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.     

13C-NMR Spectroscopic Detection of Malto-oligosaccharide Complexes

Fragments of amylose were enzymatically synthesized and purified to α-(a→4)-glucans of well defined degress of polymerization by preparative size exclusion chromatography. Maltooligosaccharides from DP 3 to 12 were subjected to ¹³C-NMR-spectroscopy. The addition of iodine as a complexing agent selectively affected the carbon atoms involved in the glycosidic bond. Resonances of C-1 and C-4 experienced a dramatic downfield shift. This is interpreted as a change of conformation of the amylose helix. The shift differences can be measured conveniently and be used for calculations of complex stability constants. Maltohexaose and higher saccharides gave strong effects upon complexation, indicating that one helical turn brings about a gain in helical stability. No lower chain-length limit for the complex-forming capacity was observed. Even the smallest fragments of amylose showed complexing behaviour.     

Increasing the thermostability of sucrose phosphorylase by a combination of sequence- and structure-based mutagenesis

Sucrose phosphorylase is a promising biocatalyst for the glycosylation of a wide variety of acceptor molecules, but its low thermostability is a serious drawback for industrial applications. In this work, the stability of the enzyme from Bifidobacterium adolescentis has been significantly improved by a combination of smart and rational mutagenesis. The former consists of substituting the most flexible residues with amino acids that occur more frequently at the corresponding positions in related sequences, while the latter is based on a careful inspection of the enzyme's crystal structure to promote electrostatic interactions. In this way, a variant enzyme could be created that contains six mutations and whose half-life at the industrially relevant temperature of 60 °C has more than doubled compared with the wild-type enzyme. An increased stability in the presence of organic co-solvents could also be observed, although these effects were most noticeable at low temperatures.     

Effect of temperature on friction and wear behaviour of CuO–zirconia composites

Results of wear tests using an alumina ball sliding against 5 wt% copper oxide doped tetragonal zirconia polycrystalline (CuO-TZP) ceramics are reported as a function of temperature up to 700 °C. The specific wear rate and friction coefficient are strongly dependent on temperature. Below a critical temperature (T < 600 °C), CuO-TZP showed a high coefficient of friction as well as a high wear rate. This was ascribed to the formation of a rough surface, caused by brittle fracture and abrasive wear, based on observations by scanning electron microscopy (SEM), laser scanning microscopy (LSM) and X-ray photoelectron spectroscopy (XPS). However, above 600 °C a self-healing layer is formed at the interface and results in low friction and wear. The mechanism of layer formation and restoration is discussed and rationalized by onset of plastic deformation caused by a reduction reaction of CuO to Cu₂O at high temperatures.     

Towards Heterogeneous and Green Versions of Os Dihydroxylation Catalysis

Os-catalyzed dihydroxylation will find more widespread application if truly heterogeneous catalysts are available which use O₂ or H₂O₂ as terminal oxidants. This paper discusses and critically evaluates the concepts by which Os can be anchored on solid supports. New methods are also available for reoxidation of hexavalent to octavalent Os.     

The Phospholipid Composition of Kangaroo Spermatozoa Verified by Mass Spectrometric Lipid Analysis

Cryopreservation of kangaroo sperm has not been successful so far, and yet there is no promising cryopreservation protocol for these cells available. However, conservation of gametes is extremely important, particularly in the context of preserving endangered species. As spermatozoa are comprised of different membrane systems, the composition of these membranes might account for difficulties in cryopreservation. Lipids, as the main components, affect the physical properties of biological membranes and play a major role in sperm maturation. Therefore, knowledge of the lipid composition is crucial for any further step toward the preservation of the species. We used MALDI‐TOF, ESI‐IT, tandem mass spectrometry, and thin layer chromatography to investigate the lipid composition of epididymal spermatozoa of four different kangaroo species. Spectra of these species were very similar with respect to the identified lipid species. Tremendous changes in the lipid composition during the transit of sperm from caput to cauda epididymis could be seen, specifically an increase in poly‐unsaturated fatty acids, ether lipids, and plasmalogens, as well as a reduction in mono‐ and di‐unsaturated fatty acids. Additionally, phosphatidylcholines containing docosatrienoic acid (22:3), a heretofore unknown fatty acid for sperm membranes, showed the highest abundance in kangaroo sperm.     

Giant Magnetoelectric Effect in Thin‐Film Composites

Highly sensitive AC magnetic field sensors are presented using magnetoelectric composites consisting of magnetostrictive and piezoelectric phases. They are offering passive nature, high sensitivity, large effect enhancement at mechanical resonance, and large linear dynamic range. Thin‐film magnetoelectric 2‐2 composites benefit from perfect coupling between the piezoelectric and magnetostrictive phases and from the reduction in size which is essential for high spatial resolution. Their design uses AlN and a plate capacitor or PZT with interdigital electrodes and magnetostrictive amorphous FeCoSiB single layers or exchanged biased multilayers. At mechanical resonance and depending on the geometry, extremely high ME coefficients of up to 9.7 kV/cm Oe in air and up to 19 kV/cm Oe under vacuum were obtained. To avoid external DC magnetic bias fields, composites consisting of exchanged biased multilayers serving as the magnetostrictive component with a maximum magnetoelectric coefficient at zero magnetic bias field are employed. Furthermore, the anisotropic response of these exchanged biased composites can be utilized for three‐dimensional vector field sensing. Sensitivity and noise of the sensors revealed limits of detection as good as to 2.3 pT/Hz^1/2 at mechanical resonance. Sensitivity between 0.1 and 1000 Hz outside resonance can be enhanced through frequency conversion using AC magnetic bias fields.     

Imidazolium-substituted ionic (co)polythiophenes: Compositional influence on solution behavior and thermal properties

A series of ionic polythiophenes, in homopolymer and random copolymer configurations, is prepared via the Grignard metathesis (GRIM) polymerization protocol and subsequent substitution on the bromohexyl side chains with N-methylimidazole. The introduced structural variations – comonomer ratio, side chain composition, counter ions – allow tuning of the thermal properties and solution behavior of the resulting conjugated polymers. As expected, the solubility depends majorly on the number of ionic groups and the counter ions. The most peculiar behavior is observed for the P3HT-P3(MIM)HT-Br 50/50 random copolymer, which shows organization of the polymer chains in solution and thin film dependent on the preparation conditions. Dynamic light scattering studies confirm that the ordered solid-state structure is somewhat maintained when the copolymer is dissolved in a bad solvent mixture. The ionic (co)polythiophenes are generally more resistant to thermal degradation than their precursors. The precursor polymers all show a clear semi-crystalline behavior, with a decrease in crystallinity upon decreasing the number of regular 3-hexylthiophene units. On the other hand, the studied ionic (co)polythiophenes are fully amorphous. Changes in the counter ions have dramatic effects on the thermal properties. Bromine counter ions render the polymers strongly hygroscopic. The novel materials are of particular appeal in the field of organic photovoltaics, in which the imidazolium-substituted (co)polythiophenes can be beneficially applied as constituents of either active layers or electron transport layers. Their processability from green solvents is also of major importance for the field.     

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.     

Improving the thickness accuracy of cold rolled narrow strip by piezoelectric roll gap control at high rolling speed

Particularly in fast rolling mills, conventional actuators reach their dynamic limits, when longitudinal thickness variations of the incoming strip shall be reduced with high accuracy by model-predictive roll gap control. Accordingly, the applicability of highly dynamic piezoelectric actuators in combination with electromechanical spindles and a high frequency precision measurement of the thickness in front of the roll gap was examined. Rolling tests in a cold rolling mill for narrow slit strips show that this novel concept is suitable to provide the required dynamic actuation especially at high rolling speed.