Application of the fractional factorial design in multiple W/O/W emulsions

In presented research, multiple W/O/W emulsions were developed by using experimental design method. A 24-1 fractional factorial design was performed by varying the following input parameters: primary polymeric emulsifier (PEG 30-dipolyhydroxystearate) concentration (0.8% and 2.4%), secondary polymeric emulsifier (Poloxamer 407) concentration (0.8% and 1.2%), electrolyte magnesium sulfate heptahydrate (0.08% and 0.4%) and electrolyte sodium chloride (0.08% and 0.4%). Multiple emulsions were prepared by a two-step emulsification process. Obtained emulsions were characterized with rheological measurements, conductivity and centrifugation tests. Factorial analysis revealed that the concentration of the primary emulsifier was the predominant factor influencing the phase separation, conductivity and maximal apparent viscosity. Additionally, electrolyte magnesium sulfate heptahydrate was more efficient in stabilizing these systems, compared to sodium chloride. The applied fractional factorial design method enabled determination of the optimal concentrations of the primary and secondary emulsifier, as well as the concentration of electrolytes, in order to obtain W/O/W emulsions with desired maximal apparent viscosities, low values of conductivity and without phase separation after centrifugation.     

Heterometallic hexanuclear isobutyrate clusters based on di- and tripodal alcohols

Four hexanuclear coordination clusters containing $\{{\mathrm{M}}_4^{\mathrm{II}}{\mathrm{M}}_2^{\mathrm{III}}\}$ cores of edge-sharing coordination octahedra exemplify how mixed-spin derivatives of a homonuclear parent structure, [${\mathrm{Mn}}_4^{\mathrm{II}}{\mathrm{Mn}}_2^{\mathrm{III}}{\mathrm{L}}_8$(N–O)₄], can be realized by a ligand ‘shrink-wrapping’ approach, resulting in [${\mathrm{Mn}}_2^{\mathrm{II}}{\mathrm{Co}}_2^{\mathrm{II}}{\mathrm{Mn}}_2^{\mathrm{III}}{\mathrm{L}}_8$(N–O)₄]- and [${\mathrm{Co}}_4^{\mathrm{II}}{\mathrm{Fe}}_2^{\mathrm{III}}{\mathrm{L}}_8$(N-O)₄]-type clusters (L = isobutyrate, N–O = methyldiethanolamine, n-butyldiethanolamine, or triethanolamine). The resulting core structures are either virtually isostructural to the parent structure or differ in the placement of the peripheral metal ions, depending on the mix of structure-directing carboxylate and alkoxyamine ligands with large, flexible alkyl chains. Whereas the $\{{\mathrm{Mn}}_4^{\mathrm{II}}{\mathrm{Mn}}_2^{\mathrm{III}}\}$ and {${\mathrm{Co}}_4^{\mathrm{II}}{\mathrm{Fe}}_2^{\mathrm{III}}$} complexes show dominant antiferromagnetic exchange, ferrimagnetic coupling features are exhibited by two {${\mathrm{Mn}}_2^{\mathrm{II}}{\mathrm{Co}}_2^{\mathrm{II}}{\mathrm{Mn}}_2^{\mathrm{III}}$} clusters.     

The influence of the conditions of the anodic formation and the thickness of Ag(I) oxide nanofilm on its semiconductor properties

The anodic formation of Ag(I) oxide nanofilms on polycrystalline silver and Ag–Au alloys as well as on low-index single crystals of silver in 0.1?М KOH was examined. By the methods of photocurrent i _ph and photopotential E _ph measurements, the n-type conductivity of Ag₂O film was established. Since the film (6–120 nm) is thinner than the space charge region, the dependence of photocurrent and photopotential appears on the film thickness L: i _ph ~L and E _ph ~L ². The transition from polycrystalline silver to single crystals as well as the addition of a small amount of gold (X _Au?≤?4 at.%) into the silver lattice decreases the degree of deviation from the stoichiometric composition Ag₂O. The parameters of Ag₂O film (optical absorption coefficient α, donor defects concentration N _D, space charge region W, and Debye’s length of screening L _D) depend on the index of a crystal face of silver, volume concentration of gold X _Au in the alloy, and film-formation potential E. At Е?=?0.52 V, the sequences of variation of these parameters correlate with the reticular density sequence. The growth of the potential disturbs these sequences. The band gap in Ag₂O formed on Ag_poly, Ag_hkl, and Ag–Au is 2.32, 2.23, and 2.19 eV. Flat band potential in Ag(I) oxide, formed on Ag_poly in 0.5 M KOH is 0.37 V. The appearance of the clear dependence between the state of the oxide/metal interface and the structure-sensitive parameters of semiconductor Ag(I) oxide phase allows considering the anodic formation of Ag₂O on Ag as a result of the primary direct electrochemical reaction, not of the precipitation from the near-electrode layer.     

IR and NMR spectra,intramolecular hydrogen bonding and conformations of para-tert-butyl-aminothiacalix[4]arene in solid state and chloroform solution

It is demonstrated that dissolution of aminothiacalix[4]arene in chloroform results in transformation of 1,3-alternate conformation, adopted in single-crystal and bulk polycrystalline solids, to the pinched-cone form. This conformer is stabilised by the intramolecular hydrogen bonds of two distal amino-groups acting as H-donors with another two amino moieties that appear as H-acceptors. The H-bonds cause quite small (ca. 10–20 cm^?1) red shift of the IR bands of the NH₂ stretching vibrations, which suggests rather weak NH?N hydrogen bonding. This latter is sufficient to stabilize the pinched-cone conformation in the chloroform solution, but the energy gap between the pinched-cone and other conformations is small, and solid-state intermolecular forces easily overcome it, leading to realisation of the 1,3-alternate conformer. The comparison of the DFT computed and experimental vibrational and NMR spectra demonstrates good quality of present quantum-chemical computations, allows complete interpretation of the spectra and reveals simple IR and NMR spectroscopic markers of the conformers of aminothiacalix[4]arenes.     

Crystal structures and spectral properties of new Cd(II) and Hg(II) complexes of monensic acid with different coordination modes of the ligand

The single crystal X-ray structures and the spectroscopic properties of complexes of monensic acid (C₃₆H₆₂O₁₁·H₂O) with toxic metal ions of Cd(II) and Hg(II) are discussed. The cadmium(II) complex (1) is of composition [Cd(C₃₆H₆₁O₁₁)₂(H₂O)₂] and crystallizes in the monoclinic system (space group P2(1), Z = 2) with a = 12.4090(8), b = 24.7688(16), c = 14.4358(11) Å, β = 91.979(7)°. Two ligand monoanions are bound in a bidentate coordination mode to Cd(II) via the carboxylate and the primary hydroxyl oxygens occupying the equatorial plane of the complex. The axial positions of the inner coordination sphere of Cd(II) are filled by two water molecules additionally engaged in intramolecular hydrogen bonds. The Hg(II) complex (2), [Hg(C₃₆H₆₀O₁₁)(H₂O)], crystallizes in the orthorhombic system (space group P2(1)2(1)2(1), Z = 4) with a = 12.7316(2), b = 16.4379(3), c = 18.7184(4) Å. The monensic acid reacts with Hg(II) in a tetradentate coordination manner via both oxygen atoms of the carboxylate function and oxygens of two hydroxyl groups. The twofold negative charge of the ligand is achieved by deprotonation of carboxylic and secondary hydroxyl groups located at the opposite ends of the molecule. Hg(II) is surrounded by five oxygen atoms in a distorted square pyramidal molecular geometry.

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Apatite type lanthanum silicate and composite anode half cells

Apatite type rare earth silicates are being extensively studied as electrolyte material for intermediate temperature solid oxide fuel cells (SOFC). In this paper we presents results on synthesis of Al and/or Fe-doped ATLS, the design of compatible anode materials, thermal expansion properties and co-sintering of half-cells from expansion matched materials using the advanced pulsed electric current sintering (PECS) technique. The issues related to the co-sintering of half cells have been addressed successfully by the combined use of nano powders and PECS.     

The Fried Average Entropy and Slow Entropy for Actions of Higher Rank Abelian Groups

We consider two numerical entropy-type invariants for actions of \({\mathbb{Z}^k}\) , invariant under a choice of generators and well-adapted for smooth actions whose individual elements have positive entropy. We concentrate on the maximal rank case, i.e. \({\mathbb{Z}^k,\,k \geq 2}\) actions on k + 1-dimensional manifolds. In this case we show that for a fixed dimension (or, equivalently, rank) each of the invariants determines the other and their values are closely related to regulators in algebraic number fields. In particular, in contrast with the classical case of \({{\mathbb Z}}\) actions the entropies of ergodic maximal rank actions take only countably many values. Our main result is the dichotomy that is best expressed under the assumption of weak mixing or, equivalently, no periodic factors: either both invariants vanish, or their values are bounded away from zero by universal constants. Furthermore, the lower bounds grow with dimension: for the first invariant (the Fried average entropy) exponentially, and for the second (the slow entropy) linearly.     

A Teacher’s Conception of Definition and Use of Examples When Doing and Teaching Mathematics

To contribute to an understanding of the nature of teachers’ mathematical knowledge and its role in teaching, the case study reported in this article investigated a teacher’s conception of a metamathematical concept, definition, and her use of examples in doing and teaching mathematics. Using an enactivist perspective on mathematical knowledge, the authors give an account of the case of Lily, a prospective, then beginning, teacher who conceived of mathematical definition as an object with particular form and function and engaged in purposeful, specialized use of examples when doing and teaching mathematics. Lily’s case illustrates how a teacher’s interpretation of examples (as exemplifications or single instances) and conception of the form and function of definitions can influence her doing and teaching mathematics. An implication is that teacher preparation should foster teachers’ abilities to use examples purposefully to provide students with rich opportunities to engage in mathematical processes such as defining.     

The Inclusion Properties of a New Watersoluble Sulfonated Calix[4]resorcinarene towards Alkylammonium and N-Methylpyridinium Cations

The inclusion behaviour of a new water-soluble sulfonated calix[4]resorcinarene towards alkylammonium and N-methylpyridinium cations has been investigated on the basis of ¹H NMR spectroscopy and pH-potentiometry data. The inclusion of the N-methylpyridinium cation has been found to be dependent on pH with the preferable inclusion of the methyl substituent in alkaline and the aromatic ring in neutral aqueous media.