Photochemie von Acylaziden. VIII [1]. Reagieren Acylnitrene wie 1,3-Dipole??

Photochemistry of Acylazides. VIII. Do Acylnitrenes React like 1,3-Dipoles? The formation of three- ore five-membered heterocyclic rings by the reaction of acylnitrenes with olefins depends on the electron density at the double bond. The generally expected formation of aziridines by a cheletropic reaction was observed by photolysis of aroylazides 1 in the presence of 2,5-dihydrofuran 2 . But with enolethers 3 and 4 oxazolines were directly formed. This [3 + 2] cycloaddition is regiospecific. The cycloaddition is modestly stereoselective by steric hindrance within the cyclic enolether 3b . Very small de-values were found with chiral substituents in the acylazide 13 . The azide decomposition was also achieved by photoinduced electron transfer. The same cycloaddition products as obtained by direct photolysis of the azides were obtained via radical anions of the acylazide. Using Michler's ketone as electron donor in the triplet state the formation of isocyanate which diminishes the yield of cycloadducts can be avoided.     

Molecular Weight Characterization and Gelling Properties of Acid-Modified Maize Starches

The reduction in the molecular weight distribution during acid hydrolysis of ordinary and waxy maize starch occured in two stages: first amylopectin degraded to intermediate high molecular weight polysac-charides, secondly, these were further hydrolyzed. The amylose moiety of ordinary and high-amylose starch was not affected very much by the hydrolysis conditions used (0.1–1 M HCI, 40°C, 0.3–4 h), but the gelling properties of starch weakened. The amylopectin degradation products, probably branched dextrins, were shown to hinder the gel formation of amylose in the starch pastes.     

Der einfluß von faseroberflächen auf die matrixhärtung bei faserverbundwerkstoffen

The influence of extraction of reinforced fibres on surface properties and the curing reaction of epoxy resin matrix in composites were investigated. With increasing fibre surface polarity, as the result of the extraction, the resin wettability was improved and the reaction rate of curing of the epoxy resin matrix increased. The wettability and the reaction rate oppositely decreased with decreasing fibre surface polarity.     

Chemical Stability of α‐Tocopherol in Colloidal Lipid Particles with Various Morphologies

Colloidal lipid particles (CLPs) are promising encapsulation systems for lipophilic bioactives, such as oil‐soluble antioxidants that are applied in food and pharmaceutical formulations. Currently, there is no clear consensus regarding the relation between particle structure and the chemical stability of such bioactives. Using α‐tocopherol as a model antioxidant, it is shown that emulsifier type (Tween 20 or 40, or sodium caseinate) and lipid composition (tripalmitin, tricaprylin, or combinations thereof) modulated particle morphology and antioxidant stability. The emulsifier affects particle shape, with the polysorbates facilitating tripalmitin crystallization into highly ordered lath‐like particles, and sodium caseinate resulting in less ordered spherical particles. The fastest degradation of α‐tocopherol is observed in tripalmitin‐based CLPs, which may be attributed to its expulsion to the particle surface induced by lipid crystallization. This effect is stronger in CLPs stabilized by Tween 40, which may act as a template for crystallization. This work not only shows how the architecture of CLPs can be controlled through the type of lipid and emulsifier used, but also gives evidence that lipid crystallization does not necessarily protect entrapped lipophilic bioactives, which is an important clue for encapsulation system design. Practical Applications: Interest in enriching food and pharmaceutical products with lipophilic bioactives such as antioxidants through encapsulation in lipid particles is growing rapidly. This research suggests that for efficient encapsulation, the particle architecture plays an important role; to tailor this, the contribution of both the lipid carrier and the emulsifier needs to be considered.     

Emissions from sawdust in packed moving bed dryers and subsequent pellet production

This study quantifies emissions of hydrocarbon terpenes from the drying of sawdust in packed moving bed dryers, through the production chain to the finished pellets, and determines the parameters suitable for emission control. The terpene content in softwood sawdust and pellets was analyzed using gas chromatography. The distribution of VOC emissions over the bed was measured with a flame ionization detector. After drying, 30–40% of the initial terpenes remain in the wood, 20–30% remain after grinding, and 10–15% remain after pelleting. Dryer emissions correlate with residence time and final sawdust moisture content. Pellet press emissions correlate with pellet moisture content.     

Investigating correlations between crack width,corrosion level and anchorage capacity

In assessing existing structures, inspection results need to be linked to the effects on load-carrying capacity; to provide such information, this study has investigated the correlation between splitting crack width, corrosion level and anchorage capacity. The study was based on 13 reinforced concrete beams that had been exposed to natural corrosion for 32 years, 11 beams with splitting cracks and 2 without. The crack pattern and widths were documented before undergoing structural testing of anchorage capacity. Thereafter, the reinforcement bars were extracted and their corrosion levels measured using two methods, gravimetric weight loss and 3D scanning. The corrosion level from the weight loss method was approximately twice as large; possible reasons are horizontal or subsurface corrosion pits, and the cleaning method. Further, for the same corrosion level, the specimens in this study had much larger crack widths and slightly lower bond capacity than the artificially corroded tests in the literature; a possible reason is that these specimens had been subjected to combined corrosion and freezing. However, the corrosion level and reduction in bond capacity related to crack width were both lower in the present than in previous studies in the literature. Thus, by formulating a damage indicator from the damage visible in the form of crack widths from artificial test data, the structural capacity is estimated to be on the safe side.     

Effect of pasture vs. concentrate diet on CLA isomer distribution in different tissue lipids of beef cattle

This study examined the effects of feeding pasture vs. concentrate on the distribution of CLA isomers in the lipids of longissimus and semitendinosus muscle, liver and heart muscle, and subcutaneous fat in beef bulls. Sixty-four German Holstein and German Simmental bulls were randomly allocated to either an indoor concentrate system or periods of pasture feeding followed by a finishing period on a concentrate containing linseed to enhance their beef content of n−3 PUFA and CLA. The concentrations of CLA isomers in the different tissues were determined by GC and silver ion HPLC. The diet affected the distribution of individual CLA isomers in the lipids of the different tissues. The concentration (mg/100 g fresh tissue) of the most prominent isomer, cis-9,trans-11 18∶2, was increased up to 1.5 times in liver and heart tissue of bulls fed on pasture as compared with concentrate. However, no diet effect was observed for cis-9,trans-11 18∶2 in the lipids of longissimus muscle and subcutaneous fat. In all tissues, the second-most abundant CLA isomer in concentratefed bulls was trans-7,cis-9 18∶2. In contrast, trans-11,cis-13 18∶2 was the second-most abundant CLA isomer in all investigated tissue lipids of pasture-fed bulls. The concentration of the trans-11,cis-13 18∶2 isomer was up to 15 times higher in tissues of pasture-fed bulls as compared with concentrate-fed animals. Furthermone, diet affected the concentrations of the CLA trans,trans 18∶2 isomers. Pasture feeding significantly increased the concentrations of some trans,trans 18∶2 isomers as compared with concentrate, predominantly trans-12,trans-14 18∶2 and trans-11,trans-13 18∶2. Overall, pasture feeding resulted in significantly increased concentrations of the sum of CLA isomers in the lipids of longissimus, muscle, subcutaneous fat, heart and liver muscle of German Holstein and German Simmental bulls, but not in semitendinosus muscle.     

Application of β-Sitosterol + γ-Oryzanol-Structured Organogel as Migration Barrier in Filled Chocolate Products

Oil migration in filled pralines is a phenomenon that is highly correlated with the occurrence of chocolate bloom. In this study the potential to suppress or prevent oil migration by incorporation of sterol/sterolster-structured organogels was evaluated. Different quantities, 2.5 or 14% (w/w), of gel with structurant levels of either 10 or 25% (w/w) were studied in a layered model system. The gel was either a part of the nougat or of the chocolate phase, or as a separate layer. Samples were monitored regularly for a period of 24 weeks at storage temperatures of 10, 18 and 28 °C. The amount of migrated oil was determined via DSC analysis of a surface sample. The results indicate that, despite the additional oil brought into the system via the oleogel, the level of oil found in the chocolate layer is reduced through the presence of the gel. In particular, the three-layer system and gelled chocolate appear to be promising routes to either suppress oil migration or improve nutritional profiles by incorporation of liquid oils.     

Extraction of heavy metals from soils using biodegradable chelating agents

Metal pollution of soils is widespread across the globe, and the clean up of these soils is a difficulttask. One possible remediation technique is ex-situ soil washing using chelating agents. Ethylenediaminetetraacetic acid (EDTA) is a very effective chelating agent for this purpose but has the disadvantage that it is quite persistent in the environment due to its low biodegradability. The aim of our work was to investigate the biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDSA), methylglycine diacetic acid (MGDA), and nitrilotriacetic acid (NTA) as potential alternatives and compare them with EDTA for effectiveness. Kinetic experiments showed for all metals and soils that 24 h was the optimum extraction time. Longer times only gave minor additional benefits for heavy metal extraction but an unwanted increase in iron mobilization. For Cu at pH 7, the order of the extraction efficiency for equimolar ratios of chelating agent to metal was EDDS > NTA> IDSA > MGDA > EDTA and for Zn it was NTA > EDDS > EDTA >MGDA > IDSA. The comparatively low efficiency of EDTA resulted from competition between the heavy metals and co-extracted Ca. For Pb the order of extraction was EDTA > NTA >EDDS due to the much stronger complexation of Pb by EDTA compared to EDDS. At higher concentration of complexing agent, less difference between the agents was found and less pH dependence. There was an increase in heavy metal extraction with decreasing pH, but this was offset by an increase in Ca and Fe extraction. In sequential extractions EDDS extracted metals almost exclusively from the exchangeable, mobile, and Mn-oxide fractions. We conclude that the extraction with EDDS at pH 7 showed the best compromise between extraction efficiency for Cu, Zn, and Pb and loss of Ca and Fe from the soil.     

Environmental factors for phage-induced fermentation problems: replication and adsorption of the Lactococcus lactis phage P008 as influenced by temperature and pH

The lactococcal phage P008 was investigated for its growth characteristics under certain environmental conditions. Phage growth was characterized by the latency period, the average burst size (determined in one-step growth experiments) and by the percentage of adsorption to the host cells after 1, 5, 10 and 15 min (determined in modified one-step growth experiments). The incubation conditions studied were temperatures from 20 to 40 degrees C and pH values of 4.8 and 6.4. The growth medium was ultrafiltration permeate of skim milk, which forms the water phase of milk. Both, the temperature and the pH influenced the growth parameters: Increased temperature as well as low pH led to a faster latency along with a higher average burst size. The percentage of adsorption was at maximum when the standard conditions of 30 degrees C and pH 6.4 were applied. Below pH 5, adsorption was reduced to below 10%. A decrease of temperature slightly reduced phage multiplication. Data were incorporated into a model to simulate phage multiplication under certain conditions, taking the percentage adsorption into account. The cell destruction of the host culture was calculated accordingly. The simulation (extrapolation) was validated by experimental growth curves of phages and phage-infected host cultures.