The use of the consecutive adsorption of pyridine bases and carbon monoxide in the IR spectroscopic study of the accessibility of acid sites in microporous/mesoporous materials

A new approach to the evaluation of the accessibility of acid sites in microporous/mesoporous materials is developed and tested using a series of dealuminated mordenites. This approach is based on an IR-spectroscopic study of the consecutive adsorption of substituted alkylpyridines (pyridine, 2,4,6-trimethylpyridine, and 2,4,6-triethylpyridine) and carbon monoxide. This method allowed us to determine the strength and number of acid sites with various degrees of accessibility. The adsorption of 2,4,6-triethylpyridine on various types of materials is studied. The extinction coefficients of alkylpyridines are determined using a McBain balance placed in a cell for IR-spectroscopic measurements. Original Russian Text N.S. Nesterenko, F. Thibault-Starzyk, V. Montouilliout, V.V. Yushchenko, C. Fernandez, J.-P. Gilson, F. Fajula, I.I. Ivanova, 2006, published in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 45–53.     

A method to calculate density distribution of adsorption centers from temperature-programmed desorption spectra

A new method to calculate the function of density distribution of adsorption centers according to the activation energies of desorption by using temperature-programmed desorption curves is suggested. The application of this method is exemplified by toluene desorption from ZSM-5 zeolite.

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Role of Hydrodynamic Conditions in the Distribution of Anodic Dissolution Rates in Cavity Etching Regions during Electrochemical Micromachining of Partially Insulated Surfaces

Experimental study of the distribution of local rates of electrochemical micromachining in the presence of photoresist masks in various hydrodynamic conditions (macroscopically nonuniform rotating disk electrode, sprayer flow, an electrode placed into a cell with chaotic bulk electrolyte mixing) shows that the maximum etching localization is achieved at the control of the dissolution rate by the mass transport rate (at achieving the anodic limiting current). The localization enhancement as compared to the primary current distribution takes place in the case of a turbulent flow at hydrodynamic conditions where the removal of dissolution products from the undercutting region is hindered. These conditions (electrochemical reaction limited by the ion mass transport rate, high resistance to the mass transport in the undercutting region) are necessary for the localization enhancement using a pulsed anodic–cathodic treatment.     

Calculation of carbon-carbon bond deformation curves for fluorinated ethylenes and the corresponding carbocations

Carbon-carbon bond deformation curves for fluorinated ethylene molecules and the corresponding carbocations were calculated by the ab initio self-consistent field method in the 5-31G basis set. The maximum force required for bond cleavage was taken as a criterion for bond strength. It has been found that for ethylene, replacement of hydrogen by fluorine insignificantly strengthens the C=C bonds in symmetric molecules. However, in molecules with an asymmetric arrangement of fluorine atoms, the bond is slightly weakened due to different charges on the carbon atoms. The configuration of the corresponding carbocations also depends on the bond polarity: an assymmetric distribution of electron density in the C=C bond region leads to the formation of σ-complexes, while a symmetric distribution of electron density (pure covalent bonding) gives π-complexes. Since the carbon-carbon bond in the σ-complexes is essentially weaker, one should expect significant weakening of the bond in high-acidity media if the bond exhibits any kind of asymmetry (chain branching, defects, etc.). For the considered molecules, an antibatic correlation has been established between the strength criterion F_max (unlike the dissociation energy) and the bond length. Institute of Physical Chemistry, Russian Academy of Sciences, Moscow. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 1, pp. 34–41, January–February, 1995. Translated by I. Izvekova     

Hierarchical condensation near phase equilibrium

A novel mechanism of new phase formation is studied both experimentally and theoretically in the example of quasi-equilibrium stationary condensation in an ion–plasma sputterer. Copper condensates are obtained to demonstrate that a specific network structure is formed as a result of self-assembly in the course of deposition. The fractal pattern related is inherent in the phenomena of diffusion limited aggregation. Condensate nuclei are shown to form statistical ensemble of hierarchically subordinated objects distributed in ultrametric space. The Langevin equation and the Fokker–Planck equation related are found to describe stationary distribution of thermodynamic potential variations at condensation. Time dependence of the formation probability of branching structures is found to clarify the experimental situation.     

Complexation of calix[4]arenehydroxymethylphosphonic acids with amino acids. Binding constants determination of the complexes by HPLC method

Host–Guest complexation process of calixarenehydroxymethylphosphonic acids with 10 amino acids in solution H₂O/MeCN (99:1) had been studied. Binding constants of the inclusion complexes from the dependence between capacity factors of the Guest and the calixarene-Host concentration in the mobile phase had been calculated. It was shown the binding constants depend on the nature of the amino acid residue, conformation of the calixarene skeleton, quantity of phosphoryl groups at the upper rim. In accordance with molecular calculation the complexation is determined by the electrostatic interactions between the positively charged nitrogen atom of amino acid and the negatively charged oxygen atom of phosphonic group of calixarene molecule, hydrogen bonds, π–π, CH–π and solvatophobic, interactions.     

Study of K^ - \to \pi ^0 e^ - \overline \nu _e \gamma decay with ISTRA+ setup

Results of study of the $K^ - \to \pi ^0 e^ - \overline \nu \gamma $ decay at the ISTRA+ setup are presented. We observed 4476 events of this decay. The branching ratio is found to be $R = \frac{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e \gamma )}}{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e )}}$ = (1.81±0.03(stat.)±0.07(syst.)) × 10^?2 for E*_γ > 10 MeV and θ*_eγ > 10°. For comparison with the previous experiment the branching ratio with cuts E*_γ > 10 MeV, 0.6 < cos θ*_eγ < 0.9 is calculated: R = $\frac{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e \gamma )}}{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e )}}$ = (0.47±0.02(stat.) ± 0.03(syst.)) × 10^?2. For the cuts E*_γ > 30 MeV and θ*_eγ > 20°, used in most theoretical papers, Br = (3.06 ± 0.09(stat.) ± 0.14(syst.)) × 10^?4. For the asymmetry we get A _ξ = ?0.015 ± 0.021. At present it is the best estimate of this asymmetry.