N-aryl-and N-vinyldiaza-18-crown-6: Synthesis and complexing ability

The nucleophilic aromatic and vinyl substitution using diaza-18-crown-6 as nucleophile afforded a number of its N,N’-diaryl-[aryl = 2,4-(NO₂)₂C₆H₃, 4-C₅F₄N, 4-CF₃C₆F₄] and N,N’-dialkenyl-substituted derivatives [alkenyl = PhC(O)CH=CH, MeOCOCH=CH, (EtO₂C)₂C=C(Ph), etc.]. Arylation of diaza-18-crown-6 with nonactivated aryl bromides, such as 4-Me₂NC₆H₄Br, 4-MeOC₆H₄Br, C₆H₅Br, and 4-CF₃C₆H₄Br, was effected under catalysis by palladium complexes. N,N’-Diaryldiaza-18-crowns-6 having electron-acceptor substituents in the aromatic rings turned out to be incapable of forming complexes with metal cations, while their analogs containing electron-donor para-methoxy and para-dimethylamino groups gave complexes with barium perchlorate.     

A fractal model of reinforcement of elastoplastic nanocomposites

Within the framework of fractal analysis and percolation theory, an alternative model of reinforcement of filled polymers is offered. Practically, this model can be used only to describe the reinforcement of nanocomposites, because, according to the treatment considered, a pronounced reinforcement can be reached only at ratios of filler particle diameter to the statistical segment length of about 10 and less. A theoretical calculation showed a good qualitative and quantitative agreement with experiments. The type of reinforcement mechanism of composites is determined by the type of the space (fractal or Euclidean) in which the structure of the polymeric matrix is formed. __________ Translated from Mekhanika Kompozitnykh Materialov, Vol. 42, No. 6, pp. 797–802, November–Decem ber, 2006.     

Laser-induced site-selective silver seeding on polyimide for electroless copper plating

Ag particles were generated on Ag⁺-doped polyimide film by laser direct writing, followed by selective copper deposition using the metallic silver particles as seeds. Laser irradiation caused in situ reduction and agglomeration of silver on the polyimide film. The copper lines were less uniform and compact with higher scanning velocity and the width of the deposited copper line could reach 25 μm. Equations of the relationship between scanning velocity and connectivity of the deposited copper patterns have been derived. The process was characterised by AFM, XPS, SEM, and semiconductor characterisation system.     

Radiochemistry in chemistry and chemistry related undergraduate programmes in Argentina

Summary The evolution of education in Argentina at the university level is described. The detailed search of the educational offer shows that less than half of the universities (35 out of 92) include chemistry and chemistry related undergraduate programmes in their curriculum. The revision of the position of radiochemistry in these programmes reveals that only seven courses on radiochemistry are currently offered. Radiochemistry is included only in few programmes in chemistry and biochemistry. With respect to the programmes in chemical engineering the situation is worse. This offer is strongly concentrated in Buenos Aires and its surroundings.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.     

Influence of the counterion size on swelling and collapse of polyelectrolyte gel

A theory that predicts the effect of the counterion size on the swelling and collapse of a weakly charged polyelectrolyte gel was developed. In addition to excluded-volume interactions between monomer units of the gel, the theory involves the counterion-monomer unit and counterion-counterion interactions in terms of the virial approximation. The character of interactions between different units in the system varies from repulsion to attraction depending on the type of solvent, counterion, and dielectric permittivity of the solvent. For solvents with a low permittivity, the effect of condensation of counterions resulting in the formation of ion pairs is taken into account.     

Magnetic ordering of YBa2(Cu1−x Fe x )3O7

The Mössbauer spectra of YBa₂(Cu_1?x Fe _x )₃O₇ at room temperature show several doublets attributed to Fe in Cu(1) sites with different oxygen configurations. Here we present a systematic study performed at 4.2 K forx=0.005, 0.01, 0.03, 0.05, 0.10, 0.15. To obtain information about the magnetic ordered state two samples, withx=0.005 andx=0.15, have been studied at 4.2 K underB _ext=5 T. The Mössbauer spectra indicate that the iron moments are polarized forx=0.005, while in the ordered state (x=0.15) they have an antiferromagnetic or spin-glass-like arrangement with high anisotropy.     

Local instability of horizontal elliptic excavations in elastoviscoplastic rock masses

In the framework of three-dimensional stability equations, we study the local instability of a horizontal excavation with elliptic cross-section under the assumption that the rock mass behaves like an elastoviscoplastic media. An estimate of the influence of the rock mass parameters on the value of the critical pressure is given.     

High order generalized upwind schemes and numerical solution of singular perturbation problems

High even order generalizations of the traditional upwind method are introduced to solve second order ODE-BVPs without recasting the problem as a first order system. Both theoretical analysis and numerical comparison with central difference schemes of the same order show that these new methods may avoid typical oscillations and achieve high accuracy. Singular perturbation problems are taken into account to emphasize the main features of the proposed methods. AMS subject classification (2000)  65L10, 65L12, 65L50