Determination of components of the Cd(II)-Pb(II)-Cu(II) system in aqueous solutions of (polyethylene imine)methylthiourea by stripping voltammetry

Conditions were studied for the stripping voltammetric determination of components of the Cd(II)-Pb(II)-Cu(II) system in aqueous solutions of (polyethylene imine)methylthiourea (PMT), the most efficient polymer complexant for the membrane preconcentration of heavy metal ions. It was shown that PMT significantly enhances the selectivity of determining Pb(II) and Cd(II) in solutions of Cu(II) by stripping voltammetry. Pb(II) and Cd(II) can be determined in the presence of up to 200- and 50-fold amounts of Cu(II), respectively. The limits of detection for Pb(II) and Cd(II) after a 40-s accumulation were 6.9 x 10^-8 and 6.8 x 10^-7 M, respectively.     

Membrane filtration for the continuous fractionation of species and macromolecules: Component distribution in the Arzhaan spring water

An improved device was proposed for the fractionation and preconcentration of particles and macromolecules. The device provides new means for the separation of water components. In the proposed method, a tangential flow of the test solution is passed through a series of successive membranes with decreasing pore size. The method was applied to the fractionation of low-mineralized water (Ty va Arzhaanes) with low concentrations of trace components.     

The effect of impermeable boundaries of arbitrary geometry on the apparent diffusion coefficient

The apparent diffusion coefficient (ADC) obtained from NMR measurements is modelled for diffusion in a compartment restricted by an impermeable boundary. For a given pulse sequence, the ADC can be determined from the connected velocity autocorrelation function (the second-order velocity cumulant), which we show can be expressed as a double surface integral over the boundary, involving the probability for molecules to diffuse from one boundary point to another. There is no restriction on the geometry of the boundary. This result allows a fast calculation of the ADC for an arbitrary time course of the diffusion-sensitizing gradient. Explicit examples are given for diffusion within three basic geometries for different pulse sequences. The ADCs measured with the Stejskal-Tanner pulse sequence and a more realistic pulse sequence with slice selection gradient and eddy current compensation are found to yield almost identical results. The application of the results are discussed in relation to determination of the microscopic structure of brain white matter.     

Molecular absorption spectrometry (MAS) by electrothermal evaporation in a graphite furnace-XIII Determination of traces of fluoride by mas of AlF after liquid-liquid extraction of fluoride with triphenylantimony(V) dihydroxide

The determination of traces of fluoride by means of the molecular absorption of AlF volatilized in graphite cuvettes is described. An extraction method for separation and preconcentration of the fluoride has been developed, to avoid matrix effects. The fluoride is extracted with 10(-3)M triphenylantimony(V) dihydroxide in M1BK, and stripped with 0.025M barium hydroxide. The method is sensitive and specific for fluoride. The detection limit is about 0.3 ng of fluoride, and the fluoride content of 6 ml of 10(-7)M solution can be determined. The determination is possible in presence of various ions, but it is estimated that usage of trace matrix separation leads to a considerable improvement in the relative detection limits (by 2-3 orders of magnitude), levels as low as 0.01 ppm being detectable in some matrices.     

Proteinases and phospholipases A-2 from the venom ofVipera berus berus

With aid of chromatography combining gel filtration and ion-exchange methods, from the venom of the common adderVipera berus berus we have isolated proteinases and phospholipase A-2 and also a component with coagulating properties which, in contrast to the other proteinases of the venom, hydrolyzes casein feebly. According to the results of get fzltrations, the molecular mass of the coagulant isolated was about 100 kDa, pH 6.5-7 0. No phospholipase A-2 activity was found in the coagulant fraction.Institute of Biochemistry, Academy of Sciences of the Republic of Uzbekistan, 700095, Tashkent, fax (3712) 62 32 56. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 479–483, May–June, 1995. Original article submitted September 13, 1994.     

The kinetics and mechanism of the reaction between 1-chloro-2,3-epoxypropane and p-cresol in the presence of basic catalysts

Rate constants for the reaction of 1-chloro-2,3-epoxypropane with p-cresol in the presence of basic catalysts were studied at the temperature range of 71–100°C. It was found that in the presence of sodium p-cresolate, three consecutive reactions proceeded giving the following products: 1-chloro-3-(tolyloxy)-2-propanol (CTP), 1-(p-tolyloxy)-2,3-epoxypropane (TEP) as a main product, and 1,3-di(p-tolyloxy)-2-propanol (DTP). Their rate constants at 71°C were: k₁ = 0.030 ± 0.009, k₂ = 1.58 ± 0.02, and k₃ = 0.033 ± 0.005 dm³/mol · min, respectively. In the presence of quaternary ammonium salts, this process consisted of 5 reactions which led to CTP as a main product as well as TEP and 1,3-dichloro-2-propanol (DCP). The rate constant of CTP formation at 71°C was established, k₁ = 0.130 ± 0.030 dm³/mol · min, as were the ratios of the other rate constants k₂/k₋₄ = 1.5 ± 0.2, k₅/k₋₄ = 20.0 ± 5.0, and k₄/k₁ = 0.6 ± 0.7. Based on the changes in Cl⁻ ion concentration during the reaction, the catalystic activity of quaternary ammonium salts was explained. The kinetic model of these reactions in the presence of basic catalysts has been proposed and appropriate kinetic equations have been presented. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 73–79, 1997.     

Excess density in oilfield water-crude oil dispersions

Extensive density measurements were performed with mixtures of 12 degassed (dead) crude oils with respective oilfield brines (formation waters). All unprocessed samples were collected directly from wellheads and contained only indigenous surfactants, such as asphaltenes and fine solids. Nonzero excess densities and excess thermal expansions (evaluated on the assumption of quasi-binary water-oil mixtures) were observed for water cuts in the range from X=0.4 to 0.6 at all studied temperatures T=5-50 degrees C. We suggest that these results are due to the formation of a dense asphaltene-mediated "middle phase" in the studied w/o dispersions. This suggestion is substantiated by plotting T-X phase diagrams which topologically strongly resemble those conventionally observed in some standard Winsor III-type systems. The formation of a complexly structured "middle phase" has been directly verified by preliminary visual/microscopic studies of a phase separation in a crude oil-water mixture.     

Photoelectron spectra and orbital structures of silatranes: Organic derivatives of pentacoordinate silicon

The photoelectron (PE) spectra of silatranes (1), 2,8,9-trioxa-5-aza-1-silabicyclo [3.3.3] undecanes, have been analyzed and partially reinvestigated. In the PE spectra of 1 the bands in the 8.2–8.9 eV region, which were previously ascribed to the lone electron pair (LEP) orbital of the nitrogen atom or the SiN bond, are due to the presence of impurities, the products of incomplete hydrolysis. Interpretation of the bands in the PE spectra of pure compounds was carried out by analysis of orbital-correlation diagrams and results of MNDO and AM1 calculations. The first ionization potential of1 is associated with a MO localized to a great extent on the axial X-Si-N fragment. The increase with shortening of the Si-N distance is related to the corresponding increase in the degree of noncoplanarity of the nitrogen atom when its LEP is involved in the hypervalent X-Si-N bond.