Olefinreaktionen in Gegenwart wolfram- und molybdänhaltiger Katalysatorsysteme vom Ziegler-Natta-Typ

Reactions of Alkenes in the Presence of Tungsten- and Molybdenum-containing Ziegler-Natta-Catalysts In connection with investigations of reactions of alkenes under the conditions of metathesis we studied the reactions of a mixture of 2-pentene/toluene in presence of the catalytic systems WCl₆/EtAlCl₂ and MoCl₅/EtAlCl₂ in homogeneous liquid phase. Alkylation of toluene, metathesis of 2-pentene and also indirect isomerisation of double bonds have been determined in dependence of the molar proportions of 2-pentene/MeCl_x, toluene/2-pentene, and MeCl_x/EtAlCl₂, the addition order (“formation”) of reactants, the “building time” of catalytic system and the reaction time. Compositions of the reaction mixtures have been determined by GLC.     

Imazalil Degradation upon Applying Ozone—Transformation Products,Kinetics, and Toxicity of Treated Aqueous Solutions

The elimination of the pesticide imazalil (IMZ) spiked into ultrapure water as well as into wastewater applying ozone (O₃) and the identification of transformation products was investigated. O₃ under hydroxyl radical suppression conditions reacted rapidly with the aliphatic double bond or the imidazole ring in IMZ, yielding several transformation products by partial oxidation. The structures of four oxidation products not yet described were characterized and identified after liquid chromatography coupled with high resolution, high mass accuracy, mass and tandem mass spectrometry (LC/MS and -MSⁿ) in ultrapure water. For two identified transformation products, generated via direct ozone attack on IMZ, formation pathways were proposed. In wastewater, only two of those transformation products were observed. Kinetics studies for the reaction of IMZ with O₃, evaluated by the competition kinetic method, resulted in a second-order rate constant k_O3,IMZ ～ (1.02 ± 0.03)?×?10⁵ M^?1 s^?1 at pH 6.6 ± 0.2, indicating that IMZ is completely transformed during the ozonation process. Tests of acute toxicity were performed applying a solution of IMZ in ultrapure water or treated wastewater to Daphnia magna. In both cases the decrease of toxicity was observed after ozone treatment.     

Functionally Graded Ceramics Fabricated with Side‐by‐Side Tape Casting for Use in Magnetic Refrigeration

Functionally graded ceramic tapes have been fabricated by a side‐by‐side tape casting technique. This study shows the possibility and describes the main principles of adjacent coflow of slurries resulting in formation of thin plates of graded ceramic material. Results showed that the small variations of solvent and binder system concentrations have a substantial effect on slurry viscosity. Varying these parameters showed that side‐by‐side tape casting with a well‐defined interface area is possible for slurries with viscosities above 3500 mPa s at a casting shear rate of 3.3 s^?1. As it was expected, the choice of de‐bindering and sintering regimes significantly influences crack formation, and a three‐step heating programme was found to result in tapes of the highest quality. The interface regions of green graded tapes were investigated structurally by scanning electron microscopy; for a distinct identification of the interface region and analysing the degree of cross‐interface diffusion, the isothermal entropy change was measured by a vibrating sample magnetometer as the magnetic transition temperature (Curie temperature) is very sensitive to the dopant level in ceramics. Also the purpose of developing this graded ceramic tape casting was applications of these specific magnetocaloric properties within the magnetic refrigeration technology.     

Measurements of normal boiling points of fatty acid ethyl esters and triacylglycerols by thermogravimetric analysis

At present, a large number of studies of biodiesel production process using simulation packages are being developed. In these studies, vegetable oils and biodiesels are characterized in the software through representative compounds because of they are not in the compounds database of commercial simulators. With the aim to achieve a successfully characterization in these kinds of software, some properties of the substances must be available. The normal boiling point (NBP) is the most important property due to the fact that this property along with group contribution methods allows other properties calculation such as, e.g., critical properties and temperature dependency properties. In this work, a thermogravimetric analysis (TGA) method for rapid measurement of normal boiling points of two triacylglycerols and four ethyl esters, i.e., triolein, tripalmitin, ethyl oleate, ethyl palmitate, ethyl linoleate and ethyl ricinoleate, was used. Nowadays, in the open literature exists few data available about ethyl esters properties; hence, the results obtained here will contribute in the proposal, analysis, and evaluation of ethyl esters (biodiesel) virtual plants using reliable simulation packages. In addition, a more accurate characterization of compounds and therefore more accurate simulation results can be obtained when they are used.     

Kinetic and stoichiometric characterisation of streptavidin-binding aptamers

Aptamers are oligonucleotide ligands that are selected for high-affinity binding to molecular targets. Only limited knowledge relating to relations between structural and kinetic properties that define aptamer-target interactions is available. To this end, streptavidin-binding aptamers were isolated and characterised by distinct analytical techniques. Binding kinetics of five broadly similar aptamers were determined by surface plasmon resonance (SPR); affinities ranged from 35-375 nM with large differences in association and dissociation rates. Native mass spectrometry showed that streptavidin can accommodate up to two aptamer units. In a 3D model of one aptamer, conserved regions are exposed, strongly suggesting that they directly interact with the biotin-binding pockets of streptavidin. Mutational studies confirmed both conserved regions to be crucial for binding. An important result is the observation that the most abundant aptamer in our selections is not the tightest binder, emphasising the importance of having insight into the kinetics of complex formation. To find the tightest binder it might be better to perform fewer selection rounds and to focus on post-selection characterisation, through the use of complementary approaches as described in this study.     

Effect of a new fermented soy milk product on serum lipid levels in normocholesterolemic adult men

This study was undertaken to verify the effect of a daily intake of a new fermented soy milk produced with Enterococcus faecium and Lactobacillus jugurti on the serum lipid levels in normocholesterolemic middle-aged men. The study was randomized, double-blind and placebo-controlled and was performed for a period of 6 weeks. Forty-four normocholesterolemic healthy, male volunteers, aged 40-55 years old were randomly separated in two groups: The F-group received 200 ml of the fermented product daily and the P-group received 200 ml of placebo (chemically fermented). The blood samples were drawn initially and after 3 and 6 weeks and serum values for total cholesterol, HDL-cholesterol and triglyceride were determined. The LDL-cholesterol value was estimated. No significant changes in the fermented group (F) were observed for total cholesterol, LDL-cholesterol or triglyceride levels, while the HDL-cholesterol level was significantly higher (p < or = 0.05) after 6 weeks. The total cholesterol and LDL-cholesterol levels were significantly higher (p < or = 0.05) in the placebo group (P), but no changes were found for the HDL-cholesterol and triglyceride levels during the experimental period. In conclusion, the intake of 200 ml/day of the fermented soy milk, produced with E. faecium and L. jugurti, for 6 weeks, did not affect the serum total cholesterol and LDL-cholesterol, and led an increase of 10% in the HDL-cholesterol level.     

The Anti-Inflammatory Effects of the Methanolic Extract and Fractions from Davilla elliptica St. Hil. (Dilleniaceae) on Bothrops jararaca Envenomation

Inflammation and haemorrhage are the main characteristics of tissue injury in botropic envenomation. Although some studies have shown that anti-venom prevents systemic reactions, it is not efficient in preventing tissue injury at the site of the bite. Therefore, this work was undertaken to investigate the anti-inflammatory effects of the methanolic extract and fractions from D. elliptica and to evaluate the role of matrix metalloproteinases (MMPs) in this process. Effects of the extract and fractions from D. elliptica were evaluated using a carrageenan-induced paw oedema model in rats, and leukocyte rolling was visualized by intravital. The quantification of MMPs activities (MMP-2 and MMP-9) extracted from the dermis of mice treated with extract and fractions alone or incubated with venom was determined by zymographic analyses. Our results show that intraperitoneal (i.p.) injection of fractions significantly reduced paw oedema after the carrageenan challenge. Treatment with the tannins fraction also resulted in considerable inhibition of the rolling of leukocytes and this fraction was able to decrease the activation of MMP-9. These results confirmed the anti-inflammatory activity of the methanolic extract and tannins fraction of D. elliptica and showed that the dermonecrosis properties of B. jararaca venom might be mediated through the inhibition of MMP-9 activity.     

Ozone Treatment of Tannery Wastewater Monitored by Conventional and Substance Specific Wastewater Analyses

Ozone is an unstable and highly reactive gas applied in drinking water or wastewater treatment to oxidize and/or mineralize pollutants. Its application in wastewater treatment leads to a destruction of persistent pollutants combined with an improvement of biodegradability. The oxidation of organic and inorganic compounds in tannery wastewater at different pHs applying O₃ was studied. Results after O₃-treatment were determined by conventional wastewater parameters, e.g., total organic carbon (TOC), biochemical oxygen demand after 5 days (BOD₅), and chemical oxygen demand (COD), as well as by substance-specific mass spectrometric analytical techniques, i.e., gas chromatography—mass spectrometry (GC/MS) and liquid chromatography—mass and tandem mass spectrometry (LC/MS and—MSⁿ). In parallel, variations in the toxicity of the tannery wastewater against water organisms before and after O₃-treatment were determined by means of biotoxicity testing, i.e., Daphnia magna Straus and Vibrio fischeri bioassays.