Hexanuclear copper(II) cages built on a central {μ3-O···H···μ3-O} moiety, 1,3-bis(dimethylamino)-2-propanolato and capping R-phosphonates: crystal structures, magnetic behavior, and DFT studies

The syntheses, structural characterization, and magnetic behavior of two new hexanuclear copper(II) complexes derived from R-phosphonic acids and 1,3-bis(dimethylamino)-2-propanol (Hbdmap) with formulas [Cu(6)(μ-bdmap)(3)(μ(3)-Ph-PO(3))(2)(μ(3)-O···H···μ(3)-O)(ClO(4))(2)(H(2)O)]·5H(2)O (1) and [Cu(6)(μ-bdmap)(3)(μ(3)-t-Bu-PO(3))(2)(μ(3)-O···H···μ(3)-O)(μ(1,3)-dca)(dca)(H(2)O)]·6H(2)O (2) (Ph-H(2)PO(3) = phenylphosphonic acid, t-Bu-H(2)PO(3) = tert-butylphosphonic acid, dca = dicyanamide) are reported. Compounds 1 and 2 are hexanuclear 3.111 R-phosphonate(2-)/1,3-bis(dimethylamino)-2-propanolato(1-) cages including in the center the [μ(3)-O···H···μ(3)-O](3-) unit. The temperature dependence of the magnetic properties of 1 and 2 clearly indicates an overall strong antiferromagnetic coupling confirmed by DFT calculations.     

Production, bleaching, and characterization of pulp from Stipa tenacissima

Alfa grass pulping was successfully performed in hydro-organic acid medium under mild conditions (107°C, atmospheric pressure, cooking time: 3 h). Use of an acetic acid/formic acid/water mixture as pulping liquor was perfectly suitable for selective isolation of pulp, lignin, and hemicelluloses. The unbleached pulp obtained in good yield was first delignified by peroxyacids in organic acid medium and then bleached with hydrogen peroxide in a basic medium to give pulp offering good physico-chemical and mechanical characteristics.     

Heterogeneous Interaction of H(2)O(2) with TiO(2) Surface under Dark and UV Light Irradiation Conditions

The heterogeneous interaction of H(2)O(2) with TiO(2) surface was investigated under dark conditions and in the presence of UV light using a low pressure flow tube reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial concentration of gaseous H(2)O(2) ([H(2)O(2)](0) = (0.17-120) × 10(12) molecules cm(-3)), irradiance intensity (J(NO(2)) = 0.002-0.012 s(-1)), relative humidity (RH = 0.003-82%), and temperature (T = 275-320 K). Under dark conditions, a deactivation of TiO(2) surface upon exposure to H(2)O(2) was observed, and only initial uptake coefficient of H(2)O(2) was measured, given by the following expression: γ(0)(dark) = 4.1 × 10(-3)/(1 + RH(0.65)) (calculated using BET surface area, estimated conservative uncertainty of 30%) at T = 300 K. The steady-state uptake coefficient measured on UV irradiated TiO(2) surface, γ(ss)(UV), was found to be independent of RH and showed a strong inverse dependence on [H(2)O(2)] and linear dependence on photon flux. In addition, slight negative temperature dependence, γ(ss)(UV) = 7.2 × 10(-4) exp[(460 ± 80)/T], was observed in the temperature range (275-320) K (with [H(2)O(2)] ≈ 5 × 10(11) molecules cm(-3) and J(NO(2)) = 0.012 s(-1)). Experiments with NO addition into the reactive system provided indirect evidence for HO(2) radical formation upon H(2)O(2) uptake, and the possible reaction mechanism is proposed. Finally, the atmospheric lifetime of H(2)O(2) with respect to the heterogeneous loss on mineral dust was estimated (using the uptake data for TiO(2)) to be in the range of hours during daytime, i.e., comparable to H(2)O(2) photolysis lifetime (～1 day), which is the major removal process of hydrogen peroxide in the atmosphere. These data indicate a strong potential impact of H(2)O(2) uptake on mineral aerosol on the HO(x) chemistry in the troposphere.     

Determination of division algebras with 243 elements

Finite nonassociative division algebras (i.e., finite semifields) with 243 elements are completely classified. Nine Knuth orbits were found, two of which are new. All are primitive, and all but the twisted field planes are fractional dimensional.     

On nonlinear coupled diffusions in competition systems

A class of reaction-diffusion systems modeling plant growth with spatial competition in saturated media is presented. We show, in this context, that standard diffusion can not lead to pattern formation (Diffusion Driven Instability of Turing). Degenerated nonlinear coupled diffusions inducing free boundaries and exclusive spatial diffusions are proposed. Local and global existence results are proved for smooth approximations of the degenerated nonlinear diffusions systems which give rise to long-time pattern formations. Numerical simulations of a competition model with degenerate/non degenerate nonlinear coupled diffusions are performed and we carry out the effect of the these diffusions on pattern formation and on the change of basins of attraction.     

Possible mechanisms of the influence of hexylresorcinol on the structure-dynamic and functional properties of lysozyme protein

The influence of hexylresorcinol on the structure, equilibrium fluctuations, and functional activity of water-soluble enzyme lysozyme was studied over a wide range of hexylresorcinol concentrations. Hexylresorcinol was found to be not only a stabilizer of lysozyme. At low hexylresorcinol concentrations (2 to 10 molecules per lysozyme globule), the activity of lysozyme sharply increased; activity began to decrease as the concentration grew. The influence of hexylresorcinol on the structural, dynamic, and functional lysozyme characteristics is well described by models of preferential hydration and preferential protein interaction with hexylresorcinol. The hexylresorcinol molecule consists of hydrophobic (alkyl radical) and hydrophilic (aromatic nucleus) moieties, which has additional regulatory action on the functional activity of lysozyme. As the concentration of hexylresorcinol increases, the effect of regions with preferential hydration begins to noticeably predominate over the effect of preferential interaction with hexylresorcinol. At hexylresorcinol concentrations higher than 100 molecules per lysozyme globule, the activity of lysozyme is fully inhibited. This is caused by the preferential hydration of the protein with the displacement of hexylresorcinol from direct contacts with it. The displacement of hexylresorcinol causes the formation of high-density hexylresorcinol micelles. Dense micelles interfere with the approach of substrates to the protein and fully inhibit its functional activity. The complete inhibition of lysozyme activity occurs at hexylresorcinol concentrations lower by an order of magnitude than glycerol inhibiting concentrations.     

Sharp Sobolev Asymptotics for Critical Anisotropic Equations

We investigate blow-up theory and prove sharp Sobolev asymptotics for a general class of anisotropic critical equations in bounded domains of .     

The micropolar fluid model for blood flow through a tapered artery with a stenosis

A micropolar model for axisymmetric blood flow through an axially nonsymmetreic but radially symmetric mild stenosis tapered artery is presented. To estimate the effect of the stenosis shape, a suitable geometry has been considered such that the axial shape of the stenosis can be changed easily just by varying a parameter （referred to as the shape parameter）. The model is also used to study the effect of the taper angle Ф. Flow parameters such as the velocity, the resistance to flow （the resistance impedance）, the wall shear stress distribution in the stenotic region and its magnitude at the maximum height of the stenosis （stenosis throat） have been computed for different values of the shape parameter n, the taper angle Ф, the coupling number N and the micropolar parameter m. It is shown that the resistance to flow decreases with increasing the shape parameter n and the micropolar parameter m while it increases with increasing the coupling number N. So, the magnitude of the resistance impedance is higher for a micropolar fluid than that for a Newtonian fluid model. Finally, the velocity profile, the wall shear stress distribution in the stenotic region and its magnitude at the maximum height of the stenosis are discussed for different values of the parameters involved on the problem.     

Anisotropic Organised Eddy Simulation for the prediction of non-equilibrium turbulent flows around bodies

The unsteady turbulent flow around bodies at high Reynolds number is predicted by an anisotropic eddy-viscosity model in the context of the Organised Eddy Simulation (OES). A tensorial eddy-viscosity concept is developed to reinforce turbulent stress anisotropy, that is a crucial characteristic of non-equilibrium turbulence in the near-region. The theoretical aspects of the modelling are investigated by means of a phase-averaged PIV in the flow around a circular cylinder at Reynolds number 1.4×10⁵. A pronounced stress–strain misalignment is quantified in the near-wake region of the detached flow, that is well captured by a tensorial eddy-viscosity concept. This is achieved by modelling the turbulence stress anisotropy tensor by its projection onto the principal matrices of the strain-rate tensor. Additional transport equations for the projection coefficients are derived from a second-order moment closure scheme. The modification of the turbulence length scale yielded by OES is used in the Detached Eddy Simulation hybrid approach. The detached turbulent flows around a NACA0012 airfoil (2-D) and a circular cylinder (3-D) are studied at Reynolds numbers 10⁵ and 1.4×10⁵, respectively. The results compared to experimental ones emphasise the predictive capabilities of the OES approach concerning the flow physics capture for turbulent unsteady flows around bodies at high Reynolds numbers.