Optimisation of extraction procedures for metallothionein-isoforms and superoxide dismutase from liver samples using spiking experiments

The speciation of trace element species in solid matrices like liver samples is still problematic due to two reasons. On the one hand direct methods with sufficient selectivity and sensitivity are currently not available. Therefore extraction procedures have to be applied which are often problematic in respect to species stability. On the other hand there are no reference materials with known amounts of metal proteins like metallothionein-isoforms (MT) and superoxide dismutase (SOD) for quality control. So the aim of this study was to develop and optimise procedures for the species-preserving extraction of the model compounds MT and SOD from liver samples. Spiking experiments were performed to overcome the lack of appropriate reference materials. In a first step the stability of the model species without liver matrix was investigated by the variation of several extraction parameters. The extractant and exposure to ultrasonic energy especially had a great influence on the recovery of the species while temperature, buffer concentration and atmospheric conditions were less critical. In a second step spiked liver samples were extracted with a selection of procedures taken from the literature. Most of these methods provided recoveries between 70% and 100%. Additionally the buffer concentration and the extractant-to-liver ratio were varied for optimisation. The metal balance of an extraction showed recoveries of 81% for Cd, 94% for Cu and 87% for Zn.     

Poincaré duality in P.A. Smith theory

Let , or more generally be a finite -group, where is an odd prime. If acts on a space whose cohomology ring fulfills Poincaré duality (with appropriate coefficients ), we prove a mod congruence between the total Betti number of and a number which depends only on the -module structure of . This improves the well known mod congruences that hold for actions on general spaces.

     

Quantitative, dynamic fuel distribution measurements in combustion-related devices using laser-induced fluorescence imaging of biacetyl in iso-octane

Knowledge of in-situ fuel distributions in practical combustion devices, such as internal combustion engines, is crucial for research and devlopment purposes. Numerous imaging techniques, mostly based on laser-induced fluorescence (LIF), have been developed and yield high levels of 2-D spatial information, but generally lack the temporal resolution (frame rates) necessary to resolve important timescales at sub-millisecond levels for sustained times. A planar LIF technique for quantitatively visualizing fuel distribution is presented which gives not only high spatial resolution, but also high temporal resolution. Using a high-speed CMOS camera, a lens-coupled image intensifier, and frequency-tripled diode-pumped Nd:YAG laser allows for capturing LIF images of biacetyl that is used as a fluorescence tracer at 12 kHz (one crank-angle resolution at 2000 RPM) for hundreds of consecutive engine cycles. The LIF signal strength of biacetyl doped in iso-octane is shown to vary substantially over a wide range of temperatures and pressures. The low absorption coefficient at 355 nm and a longpass filter in the detection path exclude bias errors due to laser beam attenuation and fluorescence trapping. An intensifier gate time of 350 ns is shown to suppress the detection of phosphorescence signals under practical conditions. An example for a quantitative high-speed measurement of fuel concentration at varying pressure and temperature conditions is presented. Quantitative equivalence ratio maps are shown for the fuel injection event within a single cycle in a spark-ignition direct-injected engine, showing the ability of the technique to not only reveal static fuel concentration maps, but also the motion of the fuel cloud along with very steep gradients. Spray velocities determined from the moving fuel cloud are in agreement with previous particle image velocimetry measurements.     

Helical growth of semiconducting columnar dye assemblies based on chiral perylene bisimides

A perylene bisimide derivative bearing two phenyl substituents with chiral solubilizing alkyl chains at the imide N atoms has been synthesized, and its self-assembly properties in solution and condensed phase have been investigated. Temperature-dependent CD spectra revealed the coexistence of two different kinds of chiral aggregates, differing in size and handedness. The chiral side chains effect a higher order within the self-assemblies, resulting in an increased charge-carrier mobility in the columnar liquid crystalline mesophase. [structure: see text]     

Compensation of steric demand by cation-pi interactions,cobaltocenium cations as guests in tetraurea calix[4]arene dimers

The affinities of ferrocene (2) and the cobaltocenium cation (3+), which have roughly the same size and differ in their charge, towards the inner cavity of the dimeric capsule formed by tetraurea calix[4]arene (1) were studied in C2D4Cl2 solutions. While 3+, which occupies more than 75% of the internal volume of the dimer, is readily encapsulated this is not the case for 2. This is probably due to cation-pi interactions, which operate only between 3+ and the aromatic rings of the calix[4]arene dimer. We found that the affinity of the cobaltocenium cation is higher than that of the tropylium cation (4+) and is only 2-3 times less than that of the tetraethylammoniun cation (5+). From the variable temperature 1H NMR spectra of this capsule, the free energy of activation at 298 K (deltaGdouble dagger(298K)) for the reorientation of the hydrogen bonded belt between the two parts of the dimer could be determined by total line shape analysis for the aromatic protons of the calixarene. The value of 14.3 +/- 0.2 kcal mol(-1) for the dimeric capsules of 3+ PF6- is very similar to the free activation energy found for dimeric capsules of 1 with 4+ PF6- and 5+ PF6- in C2D4Cl2. It becomes significantly lower, if PF6- is replaced by BF4-. We also found that ten times more DMSO is needed to disrupt the capsule 1 x 3+ x 1 than the corresponding 1 x 1 dimer containing benzene as guest. This demonstrates again the importance of the cation-pi interactions for the stability of such hydrogen-bonded dimeric capsules.     

Zeta Potential as an Analytical Tool for Graft Copolymers and for Polymer Surfaces

Polymers with electrically charged groups exhibit a zeta potential when in contact with electrolyte solutions in water. This can be measured with solid polymers as fibers, foils, or granulates. The method of streaming potential/streaming current allows the determination of the carboxyl content of cellulose grafted with poly-(acrylic acid). Since zeta-potential measurements concern the surface of the sample, the method yields information on the type of grafting; i.e., whether it takes place mainly on the surface or throughout the bulk. By measuring the pH dependence of the zeta potential it is possible to obtain the pK value of the charged groups. The significance of zeta potential as an analytical tool is emphasized.