Problems of Quantitative Spectroscopic Measurements in Heterogeneous Catalysis: Molar Absorption Coefficients of Vibrations in Adsorbed Substances

Published data on the molar absorption coefficients and integral intensities A ₀ of vibrations in physically and chemically adsorbed molecules are reviewed. Analysis of published data shows that bonds characterized by high values of the dipole momentum derivative with respect to the normal coordinate change during adsorption toward decreasing this derivative, whereas bonds characterized by a low value of the derivative change toward increasing the derivative. Thus, adsorption results in a decrease in the difference in values of the dipole momentum derivative with respect to the normal coordinate of different bonds compared with the same bonds in the individual molecules. In addition, the interval of changing the molar absorption coefficients for the surface complexes are at least two orders of magnitude lower than that for the same bonds in the molecules in the gas phase. A series for the degree of easiness in detecting complexes on the catalyst surface (the series of decreasing the molar absorption coefficient) is proposed.     

Catalytic Oxidation (4th World Congress on Oxidation Catalysis, Potsdam, Germany, September 2001)

This paper presents an overview of the plenary lectures and some of the oral and poster presentations at the 4th International Congress on Oxidation Catalysis in Potsdam (Germany). The main topics were the partial oxidation of alkanes and the oxidation of olefins by H₂O₂. Considerable attention is given to the use of modern physical methods in the mechanistic studies of oxidation catalysis and in the studies of catalyst structures.     

Azines and azoles. 64. Mass spectra and tautomerism of 2-aryl-4,6-dioxo-1,3-thiazines

Mass spectra of 2-aryl-4,6-dioxo-1,3-thiazines were studied and the general fragmentation paths of these compounds determined. Based on mass spectra of compounds with fixed structures, 2-aryl-5,5-dialkyl-4,6-dioxo-1,3-thiazines, 4-alkoxy- and 4-acyloxy-2-aryl-6-oxo-1,3-thiazines, the decomposition paths of the dicarbonyl and hydroxycarbonyl forms were determined. It was concluded on the basis of the obtained data that 2-aryl-4,6-dioxo-1,3-thiazines exist in the gas phase predominantly in the hydroxycarbonyl form.For Communication 63, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1409–1412, October, 1987.     

Ab initio Calculation of the Electronic Structure and Equilibrium Geometry of Cortisol and Its Derivatives

The molecular geometries of a series of steroid hormones including cortisol, 9-fluorocortisol, 6-fluorocortisol, and 9-chlorocortisol were optimized by 3-21G and 6-31G* ab initio calculations. The results of calculations on both levels are well consistent with each other and with the experiment. The conformational changes and electron density redistribution occurring in going from cortisol to its 6- and 9-halo derivatives were discussed. A conclusion was made that the O and F atoms can participate in hydrogen bonding with the corresponding structural groups of glucocorticoid receptors.     

Single-cell analysis using capillary electrophoresis: influence of surface support properties on cell injection into the capillary

Capillary electrophoresis (CE) is an important tool of chemical cytometry. Whole-cell analysis using CE starts with cell injection into the capillary by either siphoning or electroosmosis. However, strong adherence of the cell to the support surface can prevent efficient cell injection and lead to irreproducible analysis. Here we evaluated several surfaces as potential cell supports for HT29 cells (human colon adenocarcinoma). These cells strongly adhered to the surface of untreated glass or polystyrene. Hydrophobic coating with dimethyldichlorosilane (DMS) or Sigmacote did not significantly reduce cell adhesion. In contrast, cell adhesion was reduced significantly when the surface was modified with hydrophilic polymers (hydrogels) such as poly(2-hydrohyethyl methacrylate) (PHEMA) and polyvinyl alcohol (PVA). In addition to their pronounced antiadhesive properties, PHEMA and PVA coatings were the most biocompatible (had highest survival of cells in contact with surface). Hydrogel-coated polystyrene plates were tested as a commercial alternative to hydrogel-coated glass slides. The cell adhesive properties of such plates were similar to those of PHEMA and PVA. However, the biocompatibility of the plates was lower than that of the other surfaces tested. Moreover, in contrast to PHEMA- and PVA-coated glass slides, the plates were sensitive to UV light and therefore should not be used when fluorescent image microscopy with UV excitation precedes CE. The analyses of the data obtained showed that PHEMA- and PVA-coated glass slides were the most suitable cell supports for cell injection into the capillary.     

Reactivity and structure of the 5-dehydro-m-xylylene anion

The electronic structure of dehydro-m-xylylene anion (DMX-) has been investigated by using chemical reactivity studies and electronic structure calculations. DMX- has been generated in the gas phase via the sequential reaction of trimethyl-3,5-bis(trimethylsilylmethyl)phenylsilane with F- and two molecules of F2. Reactivity and thermochemical properties of the ion indicate a phenyl-like anion (1a), consistent with theoretical predictions. Density functional calculations predict a nonplanar triplet anion, with an allenic singlet anion slightly higher in energy. The driving force for the out-of-plane distortion is more efficient charge delocalization that is achieved at lower symmetry.     

Use of complex-forming agents for extraction separation of cerium group of rare-earth elements in systems with neutral organophosphorus extractants

The use of complexons: nitrilotriacetic (NTA) and diethylenetriaminepentaacetic (DTPA) acids have been studied in extraction systems with main classes of neutral organo phosphorus extractants: phosphates (tributyl phosphate-TBP), phosphonate (diisooctylmethyl phosphonate-DiOMP) and phosphine oxides (triisoamylphosphineoxide-TiAPO) to separate lanthanides of the Ce subgroup. Optimal conditions to use complexon have been determined (extractant and salting agent concentrations). The effect of the type of extractant on the lanthanide distribution coefficients' dependence on pH of equilibrium water solution have been studied in the presence of NTA and DTPA. Unextractable cation displacers have been used to regulate distribution coefficients. The values of lanthanide separation coefficients of Ce group have been determined in extraction systems with neutral phosphorus-containing extraction agents — complexon — salting agent compared with Nd macroconcentrations and for lanthanide microconcentrations in the presence of cation displacer. These systems have been shown to be suitable for lanthanide separation of the cerium group.     

Structure of the 1:2 complex formed by the cis-anti-cis diastereomer of dicyclohexano-18-crown-6 with 2-methylbenzenesulfamide

Applied Physics Institute, Moldovian Academy of Sciences. Technical Physics Institute, Ukrainian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 2, pp. 138–144, March–April, 1992.