Use of the Vaskovsky-Svetashev reagent for complex detection of phospholipids and in their preparative separation by the TLC method

It has been established that the Vaskovsky-Svetashev reagent has no influence on the general and positional composition of the fatty acids of phospholipids. For the qualitative identification of PLs on one plate it is possible to use successively iodine, ninhdrin, the Dragendorff reagent, the Vaskovsky-Svetashev reagent, 50% H₂SO₄, and the Malachite Green reagent.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 40–42, January–February, 1988.     

Relative reactivities of the pyridine and benzimidazole systems in the chichibabin reaction

1- (or)-Pyridyl- and 1- (or)-pyridylethylbenzimidazoles were synthesized, and their behavior with respect to methyl iodide and sodium amide was studied. The results are discussed from the point of view of the basicities, magnitudes of the dipole moments, interaction of the heterorings, and the electron density distribution in them, calculated by the Hückel MO method or estimated on the basis of the relative position of the chemical shifts in the PMR spectra. It was established that the benzimidazole system undergoes the Chichibabin reaction considerably more readily than the pyridine system. On the basis of the PMR spectral data for the pyridine and benzimidazole bases and cations, it is assumed that this is due to the greater polarizability of the C = N bond of benzimidazole as compared with the C = N bond of pyridine during coordination with NaNH₂.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1252–1263, September, 1972.The authors sincerely thank L. E. Nivorozhkin and G. V. Gorshkova for their assistance in measuring the PMR spectra.     

Copper-catalyzed arylation of amines using diphenyl pyrrolidine-2-phosphonate as the new ligand

[Chemical reaction: See text] We have developed a general, efficient, and inexpensive catalyst system for arylation of amines by using 10 mol % of CuI as the copper source, 20 mol % of diphenyl pyrrolidine-2-phosphonate (DPP) as the ligand, K3PO4 as the base, and DMF containing 2% water (v/v) as the solvent.     

NMR and X-ray diffraction studies of the influence of adsorbed molecule nature on phase transitions in a ZSM-5 silicalite

Pulsed NMR and X-ray diffraction analysis are employed to study the influence of adsorbed toluene, p-xylene, acetone, and di(ethylene glycol) (DEG) molecules on phase transitions in a ZSM-5 silicalite. In the region of phase transitions, times T₁ and T₂ of longitudinal and transverse magnetic relaxation of apolar molecules adsorbed in silicalite micropores increase and decrease in a jumpwise manner, respectively, with a rise in the total content of the liquid. Such changes in T₁ and T₂ occur for hexane, decane, toluene, and p-xylene molecules. Qualitatively different concentration dependences of T₁ and T₂ are observed for polar acetone and DEG molecules, because these liquids do not cause a earrangement in the crystal lattice of silicalite; this is confirmed by the X-ray diffraction data.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 802–806.Original Russian Text Copyright © 2004 by Pimenov, Skirda, Maksimenko, Morozov, Opanasyuk.     

Electronic interaction between the nitrogen,oxygen, and silicon atoms in the molecules of α-aziridin-1-ylalkoxy(triethyl)silanes

By the PMR method we have established the existence of a high frequency of the inversion of the nitrogen atom in the molecules of -aziridin-1-ylalkoxysilanes. This is due to the fact that the high (because of p-d bonding with the silicon atom) electronegativity of the oxygen atom in the Si-O-C-N system makes possible an interaction between the unshared electron pair of the nitrogen atom and the antibonding orbital of the C-O bond. The latter, in its turn, increases the degree of p-d bonding between the oxygen and silicon atoms (in these compounds the order of the Si-O bond is greater than in the alkoxysilanes).     

Theoretical Study of Weakly Bound Dimers between Hydrogen Fluoride and Some Polar Molecules

Weakly bound linear and bent dimers, FH—X (where X = CO, OC, CNH, NCH, N₂O and ON₂), are investigated using the DFT B3LYP and ab initio MP2 methods with the same basis sets (6–311++G(3df,2pd)). The strengths of the H—C or H—N H‐bonds in dimers FH—CO, FH—CNH, and FH—N₂O are compared with those of the H—O or H—N H‐bonds in dimers FH—OC, FH—NCH, and FH—ON₂. The results obtained for the H‐bond distances, the elongation effect of the HF bond, the red shift of the HF stretching frequency, and the energy difference between the dimer and the charge transfer reveal that the H‐bonds of the first group of dimers are stronger than those of the second. The Gibbs energies calculated for the six dimer formations indicate that the weakly bound dimers are unstable at room temperature (T = 298 K) (FH—X's → FH + X's, ΔG < 0).     

Development of a method for recovery of 233U from thorium oxalate cake in reconversion step of reprocessing of irradiated thorium rods

A method is developed for the selective leaching of ²³³U from a thorium oxalate cake. The leaching capacity of ammonium carbonate and nitric acid have been investigated, showing that (NH₄)₂CO₃ leads to higher recovery. The maximum leaching efficiency is obtained using 0.5% ammonium carbonate, with a minimal thorium pick-up. A uranium recovery of 94% is obtained after three consecutive contact experiments in carbonate media, with minimal thorium uptake in the leachate. This process was applied to an actual plant stream, allowing the reduction of the ²³³U -activity from 5.64 to 0.3 Ci/g of thorium oxalate cake.     

Nanocomposites Produced by Direct Intercalation of Secondary Doped Polyaniline in V2O5

The possibility of the production of nanocomposites based on V₂O₅ and conducting polymers by direct intercalation of macromolecules of secondary doped polyaniline into the interlayer galleries of nanoparticles of aqueous V₂O₅ sol was demonstrated for the first time. The driving force of the intercalation process is substitution of the protons present in the galleries of the V₂O₅ by a polyaniline chain carrying a positive charge.