[VS_4Cu_6(Py)_8I_3]的合成和晶体结构

在(NH4)3VS4/CuI/Py反应体系中合成了新化合物 [VS4Cu6(Py)8I3]并测定其晶体结构。该化合物(C40H40N8Cu6I3S4V)属正交晶系, 空间群为Fdd2, 晶胞参数为: a = 29.924(6), b = 13.475(3), c = 25.853(5) , V = 10425(4) ?, Dc = 2.006 g/cm3, Mr = 1573.92, Z = 8, (MoK) = 4.546 mm-1, F(000) = 6048。结构由直接法解出, 用全矩阵最小二乘法修正, 最终偏离因子R = 0.023, wR = 0.069。簇合物分子是由6个带端基配体的Cu沿着四面体单元VS4的6条SS边配位而成, 6个Cu排列成了1个八面体, V基本位于八面体的中心, 整个分子具有C2对称性。     

Shape preservation regions for six-dimensional spaces

We analyze the critical length for design purposes of six-dimensional spaces invariant under translations and reflections containing the functions 1, cos t and sin t. These spaces also contain the first degree polynomials as well as trigonometric and/or hyperbolic functions. We identify the spaces whose critical length for design purposes is greater than 2π and find its maximum 4π. By a change of variables, two biparametric families of spaces arise. We call shape preservation region to the set of admissible parameters in order that the space has shape preserving representations for curves. We describe the shape preserving regions for both families. To our friend Mariano Gasca on occasion of his 60th birthday Research partially supported by the Spanish Research Grant MTM2006-03388, by Gobierno de Aragón and Fondo Social Europeo.     

Theoretical study on the structures and electronic spectra of TCNE2-.

Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) complexes have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE2- has D2d symmetry in vacuum as well as in the solvents dichloromethane and acetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoretical results are compared to the experimental data and good agreement is achieved.     

Inferring mixed-culture growth from total biomass data in a wavelet approach

It is shown that the presence of mixed-culture growth in batch fermentation processes can be very accurately inferred from total biomass data by means of the wavelet analysis for singularity detection. This is accomplished by considering simple phenomenological models for the mixed growth and the more complicated case of mixed growth on a mixture of substrates. The main quantity provided by the wavelet analysis is the Hölder exponent of the singularity that we determine for our illustrative examples. The numerical results point to the possibility that Hölder exponents can be used to characterize the nature of the mixed-culture growth in batch fermentation processes with potential industrial applications. Moreover, the analysis of the same data affected by the common additive Gaussian noise still lead to the wavelet detection of the singularities although the Hölder exponent is no longer a useful parameter.     

Electrocatalytic activity of sol-gel-prepared RuO2/Ti anode in chlorine and oxygen evolution reactions

Electrocatalytic properties of RuO₂/Ti anode with different coating masses, which are prepared by the alkoxide sol-gel procedure, are investigated in chlorine and oxygen evolution reactions by polarization measurements and electrochemical impedance spectroscopy in H₂SO₄ and NaCl electrolytes. According to polarization measurements, the activity of anodes at overpotentials below 100 mV is independent of coating mass. However, impedance measurements above 100 mV reveal changes in the activity of anodes in chlorine evolution reaction for different coating masses. The diffusion limitations related to the evolved chlorine are registered in low-frequency domain at 1.10 V (SCE), diminishing with the increase in potential to the 1.15 V (SCE). The observed impedance behavior is discussed with respect to the activity model for activated titanium anodes in chlorine evolution reaction involving formation of gas channels within porous coating structure. Gas channels enhance the mass transfer rate similarly to the forced convection, which also increases the activity of anode. This is more pronounced for the anode of greater coating mass due to its more compact surface structure. The more compact structure appears to be beneficial for gas channels formation. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1173–1179. The text was submitted by the authors in English.     

Air-activated carbons from almond tree pruning: Preparation and characterization

In this work the results obtained in the preparation and characterization of carbons made from almond tree pruning by non-catalytic and catalytic gasification (using K and Co) with air are analyzed and discussed. The main aim was to obtain high quality activated carbons at the lowest possible cost. The variables studied have been the temperature (190-260 °C) and the time (1-10 h) in non-catalytic gasification and the influence of the catalyst type (K and Co, 1 wt.% referred to cation, at 190 °C and 1 h) and the time (1-4 h) in catalytic gasification with Co at 190 °C. The air flow rate used in all the series was 167 cm³ min⁻¹. In non-catalytic gasification the reaction normalized rate versus the conversion degree was maintained until a conversion value of 10% for the experiment made at 260 °C since, at lower temperatures, this rate drops quickly for low conversion values. The N₂ adsorption isotherms for the carbons of this series resemble type I, although there is an increase of N₂ adsorbed volume at relatively high pressures. A temperature rise produced an increase of the carbon porosity and BET specific surface (116-469 m² g⁻¹). The activation time has a positive effect on the N₂ volume adsorbed by the carbons. The isotherms shapes were similar to those previously commented. A concentration equal to 1 wt.% was used to study the influence of the catalyst type. Under the studied experimental conditions, Co drives to a bigger porosity development than K, although with both catalysts a very similar pore size distribution is obtained. The activation time, in the gasifications catalyzed with Co, gives rise to a very important porosity development in the carbons. This produces a strong increase of the carbon specific surface area with very high values in the 4 h experiment, in which a BET specific surface of 959 m² g⁻¹ was obtained.     

On Genuine Bernstein–Durrmeyer Operators

We continue the studies on the so–called genuine Bernstein–Durrmeyer operators U _n by establishing a recurrence formula for the moments and by investigating the semigroup T(t) approximated by U _n . Moreover, for sufficiently smooth functions the degree of this convergence is estimated. We also determine the eigenstructure of U _n , compute the moments of T(t) and establish asymptotic formulas. Received: January 26, 2007.     

Renormalisation group calculation of the interfacial tension for the three-dimensional Ising model

The interfacial tension of a three-dimensional Ising model in the whole temperature region is calculated by the real-space renormalisation group methods. The cumulant and the finite-cluster approximations with different projection rules are used. The results are consistent with expected low-temperature and global behaviour of the interfacial tension in the three-dimensional model.     

Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al2O3 catalysts

Four NiMo catalyst supported on Al₂O₃ with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 Å for HDS and HDN.