Remendable polymers via reversible Diels–Alder cycloaddition of anthracene‐containing copolymers with fullerenes

Poly(lauryl methacrylate)s with anthracene moieties in the side chain were converted with C₆₀‐fullerene and phenyl‐C₆₁‐butyric acid methyl ester (PCBM), resulting in new remendable (self‐healing) polymeric materials. The utilization of differently substituted anthracene monomers enabled the tuning of the reactivity and the resulting mechanical properties. Copolymers with different contents of the anthracene moieties were synthesized and characterized using size exclusion chromatography, ¹H nuclear magnetic resonance (NMR) spectroscopy as well as differential scanning calorimetry (DSC). ¹H NMR spectroscopic studies were utilized in order to investigate the reversibility of the Diels–Alder reaction between copolymers with C₆₀‐fullerene and PCBM, respectively, in solution. In order to investigate the conversion of the polymers with C₆₀‐fullerene and PCBM in bulk, additionally, DSC, nanoindentation, rheology, atomic force microscopy (AFM), 3D microscopy, simultaneous thermal analysis (STA) and FT‐Raman investigations were performed. The fullerene‐containing copolymers could be healed in a temperature range of 40–80 °C. Consequently, a new generation of low temperature remendable polymers could be established. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45916.     

Polymeric Hollow‐Fiber Bundles as Immersed Heat Exchangers

Plastic immersed heat exchangers are used in various applications where chemically neutral and noncorrosive equipment is required. Their potential competitors, namely, polymeric hollow‐fiber bundles, were investigated. Three different fiber bundles were tested as immersed coolers of a hot reservoir. Two types of polypropylene hollow fibers with various outside diameters were employed. Fibers were twisted with different curvature to achieve better distribution and improve natural convection on their outer surface. Calculation by experimental results was compared with the equation for natural convection across the horizontal cylinder, which overestimates heat transfer coefficients and can be applied for only rough estimation. Experimentally achieved pressure drops agreed well with theoretical prediction for laminar flow.     

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.     

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.     

Thermodynamic analysis and optimization of RWGS processes for solar syngas production from CO2

Process systems were investigated for syngas production from CO₂ and renewable energy (solar) by the reverse water‐gas shift (RWGS) and the reverse water‐gas shift chemical looping (RWGS‐CL) process. Thermodynamic analysis and optimization was performed to maximize the solar‐to‐syngas (StS) efficiency η_StS. Special emphasis was laid on product gas separation. For RWGS‐CL, maximum StS efficiencies of 14.2 and 14.4% were achieved without and with heat integration, respectively. The StS efficiency is dictated by the low overall efficiency of H₂ production. RWGS‐CL is most beneficial for the production of pure CO, where the StS efficiency is one percent point higher compared to that of the RWGS process with heat integration. Heat integration leads to significant reductions in external heat demand since most of the gas phase process heat can be integrated. The StS efficiencies for RWGS and RWGS‐CL achieve the same level as the reported values for solar thermochemical syngas production. © 2016 American Institute of Chemical Engineers AIChE J, 63: 15–22, 2017