

The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La₂O₃ inclusion. The selectivity depends on the NO/H₂ molar ratio (GHSV = 72,000 h⁻¹) and the extent of interaction between Pd and La₂O₃. At NO/H₂ = 0.5, the catalysts show high N₂ selectivity (60–75%) at temperatures lower than 250 °C. For NO/H₂ = 1, the N₂ selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H₂O vapor. The high N₂ selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdO_x phase interacting with La₂O₃. The formation of this phase is favored by the spreading of PdO promoted by La₂O₃. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al₂O₃ the O₂ uptake is consistent with the oxidation of PdO to PdO₂, and when La₂O₃ is present the O₂ uptake exceeds that amount (1.5 times). La₂O₃ in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N₂.     

Total Electron Detachment and Induced Cationic Fragmentation Cross Sections for Superoxide Anion (O2−) Collisions with Benzene (C6H6) Molecules

In this study, novel experimental total electron detachment cross sections for O₂⁻ collisions with benzene molecules are reported for the impact energy range (10–1000 eV), as measured with a transmission beam apparatus. By analysing the positively charged species produced during the collision events, relative total ionisation cross sections were derived in the incident energy range of 160–900 eV. Relative partial ionisation cross sections for fragments with m/z ≤ 78 u were also given in this energy range. We also confirmed that heavier compounds (m/z > 78 u) formed for impact energies between 550 and 800 eV. In order to further our knowledge about the collision dynamics governing the fragmentation of such heavier molecular compounds, we performed molecular dynamics calculations within the framework of the Density Functional Theory (DFT). These results demonstrated that the fragmentation of these heavier compounds strongly supports the experimental evidence of m/z = 39–42, 50, 60 (u) cations formation, which contributed to the broad local maximum in the total ionisation observed from 550 to 800 eV. This work reveals the reactivity induced by molecular anions colliding with hydrocarbons at high energies, processes that can take place in the interstellar medium under various local conditions.     

Activity of Fluorine‐Containing Analogues of WC‐9 and Structurally Related Analogues against Two Intracellular Parasites: Trypanosoma cruzi and Toxoplasma gondii

Two obligate intracellular parasites, Trypanosoma cruzi, the agent of Chagas disease, and Toxoplasma gondii, an agent of toxoplasmosis, upregulate the mevalonate pathway of their host cells upon infection, which suggests that this host pathway could be a potential drug target. In this work, a number of compounds structurally related to WC‐9 (4‐phenoxyphenoxyethyl thiocyanate), a known squalene synthase inhibitor, were designed, synthesized, and evaluated for their effect on T. cruzi and T. gondii growth in tissue culture cells. Two fluorine‐containing derivatives, the 3‐(3‐fluorophenoxy)‐ and 3‐(4‐fluorophenoxy)phenoxyethyl thiocyanates, exhibited half‐maximal effective concentration (EC₅₀) values of 1.6 and 4.9 μm , respectively, against tachyzoites of T. gondii, whereas they showed similar potency to WC‐9 against intracellular T. cruzi (EC₅₀ values of 5.4 and 5.7 μm , respectively). In addition, 2‐[3‐ (phenoxy)phenoxyethylthio]ethyl‐1,1‐bisphosphonate, which is a hybrid inhibitor containing 3‐phenoxyphenoxy and bisphosphonate groups, has activity against T. gondii proliferation at sub‐micromolar levels (EC₅₀=0.7 μm ), which suggests a combined inhibitory effect of the two functional groups.     

Identification of Reference Genes for RT-qPCR Data Normalization in Cannabis sativa Stem Tissues

Gene expression profiling via quantitative real-time PCR is a robust technique widely used in the life sciences to compare gene expression patterns in, e.g., different tissues, growth conditions, or after specific treatments. In the field of plant science, real-time PCR is the gold standard to study the dynamics of gene expression and is used to validate the results generated with high throughput techniques, e.g., RNA-Seq. An accurate relative quantification of gene expression relies on the identification of appropriate reference genes, that need to be determined for each experimental set-up used and plant tissue studied. Here, we identify suitable reference genes for expression profiling in stems of textile hemp (Cannabis sativa L.), whose tissues (isolated bast fibres and core) are characterized by remarkable differences in cell wall composition. We additionally validate the reference genes by analysing the expression of putative candidates involved in the non-oxidative phase of the pentose phosphate pathway and in the first step of the shikimate pathway. The goal is to describe the possible regulation pattern of some genes involved in the provision of the precursors needed for lignin biosynthesis in the different hemp stem tissues. The results here shown are useful to design future studies focused on gene expression analyses in hemp.