New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin-orbit coupling for the 11B chemical shifts

Reaction between nido-B10H14 (1) and elemental sulfur in CHCl3 in the presence of Et3N at room temperature, followed by treatment with Et3N.BH3 at 170-190 degrees C, resulted in the isolation of closo-1-SB11H11 (2) in 50% yield. Selected electrophilic halogenation reactions of compound led to the isolation of a series of monohalogenated derivatives of general constitution 12-X-closo-1-SB11H10 (12-X-, where X = Cl, Br, and I). The structures of 12-Cl- and 12-I- were determined by an X-ray diffraction analysis and the structures of all compounds were geometry optimised at the RMP2(fc)/6-31G* level. The constitution of all compounds is consistent with the results of mass spectrometry and multinuclear (1H and 11B) spectroscopy complemented by two-dimensional [11B-11B]-COSY and 1H{11B(selective)} NMR measurements. Experimental 11B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, but spin-orbit coupling must be included for nuclei bearing heavy-atom substituents such as Br or I. The dipole moments determined for the B12-X bonds show similarities to those of aliphatic C-X bonds and confirm unambiguously the B12 --> S dipole moment orientation in the SB11 cage.     

Synthesis and Structural Studies of Tetraaldehyde Phenylhydrazone and its Complex with Copper(II)

A binucleating ligand, incorporating four phenylhydrazone groups, 7,7′-methylene-bis[(E,E)-3,11-dimethyl-5,9-dioxa-4,10-diaza-3,10-tridecadiene-2,12-dione]phenylhydrazone (4) (mtph) was synthesized, its dinuclear Cu(II) complex prepared and its metal complex characterized by elemental analyses, ¹H and ¹³C-n.m.r., i.r. and mass spectrometry. The elemental analysis, stoichiometry and spectroscopic data of the dinuclear Cu(II) complex indicate that the Cu(II) ions are coordinated to the ether oxygen and nitrogen atoms (C=N) of the tetrahydrazone, the with a 2:1 metal:ligand ratio. All spectral data support the proposed structure of mtph and its Cu(II) complex. In addion, the total energy and heat of formation (Figure 3) calculated for intramolecular hydrogen bonded and non-intramolecular hydrogen bonded tetrahydrazones (4, 5) by semiempirical AM1 calculations showed that tetrahydrazone (5) having intramolecular hydrogen bonds is more stable (ca. 10 kcal/mol) than the non-intramolecular hydrogen bonded form (4).     

On the existence of almost-pure-strategy Nash equilibrium in <Emphasis Type="Italic">n</Emphasis>-person finite games

This paper gives wide characterization of n-person non-coalitional games with finite players’ strategy spaces and payoff functions having some concavity or convexity properties. The characterization is done in terms of the existence of two-point-strategy Nash equilibria, that is equilibria consisting only of mixed strategies with supports being one or two-point sets of players’ pure strategy spaces. The structure of such simple equilibria is discussed in different cases. The results obtained in the paper can be seen as a discrete counterpart of Glicksberg’s theorem and other known results about the existence of pure (or “almost pure”) Nash equilibria in continuous concave (convex) games with compact convex spaces of players’ pure strategies.     

Changes in wetting properties of alumina surface treated with DPPC in the presence of phospholipase A2 enzyme

Wetting properties of commercial Al(2)O(3) plates contacted with dipalmitoylphosphatidylcholine (DPPC) or DPPC+enzyme (phospholipase PLA(2)) in NaCl solution were determined by thin layer wicking and with the help of Washburn equation. Van Oss et al.'s approach to interfacial free energy interactions was applied to determining the solid surface free energy components. Wicking experiments were performed both for bare and alumina plates precontacted overnight with the probe liquid saturated vapours, as well as the untreated and DPPC (or DPPC+PLA(2)) treated alumina plates. For this purpose the penetration rates of n-octane, water and formamide were measured. From these experiments it resulted that original alumina surface is strongly polar with electron-donor interactions originating from the surface hydroxyl groups. Adsorption of DPPC on Al(2)O(3) plates slightly increased the hydrophobic character of the alumina surface (considerable decrease of the electron-donor, γ(s)(-) parameter and γ(s)(AB) component was visible) in such a way that the hydrocarbon chains were directed outwards and the polar part towards the alumina surface. However, after the enzyme action the products of DPPC hydrolysis by PLA(2) (palmitic acid and lysophosphatidylcholine) increased again the hydrophilic character of Al(2)O(3) surface (a minor increase in γ(s)(AB) component and drastic increase of the electron-donor γ(s)(-) parameter was noticeable). After treatment with DPPC or DPPC+enzyme PLA(2) solution the changes of the total surface free energy of alumina and its Lifshits-van der Waals (γ(s)(LW)) component were in the range 7-10 mJ/m(2), but the most considerable and delivering more interesting information were the changes of the electron-donor (γ(s)(-)) parameter ranging from 27 to 35 mJ/m(2). Moreover, the changes of the alumina surface wettability were dependent on the time of the enzyme contacting with DPPC in NaCl solution. On the basis of the obtained results it seems that the thin layer wicking method can be an additional useful tool in investigations of the effect of phospholipid and PLA(2) action on the hydrophilic-hydrophobic character of alumina surface.     

Comparison of n-tetradecane/electrolyte emulsions properties stabilized by DPPC and DPPC vesicles in the electrolyte solution

The properties of n-tetradecane/electrolyte emulsions with DPPC or DPPC vesicles in the electrolyte solution were investigated. The DPPC molecules form different aggregates, which possess different surface affinity, size and structure, and therefore we assumed some differences in the adsorption at the oil droplet/water interface. The n-tetradecane emulsions in 1:1, 1:2 and 1:3 electrolytes were prepared by mechanical stirring in the presence of DPPC at natural pH. Electrokinetic properties of the systems were investigated taking into account the effective diameter and multimodal size distribution of the droplets as well as the zeta potentials using the dynamic light scattering technique. The zeta potential of the droplets was negative in all systems with NaCl. In the emulsions with CaCl(2) at a higher concentration of electrolyte and emulsions with LaCl(3) with all investigated concentrations, positive values were observed. Similar measurements were performed for DPPC vesicles in the electrolyte solution. The pH and ionic strength changes induce those in the electrical charge of DPPC layer or vesicle surface. This is due to the fact that the DPPC molecule contains -PO(-) and -N(CH(3))(3) groups, which are in equilibrium with H(+) and OH(-), as well as other ions present in the solution, i.e. Na(+), Ca(2+), La(3+) or Cl(-). In the n-tetradecane/electrolyte emulsion stabilized by DPPC or DPPC vesicles the zeta potential may be also related to acid-base interactions. The effect of the ions from the solution on the DPPC layer adsorbed on n-tetradecane droplets or DPPC vesicles is discussed.     

All -cotilting modules are pure-injective

We prove that all -cotilting -modules are pure-injective for any ring and any . To achieve this, we prove that is a covering class whenever is an -module such that is closed under products and pure submodules.

     

Redox-complexometric determination of iron and cobalt and its application to the analysis of multi-component alloys

A redox-complexometric determination of iron and cobalt is based on potentiometric titration of iron with EDTA, followed by that of cobalt with iron(III) chloride after addition of 1,10-phenanthroline. This method simplifies the complexometric analysis of more complicated materials.