Formation of Pyrogenic Silica: Spectroscopic and Quantum Chemical Insight

This article describes the genesis of amorphous silica under high-heat conditions from SiO₂ molecules through protoparticles, primary particles, and aggregates to agglomerates using vibrational spectra and quantum chemical simulations data. The impact of small molecules (water, HCl, CO₂) is also discussed. The article also explains the nature of the pyrogenic silica amorphism.     

Quartz crystal microbalance simulation of the directionality of Si etching in CF4 glow discharges

Two quartz crystal microbalances have been mounted in a planar rf discharge system in such a way that the potential of the microbalances with respect to the glow discharge can be varied. This apparatus allows a rapid simulation of the etching directionality that can be expected in real pattern transfer situations in that operating one microbalance at ground and one at a negative potential gives a measure of the sidewall and vertical etch rates, respectively. The voltage threshold for ion-assisted etching has been determined to be 20 V which is the approximate value of the plasma potential in this asymmetric system.     

Heterometallic Cu/Co and Cu/Co/Zn complexes bearing rare asymmetric tetranuclear cores: synthesis, structures, and magnetic and catalytic properties toward the peroxidative oxidation of cycloalkanes

The three novel heterometallic complexes [CuCo(III)Co(II)(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.55)(H(2)O)(0.45)](H(2)O)(0.45) (1), [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.74)(H(2)O)(0.26)](H(2)O)(0.26) (2), and [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(DMF)] (3) have been prepared using a one-pot reaction of copper powder with cobalt chloride (1) and zinc nitrate (2, 3) in a methanol (1, 2) or dimethylformamide (3) solution of N-methyldiethanolamine. A search of the Cambridge Structural Database shows that the tetranuclear asymmetric cores M(4)(μ(3)-X)(μ-X)(5) of 1-3 represent an extremely rare case of M(4)X(6) arrays. The magnetic investigations of 1 disclose antiferromagnetic coupling in a Co(II)-Cu(II)-Co(II) exchange fragment with J(Co-Cu)/hc = -4.76 cm(-1), J(Co-Co)/hc = -2.76 cm(-1), and D(Co)/hc = +34.3 cm(-1). Compounds 1-3 act as precursors for the mild peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone with overall yields up to 23%. The synthetic and structural features as well as the thermogravimetric behavior and electrospray ionization mass spectrometry data are discussed.     

A comparative electrochemical study of diffusion in room temperature ionic liquid solvents versus acetonitrile.

Measurements on the diffusion coefficient of the neutral molecule N,N,N',N'-tetramethyl-para-phenylenediamine and the radical cation and dication generated by its one- and two-electron oxidation, respectively, are reported over the range 298-348 K in both acetonitrile and four room temperature ionic liquids (RTILs). Data were collected using single and double potential step chronoamperometry at a gold disk electrode of micrometer dimension, and analysed via fitting to the appropriate analytical expression or, where necessary, to simulation. The variation of diffusion coefficient with temperature was found to occur in an Arrhenius-type manner for all combinations of solute and solvent. For a given ionic liquid, the diffusional activation energies of each species were not only closely equivalent to each other, but also to the RTIL's activation energy of viscous flow. In acetonitrile supported with 0.1 M tetrabutylammonium perchlorate, the ratio in diffusion coefficients of the radical cation and dication to the neutral molecule were calculated as 0.89 +/- 0.05 and 0.51 +/- 0.03, respectively. In contrast, amongst the ionic liquids the same ratios were determined to be on average 0.53 +/- 0.04 and 0.33 +/- 0.03. The consequences of this dissimilarity are considered in terms of the modelling of voltammetric data gathered within ionic liquid solvents.     

In situ and online monitoring of hydrodynamic flow profiles in microfluidic channels based upon microelectrochemistry: optimization of electrode locations.

Herein, we extend our previous approach concerning the reconstruction of profiles of pressure-driven hydrodynamic flow in microfluidic channels based on current measurements at band electrode(s) [see the preceding paper ChemPhysChem 2005, 6, 1581]. We address the central issue of optimization of geometrical parameters describing the electrode(s) assembly (a single band and two bands working in generator-collector mode) within the channel flow cell to enhance the speed and precision of the flow profile reconstruction method.     

Ethers of indoxylie acid

O-alkylations of indoxylie acid (2b) to produce 3-indolyl-alkyl ethers and a synthesis of 5-melhoxy-2-earboxyindol-3-oxyaeetic acid (25) are described.     

Forbidden domains of a toroidal magnetic shield

Russian Physics Journal -     

Wave diffraction from the Biconical Section in the semi-infinite conical region

The electromagnetic problem by the finite bicone, which is formed with the perfectly conducting semi-infinite cone and the finite cone with truncated vertex, is studied. Bicone is excited axial-symmetrically by the ring magnetic source. The diffracted field is represented through the series of the transversal magnetic (TM) modes; the lower mode among them is called the transversal electromagnetic wave (TEM). On the basis of this representation and using the mode matching technique, we derive the series equations to determine the unknown complex modes magnitudes. In view of the electric field singularities at the conical edges, these equations are represented in the form of the limiting transition from the finite sums to the series. We derive the rule of this transition, as well as the procedure for reducing them to the infinite system of linear algebraic equations (ISLAE) of the first kind. We study asymptotic properties of the matrix elements and find that the main part of their static limit and their behavior for large indexes form the matrix operator of the convolution type; the corresponding inverted operator in the analytical form is obtained. Both these operators, which we call the regularization operators, are used for the transition from the ISLAE of the first kind to the ISLAE of the second kind. The ISLAE thus obtained allow for the solution of any geometrical parameters and frequency with the given accuracy. The asymptotic properties of their solutions are analyzed, and the numerical examinations of the far field patterns are provided.     

From Isomorphic Rooted Trees to Isometric Ultrametric Spaces

For every finite ultrametric space X we can put in correspondence its representing tree T_X. We found conditions under which the isomorphism of representing trees T_X and T_Y implies the isometricity of ultrametric spaces X and Y having the same range of distances.