Cation deficient layered Ruddlesden-Popper-related oxysulfides La2LnMS2O5 (Ln=La, Y; M=Nb, Ta)

The structures of the new oxysulfide Ruddlesden-Popper phases La2LnMS2O5 (Ln=La, Y; M=Nb, Ta) are reported together with an iodide-containing variant: La3-xNb1+xS2O5I2x (0相似文献   

Nonlinear Multigrid Methods for Numerical Solution of the Unsaturated Flow Equation in Two Space Dimensions

Picard and Newton iterations are widely used to solve numerically the nonlinear Richards’ equation (RE) governing water flow in unsaturated porous media. When solving RE in two space dimensions, direct methods applied to the linearized problem in the Newton/Picard iterations are inefficient. The numerical solving of RE in 2D with a nonlinear multigrid (MG) method that avoids Picard/Newton iterations is the focus of this work. The numerical approach is based on an implicit, second-order accurate time discretization combined with a second-order accurate finite difference spatial discretization. The test problems simulate infiltration of water in 2D unsaturated soils with hydraulic properties described by Broadbridge–White and van Genuchten–Mualem models. The numerical results show that nonlinear MG deserves to be taken into consideration for numerical solving of RE.     

On the local existence of solutions to a class of nonconvex evolution inclusions

We prove the local existence of solutions to the Cauchy problemx'∈-?_F V(x)+F(x+f(t,x),x(0)=x ₀, where? _FV is the Fréchet subdifferential of a functionV with aψ-monotone subdifferential of order 2,F is an upper semicontinuous set-valued map contained in the Fréchet subdifferential of aφ- convex function of order two andf is a Carathéodory mapping.     

Mechanism of pyridine-ligand exchanges at the different labile sites of 3d heterometallic and mixed valence mu3-oxo trinuclear clusters

The syntheses and single crystal X-ray structural analysis of five novel hetero- and homometallic mu 3-oxo trinuclear cluster with the formula [Fe (III) 2M (II)(mu 3-O)(mu-O 2CCH 3) 6(4-Rpy) 3]. x(4-Rpy). y(CH 3CN) where R = Ph for 1(Fe 2Mn), 2(Fe 2Fe), 3(Fe 2Co), 4(Fe 2Ni) and R = CF 3 for 5(Fe 2Co), are reported. The persistence of the structure for compounds 2- 5 in dichloromethane solution in the temperature range 190-320 K is demonstrated by (1)H and (19)F NMR spectroscopy. Even at the lowest temperature, the electron exchange in the homometallic mixed-valence compound 2(Fe 2Fe) is in the fast regime at the NMR time scale. Variable temperature and pressure NMR line broadening allowed quantifying the fast coordinated/free 4-Rpy exchanges at the two labile metal centers in these clusters: 2: Fe (III)( k (298)/10 (3) s (-1) = 16.6; Delta H (++) = 60.32 kJ mol (-1); Delta S (++) = + 34.8 J K (-1) mol (-1); Delta V (++) = + 12.5 cm (3) mol (-1)); 3: Fe (11.9; 58.92; +30.7; +10.6) and Co (2.8; 68.24; +49.8; +13.9); 4: Fe(12.2; 67.91; +61.0; -) and Ni (0.37; 78.62; +67.8; +12.3); 5: Fe (46; 58.21; +39.3; +14.2) and Co (4.7; 55.37; +11.2; +10.9). A limiting D mechanism is assigned to these exchange reactions. This assignment is based on a first-order rate law, the detection of intermediates, the positive and large entropies and volumes of activation. The order of reactivity k (Co) > k (Ni) is expected for a D mechanism at these metal centers: their low exchange rates are due to their strong binding with the 4-Rpy donor. Surrounded by oxygen donors the d (5) iron(III) usually reacts associatively; however, here due to low affinity of this ion for nitrogen the mechanism is D and the rate of exchange is very fast, even faster than on the divalent ions. There is no significant effect of the divalent ion in cluster 2, 3, and 5 on the exchange rates of 4-Phpy at the iron center, which seems to indicate that the specific electronic interactions between the three ions making the clusters do not influence the Fe (III)-N bond strength.     

Study of the corrosion products formed on carbon steel surface in hydrochloric acid solution

Effect of an antibacterial drug, sulfacetamide, IUPAC name N-[(4-aminophenyl) sulfonyl] acetamide (APSA), on the corrosion products formed on carbon steel surface in 1.0?mol?L^?1 HCl solution has been investigated using mass loss, X-ray photoelectron spectroscopy (XPS), and simultaneous thermal and differential scanning calorimetry/differential thermal analysis (TG/DSC/DTA). Mass loss measurements reveal that the corrosion rate of carbon steel is retarded by APSA and that the inhibition efficiency of this inhibitor increases with increasing the concentration. XPS analysis shows that, at this stage, the main product of corrosion is a non-stoichiometric Fe³⁺ oxyhydroxide, consisting of a mixture of FeO(OH) in anhydrous or hydrated forms, containing Cl^? inclusions and adsorbed APSA molecules. The mechanism of inhibition was discussed in light of the chemical structure of the investigated inhibitor. The corrosion products were analyzed using TG/DSC/DTA technique.     

Synthesis, structural and spectral studies of Cu(II) and V(IV) complexes of a novel Schiff base derived from pyridoxal. Antimicrobial activity

A novel Schiff base, N-(4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one)pyridoxaldimine (HL·HCl), was prepared and structurally characterized on the basis of elemental analyses, ¹H and ¹³C NMR, and IR spectral data. The synthesis and characterization of several Cu(II) (1-6) and V(IV) (7) complexes with N-(4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one)pyridoxaldimine are reported. The composition and structures of the copper(II) and vanadium(IV) complexes were proposed based on elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic and EPR spectroscopy. In addition, the structures of the ligand and the complex [CuL(H₂O)₂]NO₃·2.25H₂O (1) have been determined by single-crystal X-ray diffraction, showing that the Cu(II) center has a distorted square-pyramidal geometry. The ligand and the complexes were also tested for their in vitro antibacterial activity.     

The chemistry of the phosphates of barium and tetravalent cations in the 1:1 stoichiometry

The chemistry of phosphates of barium and tetravalent cations [BaM^IV(PO₄)₂] is reviewed. Such phosphates crystallise in the C2/m space group for M^IV=Ti, Zr, Hf, Ge, Sn, and Mo, and in the P2₁/n space group for BaTh(PO₄)₂. The existence of BaM^IV(PO₄)₂ in which M^IV=Pb, Ce, and U is further evaluated. Several aspects, such as phase transitions in the compounds with yavapaiite structure, solid solutions of BaM^IV(PO₄)₂ compounds and practical applications are briefly discussed.     

Ordered structure and preferred orientation of boehmite films prepared by the sol-gel method

Several boehmite films were produced using the sol-gel route. The drying process, the film structure evolution and the final texture of the samples were investigated by means of combined X-ray diffraction and weight variation. A remarkable (0 1 0) preferred orientation (about 97% of the crystallites) was found for xerogel films with thickness ranging from 1.5 to 24 μm. The ordered structure is already present in the sol state and is appeared and enhanced during drying, before gelling. This phenomenon may be attributed to the particular boehmite structure that induces special crystallite organization in the aquagel.     

Calorimetric measurements of diluted spin crossover complexes [FexM1−x(btr)2(NCS)2]·H2O with M = Zn and Ni

Motivated by the application of the First Order Reversal Curve (FORC) technique to obtain a distribution of like spin domains in the spin crossover complexes [Fe_xM_1−x(btr)₂(NCS)₂]·H₂O with M^II = Zn and Ni, we have performed Differential Scanning Calorimetry (DSC) experiments. We have measured the heat capacity in the heating and cooling modes and then calculated the enthalpy and the entropy variations at the phase transition. In the framework of an Ising-like model, we have converted the experimental thermal hysteresis into terms of physical parameters related to these compounds. We have also performed a statistical analysis of these parameters and concluded that the correlation between them increases with the dilution degree of these spin crossover complexes.