Kinetics of Multi‐Step Redox Processes by Time‐Resolved In Situ X‐ray Diffraction

The kinetics of redox reactions of iron oxide in oxygen carrier 50Fe₂O₃/MgAl₂O₄ are examined using different time‐resolved techniques. Reduction kinetics are studied by H₂ temperature‐programmed reduction (H₂‐TPR) monitored by time‐resolved in situ XRD. In contrast to conventional TPR, in situ XRD distinguishes the three‐stage reduction of Fe₂O₃ → Fe₃O₄ → FeO → Fe. It also shows that the oxidation of Fe → Fe₃O₄ by CO₂ has no intermediate crystalline phases, explaining why its kinetics can easily be investigated by conventional CO₂ temperature‐programmed oxidation (CO₂‐TPO). A shrinking core model which takes into account solid state diffusion allows describing the experimental data.     

The P2Y2 Receptor C-Terminal Tail Modulates but Is Dispensable for β-Arrestin Recruitment

The P2Y₂ receptor (P2Y₂R) is a G protein-coupled receptor that is activated by extracellular ATP and UTP, to a similar extent. This allows it to play roles in the cell’s response to the (increased) release of these nucleotides, e.g., in response to stress situations, including mechanical stress and oxygen deprivation. However, despite its involvement in important (patho)physiological processes, the intracellular signaling induced by the P2Y₂R remains incompletely described. Therefore, this study implemented a NanoBiT^® functional complementation assay to shed more light on the recruitment of β-arrestins (βarr1 and βarr2) upon receptor activation. More specifically, upon determination of the optimal configuration in this assay system, the effect of different (receptor) residues/regions on βarr recruitment to the receptor in response to ATP or UTP was estimated. To this end, the linker was shortened, the C-terminal tail was truncated, and phosphorylatable residues in the third intracellular loop of the receptor were mutated, in either singly or multiply adapted constructs. The results showed that none of the introduced adaptations entirely abolished the recruitment of either βarr, although EC₅₀ values differed and time-luminescence profiles appeared to be qualitatively altered. The results hint at the C-terminal tail modulating the interaction with βarr, while not being indispensable.     

Nanostructured Polymer Blends: From Core/Shell Nanoobjects to Continuous Three‐Phase Morphologies

A PS‐b‐PIP‐b‐PMMA copolymer has been melt‐blended with homo‐PMMA with a similar molecular weight as the PMMA block. For a 50:50 wt.‐% mixture, the components form 3D bicontinuous lamellae. Upon annealing at 190 °C, a more regular network is observed, which consists of PMMA and 55 nm‐thick bilayered lamellae of triblock copolymer, both being continuous. This co‐continuity persists even when $\overline {M} _{{\rm n}} $ of the homo‐PMMA is twice that of the PMMA block in the copolymer. For 30:70 and 20:80 wt.‐% copolymer/homopolymer pair, the copolymer forms cylindrical and spherical phases, respectively. Blends have also been prepared by solvent casting. Large domains of copolymer interconnected by few lamellae are observed in the 50:50 blend that reorganize into a bicontinuous network upon annealing.

     

Synthesis and Surface-Active Properties of Uronic Amide Derivatives,Surfactants from Renewable Organic Raw Materials

Short chemical syntheses were developed to produce a new set of surfactants from uronic acids derived from widely available raw materials. Three different strategies were used to synthesize uronic amide derivatives, the structures of which were totally characterized by spectrometric methods (IR, MS, ¹H-RMN and ¹³C-RMN). The best one, using an acid chloride as the synthetic intermediate, furnished the expected amides as a mixture of anomers in 46–58% global yield. Surface-active properties (CMC, γ_cmc, Γ_max, A _min) of homologous series of uronic acid N-alkylamides from C8 to C18 were also assessed. In general, these sugar-based surfactants exhibited good surface-activities, and appeared as valuable nonionic surfactants compared to octylphenol 9–10 ethylene oxide condensate, the most well-known nonionic surfactant. Increasing the alkyl chain length influenced the CMC values for both glucuronic and galacturonic N-alkylamide derivatives. The galacturonic N-alkylamides decreased γ_cmc at slower values than their counterpart’s glucuronic N-alkylamides.     

Multidimensional characterization,Landau levels and Density of States in epitaxial graphene grown on SiC substrates

Using high-temperature annealing conditions with a graphite cap covering the C-face of, both, on axis and 8° off-axis 4H-SiC samples, large and homogeneous single epitaxial graphene layers have been grown. Raman spectroscopy shows evidence of the almost free-standing character of these monolayer graphene sheets, which was confirmed by magneto-transport measurements. On the best samples, we find a moderate p-type doping, a high-carrier mobility and resolve the half-integer quantum Hall effect typical of high-quality graphene samples. A rough estimation of the density of states is given from temperature measurements.     

Effects of mechanical interactions on the hydrostatic stress in randomly distributed rubber particles in an amorphous polymer matrix

The equivalent inclusion method (EIM) assuming linear elasticity is used to calculate the mechanical interactions between spherical rubber particles in an amorphous matrix, as in a rubber toughened polymer. The influences of the various calculation parameters are examined and it is shown that the method can provide reliable results with regard to the level of hydrostatic stress in the particles. Damage of the material is simulated by replacing the most stressed particles by voids. Numerical simulations for several hundreds of interacting particles give information on the kinetics and spatial organisation of the damage. It appears that, as the volume fraction of particles increases from 10 to 20%, the spatial configuration of the damage evolves from a localised to a diffuse mode. These results are discussed in relation to the efficiency of rubber toughening.     

Emulsifying and foaming properties of native and chemically modified peptides from the 2S and 12S proteins of rapeseed (Brassica napus L.)

The 2S and 12S proteins of rapeseed were isolated and subsequently hydrolyzed by pepsin or a combination of pepsin plus trypsin. The resulting hydrolysates had a 15% degree of hydrolysis and were purified by gel filtration chromatography in order to obtain homogeneous peptide fractions. Three major fractions, having an average peptide chain length of 7.5–11 amino acids, were recovered. Purified peptide fractions were acylated with butyric anhydride and sulfamidated with p-toluenesulfonyl chloride. The degree of modification was always higher than 90%. Emulsifying and foaming properties of native and chemically modified peptides were studied and compared to those of sodium dodecyl sulfate (SDS) as standard. A peptide fraction from the 15% hydrolysis of the 12S protein exhibited the best foaming properties. After sulfamidation, this peptide fraction showed a foam formation similar to that of SDS. Whereas the attachment of toluene groups generally improved the surface properties, the incorporation of an aliphatic chain of four atoms of carbon was detrimental in most of the cases. On the other hand, none of the native or hydrophobized peptide fractions was able to form a stable emulsion.