Aspects of polyaniline electrodeposition on aluminium

Electrodeposition of polyaniline (PAni) from acid solutions on spontaneous passivating electrodes such as Al is not so obvious as on active metals (Fe and Ni). The methods that can result in deposition are: (1) surface pre-treatment with a chelating agent (alizarin) to block the hydrogen evolution reaction on aluminium and (2) a suitable monomer concentration (critical monomer concentration) to decrease the polymerisation induction time. The oxidation of aluminium to thick porous film limits the growth kinetics of PAni during deposition by cyclic voltammetry. We found that after reducing hydrogen evolution by surface chelation, for film growing in 0.5 M H₂SO₄ a concentration of 0.4 M aniline is required.     

Hydrogen Bonding Directed Self-Assembly of a Binuclear Ag(I) Metallacycle into a 1D Supramolecular Polymer

An Ag(I) metallacycle obtained unexpectedly during the preparation of Pd(II) complexes of the bifunctional ligand 5-([2,2′-bipyridin]-5-yl)pyrimidine-2-amine (L) has been characterized using X-ray structure determination as a binuclear, metallacyclic species [Ag₂L₂](SbF₆)₂, where both the bipyridine and pyrimidine-N donors of L are involved in coordination to the metal. The full coordination environment of the Ag(I) defines a case of highly irregular 4-coordination. In the crystal, the Ag-metallacycles assemble into one-dimensional supramolecular metalladynamers linked together by hydrogen-bonding interactions.     

Studies of Benzothiazole and Benzoselenazole Squaraines as Fluorescent Probes for Albumins Detection

Series of squaraine benzothiazole and benzoselenazole dyes were studied as possible fluorescent probes for the detection of proteins, particularly albumins. It was shown that majority of the studied squaraines give significant fluorescent response on the human serum albumin (HSA) and bovine serum albumin presence. For squaraine dyes with N-hexyl pendent groups (P-1, P-2, P-3, P-5) about 100−540-fold fluorescence intensity increase upon albumins addition was observed. At the same time in presence of other proteins, namely insulin, avidin from hen egg white, immunoglobulin G (IgG), carbonic anhydrase fluorescence enhancement values were considerably lower —up to 43 times in IgG presence. It was noted that generally, squaraines with long N-hexyl pendent groups demonstrate higher emission increase values upon proteins addition comparing with their analogues with short N-ethyl tails. It was shown that fluorescence intensity enhancement for benzothiazole squaraine dye P-3, relates linearly to the HSA concentration over the wide range—from 0.2 to 500 μg/ml. Together with noticeable selectivity of this dye to albumins, existence of wide dynamic range gives possibility to propose P-3 dye as probe for HSA quantification.     

The effect of cryopreservation process on morphology and fertilising ability of Japanese quail (Coturnix japonica) spermatozoa

Changes in the morphology and fertilising ability of Japanese quail spermatozoa were studied after semen dilution, equilibration and freezing-thawing process in order to determine the optimal diluent, cryoprotectant and the freezing-thawing method. Subsequent stages of quail semen cryopreservation caused significant decline in spermatozoa morphology and their ability to fertilise the ovum. Semen dilution with Lake's extender alone reduced the number of morphologically normal spermatozoa and decreased their fertilising ability. Dimethylacetamide (DMA) was the least detrimental but equilibration of quail spermatozoa with this cryoprotectant caused further decline in the number of morphologically normal cells. However, despite these changes, after artificial insemination with semen equilibrated with DMA 25.8 percent of fertile eggs were obtained. Further loss in the number of normal spermatozoa was observed following the freezing-thawing process. Of the two investigated freezing-thawing methods, the rapid rate (60 C/min) appeared less detrimental to spermatozoa morphology and their ability to fertilize the ovum than the "slow" rate. Also the number of sperm holes appearing in the inner perivitelline layer and the number of spermatozoa trapped in the outer perivitelline layer of the ovum was higher after the rapid than the 'slow' freezing-thawing procedure. Nevertheless, both rates did not yield any fertile eggs.     

Characterization of a-B5C:H prepared by PECVD of orthocarborane: Results of preliminary FTIR and nuclear reaction analysis studies

The electronic properties of a-Si:H vary with hydrogen passivation of dangling bond defects. It appears this effect is also operative in semiconducting amorphous hydrogenated boron carbide (a-B₅C:H). Therefore, the ability to quantify the amount of hydrogen will be key to development of the materials science of a-B₅C:H. The results of an initial investigation probing the ability to quickly correlate hydrogen concentration in a-B₅C:H films with infrared spectroscopy are reported. a-B₅C:H thin films were growth on Si (1 1 1) substrates by plasma-enhanced chemical vapor deposition (PECVD) using sublimed orthocarborane and argon as the precursor gas. Nuclear reaction analysis (NRA) was performed to quantify the atomic concentration of H in the a-B₅C:H films. While the observed vibronic structure does not show stretches due to terminal C–H or bridging B–H–B, analysis of the terminal B–H stretch at ～2570 cm^?1 gives a proportionality constant of A = 2 × 10²² cm^?2. We conclude that the methods previously developed for correlating H concentration to infrared data in a-Si:H are similarly viable for a-B₅C:H films.     

Large Eddy Simulation of Spark Ignition in a Gas Turbine Combustor

Ignition in an aircraft gas turbine combustion chamber is simulated using Large Eddy Simulation (LES) in conjunction with the filtered probability density function (pdf) equation approach, which is solved using the Eulerian stochastic field method. The LES-pdf methodology is used for both dispersed (liquid) and gas phases. The liquid phase is described using a Lagrangian formulation whilst an Eulerian approach is employed for the gas phase. The spark energy deposition was mimicked by a distributed energy source term added to the enthalpy equation. Unsuccessful and successful ignition sequences have been simulated and the results suggest that spark ‘size’ is an important parameter in the ignition of kerosene fuelled combustion chambers.     

Interactions of hydrosiloxane and vinylsiloxane groups with aluminum oxide surfaces

Silicone-based materials often contain vinylsiloxane and hydrosiloxane groups for cross-linking by a radical or addition reaction. Such functional groups can influence the interactions with fillers or with surfaces of substrates when used as adhesives. This work examined how these functional groups interact with aluminum oxide surfaces. For this purpose, aluminum oxide powders with large surface areas of 150 m²/g and different acid-base properties were examined. Siloxanes were applied as thin layers to mainly obtain information from the interphase by vibrational spectroscopy. It was observed that vinyl groups show low interactions with aluminum oxide surfaces even at elevated temperatures. In contrast to this, hydrosiloxanes undergo strong interactions and reactions with aluminum oxides already at room temperature. Activated Si─H species were observed as an intermediate state. On the one hand, interactions and reactions might contribute to adhesion, but on the other hand, the cross-linking reaction can be influenced near the surface, leading to lower mechanical strength.     

PIV studies of coherent structures generated at the end of a stack of parallel plates in a standing wave acoustic field

Oscillating flow near the end of a stack of parallel plates placed in a standing wave resonator is investigated using particle image velocimetry (PIV). The Reynolds number, Re _d , based on the plate thickness and the velocity amplitude at the entrance to the stack, is controlled by varying the acoustic excitation (so-called drive ratio) and by using two configurations of the stacks. As the Reynolds number changes, a range of distinct flow patterns is reported for the fluid being ejected from the stack. Symmetrical and asymmetrical vortex shedding phenomena are shown and two distinct modes of generating “vortex streets” are identified.     

Unbiased estimators for spatial distribution functions of classical fluids

We use a statistical-mechanical identity closely related to the familiar virial theorem, to derive unbiased estimators for spatial distribution functions of classical fluids. In particular, we obtain estimators for both the fluid density rho(r) in the vicinity of a fixed solute and the pair correlation g(r) of a homogeneous classical fluid. We illustrate the utility of our estimators with numerical examples, which reveal advantages over traditional histogram-based methods of computing such distributions.     

Possibilities for recycling cellulases after use in cotton processing: part II: Separation of cellulases from reaction products and released dyestuffs by ultrafiltration

The adsorption and activity of a total cellulase (Trichoderma reesei) was measured and compared on undyed and dyed cotton fabrics. Recovery of enzymes from the reaction mixture and by desorption from the cotton substrate was evaluated. About 80% of the initial protein could be recovered. The removal of released products (soluble reducing sugars and dyes) from the treatment liquor and subsequent concentration of cellulase proteins was performed using an ultrafiltration membrane. Strong protein-dye interactions made it impossible to separate efficiently the dyes from the enzyme-containing treatment liquors. The use of surfactants did not enhance cellulase desorption from cotton fabric. Although anionic surfactants have a deactivating effect on cellulases, this effect seems to be reversible, since after ultrafiltration the cellulase activity was similar to that of enzymes desorbed with buffer only. Humicola insolens cellulases were shown to be much more sensitive to anionic surfactant than T. reesei cellulases. The use of cellulases that bind reversibly to cellulose is suggested for achieving more efficient cellulase recycling and for reducing backstaining by dye-cellulase complexes.