Approximation by a binomial type law

Kaunas Academy of Agriculture, 4324 Noreikiškés, Lithuania. Translated from Lietuvos Matematikos Rinkinys, Vol. 32, No. 2, pp. 221–228, April–June, 1992.     

Vertical migration of 85Sr, 137Cs and 131I in various arable and undisturbed soils

The vertical migration of ⁸⁵Sr, ¹³⁷Cs and ¹³¹I in some arable and undisturbed single-contaminated soils was studied by gamma-spectrometry measurements under lysimetric laboratory conditions during irrigation of the soil profiles with wet atmospheric precipitation for about one year, except ¹³¹I. A new simple exponential compartment (box) model was derived, which makes it possible to calculate the migration rate constants and migration rates in the individual soil layers (vertical sections) as well as the total vertical migration rate constants and total vertical migration rates of radionuclides in the bulk soil horizon. The relaxation times of radionuclides in respective soil horizons can also be evaluated.     

Durch Bromierung ausgelöste Umlagerung tertiärer Allylalkohole: Der Einfluss eines Fluor-Substituenten auf Reaktionsgeschwindigkeit und Reaktionsverlauf

Rearrangement of Tertiary Allyl Alcohols Induced by Bromination: The Effect of a Fluorine Substituent on the Rate and the Outcome of the Reaction The allyl alcohol bearing a methyl and a t-butyl group at the hydroxylated position was found to undergo a rearrangement when treated with bromine (or N-bromosuccinimide) in an aqueous medium and to afford a product mixture containing two regioisomeric ketones and one oxirane. Introduction of an additional methyl group or a fluorine atom at the non-terminal olefinic center led to a more selective discrimination between potential migratory groups. As the result of an exclusive t-butyl shift only one product, a ketone, was formed in both cases. Whereas the reaction rate was only slightly affected by the additional methyl group, it was substantially decreased by the fluorine atom.     

Symmetry of electronic states in garnets

The paper presents the classification of the electronic empty lattice eigenvalues and the classification of the Bloch sums for the garnet structureIa3d (O _h ¹⁰ ) at the symmetry points, H, P, andN of the Brillouin zone. This provides a starting point for the energy band studies of these technologically important materials.The author thanks Dr. V. Frei for useful comments.     

The (CF3S)2N. radical : preparation,dimerization, ESR-studies

The Bis (trifluormethylmercapto) amino radical (CF₃S)₂N· has been prepared by oxidation of Bis (trifluormethylmercapto) amine, (CF₃S)₂NH with activated lead diooxide in CCl₃F solution at room temperature. The 10^?5 – 10^?6 molar solution of the radical shows in the ESR- spectrum a triplett of septetts with a isotropic nitrogen hyperfine splitting constant a(¹⁴N) = 13,2 G, a(¹⁹F) = 1.95 G, indicating that the radical is a planar sp² species where the unpaired electron is located predominantly in the nitrogen 2p orbital. It is suggested that in solution an thermal equilibrium exists between the (CF₃S)₂ N radical and its dimer Tetrakis (trifluormethylmercapto)-hydrazine:

Aspects of preparation as well as thermodynamic and kinetic details of the hydrazine (NN bond strength 7 kcal/mol^?1) and the equilibrium, which can be followed by ESR-spectroscopy will be given.     

Five-membered ring formation in unimolecular reactions of peptides: a key structural element controlling low-energy collision-induced dissociation of peptides

Unimolecular fragmentation reactions of peptides in low-energy collision-induced dissociation are reviewed in the mechanistic context of five-membered ring formation. This structure of intermediates or of fragment ions is recognized as a key element that governs unimolecular peptide fragmentation within the structural framework determined by the peptide backbone and its side-chains. A collection of collision-induced dissociation reactions is presented covering (i) b-ion formation, (ii) the fragmentation of N-terminally acylated peptides, (iii) neutral loss of the C-terminal amino acid in alkali or silver cationized peptides, (iv) the fragmentation of isoAsp-containing peptides and (v) the fragmentation of negatively charged Asp- or Glu-containing peptides. It appears that for all possible nucleophile-electrophile interactions leading to a five-membered ring structure an associated unimolecular peptide fragmentation reaction can be observed.     

Trifluoromethoxy substituted anilines: metalation as the key step for structural elaboration

Trifluoromethoxy-substituted anilines undergo hydrogen/lithium permutation ("metalation") with optional site selectivity depending on the N-protective group employed. N-tert-Butoxycarbonyl-2- and -4-(trifluoromethoxy)aniline react with tert-butyllithium at the nitrogen-adjacent 6- and 2-position affording, after electrophilic trapping, products 1-6. In contrast, deprotonation of the para isomer occurs at the oxygen-neighboring 3-position, giving rise to the acid 12, when the amino group is carrying two trimethylsilyl groups. sec-Butyllithium attacks 3-trifluoromethoxy-N-mono(trimethylsilyl)aniline at the 2-position, but 3-trifluoromethoxy-N,N-bis(trimethylsilyl)aniline at the 4-position to provide respectively the acids 10 and 11 after carboxylation. The synthesis of two new benzodiazepines illustrates (19 and 22) the preparative potential of the aniline functionalization mediated by organometallic reagents.     

Synthèses de produits organofluorés VI Solvolyse de chlorofluorocyclopropanes

Fluoro-organic Syntheses VI: The Solvolysis of Chlorofluoro-cyclopropanes 2-Fluoro-allylic carbocations, generated from 1-chloro-1-fluoro-cyclopropanes or 2-fluoro-allyl p-toluene-sulfonates in water or acetic acid, undergo either proton loss or addition of hydroxyl or acetoxyl. In the latter case, an alkyl-substituted 2-fluoro-allyl ion leads predominantly to the more branched product (e.g. 3-fluoro-2-methyl-3-buten-2-ol) which may be converted into the less branched one (e.g. 2-fluoro-3-methyl-2-buten-2-ol) through reversible reactions.     

On the possibility of measuring the thickness of very thin films using electron probe microanalyzer

The measurement of the thickness of thin aluminum and silver films using an electron probe microanalyzer is described. The method of measurement was studied in order to investigate very thin discontinuous aluminum layers, originated from inorganic residues of photoresists removed from the surface of silicon and other materials by plasma oxidation. The calibration curves, i.e. the dependences of the intensity of the characteristic X-ray emission on the thickness of thin standard films evaporated on the same substrate, were determined for the evaluation of the measurements. These dependences were measured till the smallest thickness 15 nm of the standard film. Then the curves were extrapolated to the origin of coordinates and the film thickness was calculated using the value of the slope of tangent to the calibration curve in the origin. In order to estimate the accuracy of this procedure, the calibration curves were expressed analytically using the mathematical representation of the electron excitation function. It follows from the results that the shape of the calibration curves may be influenced mainly due to electrons scattered from the substrate back into the film and due to fluorescence excitation of X-ray emission. The last effect was markedly observed in Al/Si system.