Determination of diffusion coefficients of Cu(I) ions in concentrated perchlorate solutions

The diffusion coefficients of Cu(I) ions in concentrated aqueous Ca(ClO₄)₂ solutions have been determined from the limiting currents of anodic oxidation at the rotating disc electrode.

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Zur Bestimmung der Diffusionskoeffizienten von Cu(I)-Ionen in konzentrierten Perchloratlösungen (Kurze Mitteilung)

Zusammenfassung Diffusionskoeffizienten von Cu(I)-Ionen in konzentrierten wäßrigen Ca(ClO₄)₂-Lösungen wurden durch Messung der anodischen Grenzströme an der rotierenden Scheibenelektrode bestimmt.

     

Efficient Large-eddy Simulations of Low Mach Number Flows Using Preconditioning and Multigrid

In the present paper, an implicit time accurate approach combined with multigrid, preconditioning and residual smoothing is used for the large-eddy simulation (LES) of low Mach number flow. In general, due to the restriction imposed on the time step by the physics of the flow, the advantage of an implicit method over an explicit one for LES is not obvious. It is shown that for the test cases considered in this paper, the present approach allows an efficiency gain of a factor 4–7 compared to the use of a purely explicit approach. The efficiency varies according to the test case, grid clustering, physical time step and requested residual drop. Numerical difficulties are catalogued and mitigatory procedures are introduced. Several problems with available experimental and DNS data are employed to verify the efficiency of the method.     

Einsatz der flammenlosen Atom-Absorption (Graphitrohrküvette) zur Bestimmung von Kupferspuren in Stahl und anderen Metall-Legierungen nach Extraktion

The determination of small and smallest amounts of copper in steel and other metal alloys by atomic absorption spectroscopy was investigated. It has been found, that the interferences caused by accompanying elements in the determination in aqueous solution with the flame can be completely removed by extracting the copper with Pb-DDTC in chloroform and determining this extract with the heated graphite atomizer. Moreover, it was recognised, that working with the heated graphite atomizer in organic solutions shows great advantages compared with the flame, because any solvent may be used. The methods of continuous variation by Job and the molar ratio by Yoe and Jones for the determination of the complex stoichiometry were transferred to the system Cu-DDTC by working with the heated graphite atomizer.     

The effect of the double layer on the rate of the Fe3+/Fe2+ reaction on a platinum electrode and the contemporary electron transfer theory

The kinetics of the Fe³⁺/Fe²⁺ reaction on a Pt rotating disc electrode was studied in solutions of 0.5 M H₂SO₄ and 0.5 M Na₂SO₄ (pH 2.2). Taking into account formation of sulphate complexes the conclusion was made that the main contribution to the reaction rate is due to FeSO₄⁺ and FeSO₄ complexes. Extended Tafel plots obtained by Randles analysis from experimental current-voltage curves were corrected for the ₂ potential. The latter was evaluated according to the Gouy-Chapman theory by using the surface charge density values deduced from thermodynamic theory and measurements of other authors. Tafel plots were approximated by parabolas and the reorganization energy was calculated as 33 kJ mol^?1 and 51 kJ mol^?1 for Fe³⁺/Fe²⁺ in H₂SO₄ and Na₂SO₄, respectively. The comparison of these values with theoretically predicted ones was made. From the magnitude of the pre-exponential factor of the true rate constant it was concluded that the Fe³⁺/Fe²⁺ electron transfer reaction is non-adiabatic in nature.     

Hydrodynamics of interaction of particles (including cells) with surfaces

The study of the phenomena related to the motion of particles flowing in the proximity of the wall is pursued for purely cognitive reason as well as for some important practical purposes in various fields of technology, biology and medicine.When small spherical rigid particles move in the direction parallel to the surface their velocity is smaller than that of the fluid and depends on the ratio of the distance from the wall to the particle radius. The velocity of a particle falling down in a vertical cylinder is maximal in an eccentric position. A sphere in contact with the wall remains stationary. Translational velocity of spherical rigid particles the dimension of which are comparable to that of the tube is only slightly dependent of their lateral position. The differences in the flow parameters of deformable particles in comparison with rigid ones depend on the particle and fluid viscosity coefficient. When the particles move perpendicularly toward the wall, their velocity decreases as the particle approaches the surface. The change of particle velocity is inversely proportional to the gap.There are several theories explaining the influence of the channel diameter on the suspension viscosity (sigma phenomenon); a modern approach is based on the analysis of rheological properties of suspensions. The explanations of the Fahraeus effect (i.e. the fact that the concentration of particles flowing in a tube linking two containers are smaller than that in the containers) are based on non-uniform particle distribution in a transverse cross section and on the differences of velocities of particles and medium. The deviation of the velocity profile of a suspension of rigid particles flowing through a tube from the parabolic shape (blunting) does not depend on the flow velocity; as concerns deformable particles, however, this effect is the smaller the greater is the flow velocity.When the Reynolds number for particles is greater than 10^-3, there appears a component of particle velocity perpendicular to the streamline direction.This phenomenon is the cause of the lateral migration of particles. Neutrally buoyant rigid particles migrate to a certain concentrical region situated between the tube axis and the wall (tubular pinch region). Deformable neutrally buoyant particles migrate towards the tube axis, and deformable non-neutrally buoyant particles may move either toward the tube axis or toward the wall.In the research on the influence of the flow delimiting surface on the motion of particles in suspension a considerable progress has recently been made.However, the phenomena in this field are extremely complex. At present, two main types of approach may be distinguished. On a microscopic level direct interactions between particles and surfaces are analyzed. A macroscopic approach consists in treating particle suspension as fluid, and overall influence of the surface on its properties are studied. A comprehensive theory linking these two levels has not yet emerged.     

Understanding binding affinity: a combined isothermal titration calorimetry/molecular dynamics study of the binding of a series of hydrophobically modified benzamidinium chloride inhibitors to trypsin

The binding of a series of p-alkylbenzamidinium chloride inhibitors to the serine proteinase trypsin over a range of temperatures has been studied using isothermal titration (micro)calorimetry and molecular dynamics simulation techniques. The inhibitors have small structural variations at the para position of the benzamidinium ion. They show small differences in relative binding affinity but large compensating differences in enthalpy and entropy. Binding affinity decreases with increased branching at the first carbon but increases with increasing the length of a linear alkyl substituent, suggesting that steric hindrance and hydrophobic interactions play dominant roles in binding. Structural analysis showed that the backbone of the enzyme was unaffected by the change of the para substituent. In addition, binding does not correlate strongly with octanol/water partition data. To further characterize this system, the change in the heat capacity on binding, the change in solvent-accessible surface area on binding, the effect of inhibitor binding on the hydration of the active site, the pK(a) of His57, and interactions within the catalytic triad have been investigated. Although the changes in inhibitor structure are small, it is demonstrated that simple concepts such as steric hindrance, hydrophobicity, and buried surface area are insufficient to explain the binding data. Other factors, such as access to the binding site and the cost of dehydration of the active site, are of equal or greater importance.     

LIGHT-INDUCIBLE ABSORBANCE CHANGES AND VANADATE-SENSITIVE ATPase ACTIVITY ASSOCIATED WITH THE PRESUMPTIVE PLASMA MEMBRANE FRACTION FROM CAULIFLOWER INFLORESCENCES

Sucrose density gradient centrifugation of a microsomal membrane fraction of cauliflower inflorescences showed a strong correlation between a blue light mediated cytochrome b reduction (LIAC) and an ion stimulated nitrate-insensitive but a vanadate-sensitive ATPase activity at 38-40% sucrose. LIAC activity and vanadate-sensitive ATPase might be assigned to the same type of membrane different from ER, Golgi, tonoplast and mitochondria. The Mg²⁺-dependent ATP-hydrolytic activity obtained after purification of the microsomal fraction on an aqueous polymer two phase system was partially characterized. Temperature optimum (40°C), pH optimum (pH 7.0), vanadate inhibition (I₅₀ at 20 μ M ), substrate kinetics ( K _m= 1.37 m M Mg.ATP) and inhibitor studies all point to the presence of the frequently described plasma membrane ATPase. Potassium and Na⁺ stimulated the enzyme activity (20-40%). In general our data arc strongly in favour of the hypothesis that LIAC activity is localized on the plant plasma membrane. The cytochrome b involved in the light reaction has a midpoint potential near +150 mV. This cytochrome which has been previously shown in a cauliflower microsomal fraction is a constituent of the plasma membrane.     

Formation of coordination compounds with aniline in the interlayer space of Ca<Superscript>2+</Superscript>-, Cu<Superscript>2+</Superscript>- and Fe<Superscript>3+</Superscript>-exchanged montmorillonite

The influence of Ca²⁺-, Cu²⁺- and Fe³⁺-exchanged montmorillonite (MMT) on the type of interaction with aniline in the interlayer space of MMT has been studied by means of X-ray powder diffraction and infrared spectra. Results of X-ray diffraction showed that aniline was successfully intercalated into the interlayer space of MMT. Based on IR spectra evaluation, aniline was indirectly coordinated through a water-bridge in Ca²⁺- and Fe³⁺-MMT and it was indirectly coordinated through a water-bridge as well as protonated in Cu²⁺-MMT (the spectrum of protonated aniline showed deformation and changes in the NH ₃ ⁺ absorption at approximately 1521 cm^?1). It is important to point out that Cu²⁺-MMT indirect coordination and protonation occur simultaneously.