Synthesis and characterization of polyurethane/titanium dioxide nanocomposites obtained by in situ polymerization

The development of new polymeric and polymeric based materials is fundamental to meet the market demands. This work aims the synthesis and characterization of polyurethane/titanium dioxide nanocomposite, using low cost commercial raw materials. Nanocomposites were synthesized by in situ polymerization reactions in which titanium dioxide were added in the following proportions, by weight, in relation to the mass obtained from the pure polymer: 0.5, 1.0, 2.0, 3.0, 5.0, 7.0, and 10.0 %. These reactions were based in poli (ε-caprolactone) and 1,6-diisocyanatohexane. The materials were characterized by infrared spectroscopy Fourier transform, scanning electron microscopy, differential scanning calorimetry analysis, thermogravimetric analysis, dynamic mechanical thermal analysis, and UV–Vis spectroscopy. Based on the obtained results it was concluded that the nanocomposites synthesized by in situ polymerization presented, in general, thermal properties (degradation temperature) and mechanical properties higher than the pure polymer.     

Degradation kinetics of epoxidized soybean oil composites filled with sisal fiber

Epoxidized soybean oil (ESO) composites were cured with methyl tetrahydrophthalic anhydride (MTHPA) and 2,4,6-tris(dimethylaminomethyl)phenol (DEH 35) as a catalyst, sisal fibers were added at 10% and 30% of percent per weight. Composites curing was monitored using Fourier transform infrared spectroscopy, whereas the thermal stability and the degradation kinetics were investigated using thermogravimetry (TG). ESO/MTHPA/DEH35/S10 and ESO/MTHPA/DEH35/S30 composites displayed curing temperatures approximately 100°C lower related to ESO/MTHPA/DEH35, as well as higher degree of conversion. Sisal addition improved the thermal stability, shifting the weight loss shifting the weight loss onset to higher temperature (from 82 to 120°C). Thermal degradation energy $$ was determined using Friedman, Kissinger-Akahira-Sunose and Ozawa-Flynn-Wall models. Sisal significantly increased $$, especially in the intermediate phase (α = 0.2 and 0.8). The degradation kinetics was investigated by TG, and the degradation mechanisms modeled using Kamal-Sourour, Sestack-Berggren, and 1st order (F1), showed excellent fit, with R² > 0.99. Acquired results demonstrate that sisal fiber addition benefited the curing process and increased the thermal stability of ESO composites.     

Strength Degradation and Failure Mechanisms of Electron-Beam Physical-Vapor-Deposited Thermal Barrier Coatings

Failure mechanisms were determined for electron-beam physical-vapor-deposited thermal barrier coating (TBC) systems from the degradation of mechanical properties and microstructural changes in a furnace cycle test. Bond strength degradation for TBCs resulted from the initiation and growth of interfacial delamination defects between the yttria-stabilized zirconia topcoat and the thermally grown alumina (TGO). It is proposed that defects started from concave depressions in the bondcoat surface created by the grit-blast-cleaning process and that defect growth was driven by the reduction in compressive strain in the TGO as the alumina deformed into and displaced the bondcoat during the cooling cycles. Inclusion of yttrium in the substrate resulted in a doubling of the furnace cycle life of the TBCs because of enhanced fracture toughness of the TGO-bondcoat interface.     

Single-phase and binary phase nanogranular ferrites for magnetic hyperthermia application

The study demonstrates the performance of heating efficiency in single-phase and binary phase spinel ferrite nanosystems. Ferrimagnetic cobalt ferrite (CoFe₂O₄) (CFO) and superparamagnetic copper ferrite/copper oxide (CuFe₂O₄/CuO) (CuF) nanosystems of different particle sizes were synthesized through a microwave-assisted coprecipitation method. The heating behavior was observed in range of both field amplitudes (8-24 kA/m at 516 kHz) and frequencies (325-973 kHz at 12 kA/m). The heating efficiency was analyzed and compared by means of particle size, magnetization, effective anisotropy constant, and Néel relaxation mechanism. Indeed, the heating rate was maximized in larger ferrite particles with low effective anisotropy constant. Moreover, though the magnetization and effective anisotropy constant of single-phase CoFe₂O₄ nanoparticles were higher, the binary phase CuFe₂O₄/CuO nanosystems of similar crystallite size (28 nm) exhibited superior heating efficiency (4.21°C/s). For a field amplitude and frequency of 24 kA/m and 516 kHz, the heating rate of CuF and CFO ferrites with different crystallite sizes decreased in the order of 4.21 > 2.14 > 0.58 > 0.52°C/s for 29 nm > 25 nm > 12 nm > 15 nm, respectively. The results emphasize that binary phase ferrite nanoparticles are better thermoseeds than the single-phase ferrites for the magnetic hyperthermia application.     

Prediction and comparison of textural properties of magnetic copolymer supports for enzyme immobilization

Magnetic polymers supports have proven to be valuable materials for enzyme immobilization, as they allow recovering the catalyst by magnetic separation, precluding the need for costly and time-consuming separation steps. In this study, magnetic copolymer supports were synthesized using styrene (STY) and different crosslinking agents (divinylbenzene, ethylene glycol dimethacrylate, or triethylene glycol dimethacrylate) and initiators (azobisisobutyronitrile or benzoyl peroxide) and used to immobilize Candida antarctica lipase B (CALB). The aim was to obtain biocatalysts with high enzymatic activity and satisfactory morphological properties for use in biotransformation reactions. Two morphological properties known to influence the immobilization yield were taken into consideration, specific surface area, and swelling index. Experimental data were compared to the predictions of a model based on molar balance, method of moments, numerical fractionation, and elementary gel structures. The high correlation (R² = 0.9974) between experimental and predicted values demonstrated the suitability of the model for estimating the textural properties of enzyme supports. CALB was successfully immobilized, showing high hydrolytic activity (500–700 U g⁻¹) and good thermal stability at 50°C. CALB/STY-EGDMA-M was 14 times more stable than free CALB. The results confirm the efficiency of the immobilization method and the suitability of the copolymers for enzyme immobilization.     

In situ compatibilization of a polyethylene,polypropylene, and polystyrene ternary blend through Friedel–Crafts alkylation

The Friedel–Crafts alkylation reaction has been applied to reactively compatibilize a ternary blend of high-density polyethylene (HDPE), polypropylene (PP), and polystyrene (PS). The reactions were carried out in an internal mixer using varying catalyst concentrations. The resulting compatibilizer was quantified after Soxhlet extraction. In addition, p-substitution due to the grafting of alkyl groups onto the PS benzene ring was identified via nuclear magnetic resonance spectroscopy. The size of the PS domain in the reactive compositions is decreased by 80%. Moreover, the phase in which PS droplets were dispersed varied, that is, in the nonreactive blends they were found in the PP phase and in the reactive blends they shifted toward the HDPE phase. The effect of the compatibilizing agent was to improve the mechanical properties of the blend. Even with the lowest catalyst content, the properties of elongation-at-break, tensile strength, toughness, and elastic modulus showed improvements. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48295.     

Activity of α‐Aminoadipate Reductase Depends on the N‐Terminally Extending Domain

L ‐α‐Aminoadipic acid reductases catalyze the ATP‐ and NADPH‐dependent reduction of L ‐α‐aminoadipic acid to the corresponding 6‐semialdehyde during fungal L ‐lysine biosynthesis. These reductases resemble peptide synthetases with regard to their multidomain composition but feature a unique domain of elusive function—now referred to as an adenylation activating (ADA) domain—that extends the reductase N‐terminally. Truncated enzymes based on NPS3, the L ‐α‐aminoadipic acid reductase of the basidiomycete Ceriporiopsis subvermispora, lacking the ADA domain either partially or entirely were tested for activity in vitro, together with an ADA‐adenylation didomain and the ADA domainless adenylation domain. We provide evidence that the ADA domain is required for substrate adenylation: that is, the initial step of the catalytic turnover. Our biochemical data are supported by in silico modeling that identified the ADA domain as a partial peptide synthetase condensation domain.     

Comparison of 10,11‐Dehydrocurvularin Polyketide Synthases from Alternaria cinerariae and Aspergillus terreus Highlights Key Structural Motifs

Iterative type I polyketide synthases (PKSs) from fungi are multifunctional enzymes that use their active sites repeatedly in a highly ordered sequence to assemble complex natural products. A phytotoxic macrolide with anticancer properties, 10,11‐dehydrocurvularin (DHC), is produced by cooperation of a highly reducing (HR) iterative PKS and a non‐reducing (NR) iterative PKS. We have identified the DHC gene cluster in Alternaria cinerariae, heterologously expressed the active HR PKS (Dhc3) and NR PKS (Dhc5) in yeast, and compared them to corresponding proteins that make DHC in Aspergillus terreus. Phylogenetic analysis and homology modeling of these enzymes identified variable surfaces and conserved motifs that are implicated in product formation.     

Produktschonende Betriebs‐ und Designparameter von Wärmeübertragern für temperaturempfindliche Prozessströme

To allow the calculation of product degradation rates as extension to the currently used thermotechnical design calculations for heat exchangers, a volume‐related, reaction‐kinetic approach was developed. Therefore, a model system was selected and the product protection design parameters were determined for a lab‐scale heat exchanger with the help of simulations. The validation was demonstrated in an experiment. Additionally, the product‐protecting operating parameters for the heat exchanger were calculated with a technically relevant set of compounds.