Studies on the Autoxidation of Phenylacetylene

Phenylacetylene is oxidized slowly by molecular oxygen at 110°C. The main oxidation products are benzoic acid, benzoic anhydride, and benzaldehyde. Besides the oxidation, thermal dimerization, oligomerization, and polymerization processes also take place. As individual products 1,4-diphenylbut-1-yn-3-ene and 1,3,5-triphenylbenzene were identified. About 80% of the phenylacetylene consumed are converted into products of low volatility which could not be detected by gas chromatography. The autoxidation of acetylenic hydrocarbones [1] preferably yields products of the attack at C H bonds in α-position to the CC triple bond. An attack at the CC riple bond was a first proved in the case of phenylacetylene, which besides polymeric products yielded benzaldehyde, acetophenone, and organic acids [2]. Later, in the causes of the isomeric octynes [3] and of various 1-Phenylalk-1-ynes [4] an attack at the CC triple bond was also proved. As the primary products of the oxidative attack at the CC triple bond short-lived oxirenes or their valence isomers, the corresponding ketocarbenes are to be expected. Indeed, their rearrangement products were found in the oxidation mixtures of both the isomeric ocytnes [3] and the 1-phenylalk-1-ynes [4]. Other products of the oxidative attack at the CC triple bond are lower carboxylic acids, formally produced by oxidative cleavage of the CC triple bond [3, 4].     

Residual stress measurements in irradiated solution-annealed type 304 stainless steel tubing

Immersion density and residual stress measurements were made on solution-annealed type 304 stainless steel capsule tubing irradiated up to fluence levels of 9 × 10²² n/cm² (E > 0.1 MeV). The measured residual stress is dependent on the competition between differential swelling which builds up differential stresses, and irradiation creep which relaxes these stresses. The measurements were analyzed using a bilinear swelling equation formulated with swelling data from the same heat of material. The temperatures and fluence levels of the swelling and slit tube data were each calculated with the same computer code. At high fluence, when swelling was in the steady-state region, the effective irradiation creep rate increased by a factor of about three. Further analysis was made assuming that stress-enhanced swelling and swelling-enhanced irradiation creep were the enhanced relaxation mechanisms.     

Influence of Methanol on Prion Reduction during High Temperature and High Pressure Oleochemical Processes

Prion‐reduction in standard biodiesel processes is caused by acidic and alkaline conditions. In the alternative RepCat biodiesel process, efficient prion‐reduction can be achieved by high‐temperature/pressure. However, a possible increase in thermostability of prions in the presence of methanol during these conditions has not previously been investigated, and is verified in this work. Samples are spiked with prions, treated with methanol, and incubated at 220 °C at 80 bar for 30 min. No traces of protease‐resistant prion protein (as proxy for prions) are detected in tallow or glycerine (as the final by‐product) after treatment. Serial dilutions of spiked prions show at least 6 log₁₀ prion reduction. More importantly, similar effects are detected using milder conditions of 200 °C at 70 bar for 15 min, representing the worst‐case conditions of the process. In conclusion, this study shows that methanol does not increase the thermostability of prions and the RepCat process can efficiently eliminate prions and is therefore safe for the usage of category 1 tallow. Practical Applications: The study further supports the applicability of RepCat process in reducing prion‐contamination in the presence of methanol. Furthermore, the conditions leads to a considerable reduction of prions in glycerine obtained as by‐product.     

L?slichkeit und gel-elektrophoretische Muster hitzedenaturierter Proteine, auch von st?rkehaltigen Proben, nach Einwirkung von Na-dodecylsulfat (SDS)

Zusammenfassung Das Lösungsvermögen des Anionendetergents Na-dodecylsulfat (SDS) in Gegenwart disulfidbrückenspaltender Reagentien auf native und auf hitzedenaturierte Proteine wird an Fleisch-und Kartoffelproteinen mit Hilfe elektrophoretischer Methoden untersucht. Die zur Resolubilisierung notwendige Menge an SDS und die erforderliche Incubationszeit werden für die verschiedenen Proben ermittelt. Die Proteine des Skeletmuskels von Rind, Schwein, Huhn und Pute einerseits und die Proteine der europäischen Kartoffelsorten und der südamerikanischen Primitivkultivare andererseits zeigen in der SDS-PAGE ein sehr ähnliches Bandenmuster, das speziesdifferenzierend kaum ausgewertet werden kann, aber ein gutes Charakteristikum für Muskel-bzw. Kartoffelproteine ist.

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Solubility and electrophoretic patterns of heat-denaturated proteins (including samples containing starch) after treatment with SDS (sodiumdodecylsulfat)

Summary The ability of the anionic detergent SDS (sodium-dodecylsulfate) to solubilize native and heat-denaturated proteins of meat and potatoes in presence of disulphide reducing agents was checked by electrophoretic methods. Skeletal muscle proteins of beef, pork, chicken and turkey have shown very similar patterns in SDS-gelelectrophoresis, which could hardly be used for species identification but they are characteristic for fresh or boiled muscles. Proteins of European potato cultivars and primitive cultivars from South America have almost identical SDS-patterns even if taken from boiled potatoes. Their patterns are different from the proteins of other European crops plants and may serve for detection of the presence of potatoes in food mixtures.

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Diese Arbeit ist Teil der Dissertation von I. de Wreede. Die Analyse der tierischen Proteine bearbeitete I. de Wreede.Sonderdruckanfragen an: I. de Wreede (Adresse siehe oben)     

Thrombomodulin modulates growth of tumor cells independent of its anticoagulant activity

Thrombomodulin (TM), recognized as an essential vessel wall cofactor of the antithrombotic mechanism, is also expressed by a wide range of tumor cells. Tumor cell lines subcloned from four patients with malignant melanoma displayed a negative correlation between TM expression and cell proliferation in vitro and in vivo. Overexpression of wild-type TM decreased cell proliferation in vitro and tumor growth in vivo. TM mutants with altered protein C activation capacity lead to a similar effect. In contrast, transfection of melanoma cells with mutant TM constructs, in which a portion of the cytoplasmic or lectin domain was deleted, abrogated the antiproliferative effect associated with overexpression of wild-type TM. Experiments performed with either peptide agonists/antagonists of the thrombin receptor, with hirudin, or with inhibitors of thrombin-TM interaction did not alter the growth inhibitory effect of TM overexpression. These data suggest that TM exerts an effect on cell proliferation independent of thrombin and the thrombin receptor, possibly related to the binding of novel ligands to determinants in the lectin domain which might trigger signal transduction pathways dependent on the cytoplasmic domain.     

Finite‐Element Implementation of a Self‐consistent Texture Model with a Hardening Law Based on Dislocation Densities

A self‐consistent texture model is implemented in the finite‐element code ABAQUS/Explicit®. Hardening of the slip systems is described by evolution laws for dislocation densities, and the Bauschinger effect is included. With these ingredients the cold rolling of an IF‐steel is simulated and the evolution of texture and anisotropy is examined. The use of the dislocation based hardening law is found to have a significant effect on the evolution of the anisotropic yield surface, but only very little influence on the texture. Furthermore, the hardening model is used to investigate the evolution of dislocation densities in differently oriented grains during plane strain compression. It is found that the dislocation density varies greatly depending on orientation, an observation which can help to explain the orientation dependence of recrystallization.     

Carbon nanowalls deposited by inductively coupled plasma enhanced chemical vapor deposition using aluminum acetylacetonate as precursor

Well aligned carbon nanowalls, a few nanometers thick, were fabricated by continuous flow of aluminum acetylacetonate (Al(acac)₃) without a catalyst, and independent of substrate material. The nanowalls were grown on Si, and steel substrates using inductively coupled plasma-enhanced chemical vapor deposition. Deposition parameters like flow of argon gas and substrate temperature were correlated with the growth of carbon nanowalls. For a high flow of argon carrier gas, an increased amount of aluminum in the film and a reduced lateral size of the carbon walls were found. The aluminum is present inside the carbon nanowall matrix in the form of well crystallized nanosized Al₄C₃ precipitates.     

Emergent membrane-affecting properties of BSA-gold nanoparticle constructs

By adsorbing bovine serum albumin (BSA) on gold nanoparticles (Aunps) with diameters 30 nm and 80 nm, different degrees of protein unfolding were obtained. Adsorption and adlayer conformation were characterized by UV-vis spectroscopy, ζ-potential measurements, steady-state and time-resolved fluorescence. The unfolding was also studied using 1-anilino-8-naphthalene sulfonate (ANS) as an extrinsic probe, showing that BSA unfolds more on 80 nm Aunp than on 30 nm Aunp. Langmuir monolayer studies using two distinct methods of introducing the BSA and BSA-Aunp constructs accompanied with Brewster Angle Microscopy (BAM) and Digital Video Microscope (DVM) imaging demonstrated that BSA-Aunp constructs induce film miscibility with L-α-phosphatidylethanolamine not seen for BSA or Aunp alone. The changes induced by partial unfolding clearly give better film-penetration ability, as well as disruption of liquid crystalline domains in the film, thereby inducing film miscibility. Gold or protein only does not possess the nanoscale film-affecting properties of the protein-gold constructs, and as such the surface-active and miscibility-affecting characteristics of the BSA-Aunp represent emergent qualities.