Practical aspects of Mössbauer spectroscopy instrumentation

The setting up and updating of a Mössbauer laboratory imply the acquisition and assembling of different units. Guidelines concerning either the construction or the acquisition of the various parts which compose a Mössbauer spectrometer are given in this paper.     

Iron-57 Mössbauer spectroscopic studies of materials of composition Fe x NbTiP3O12: materials with low concentrations of iron and the effects of treatment in air

The⁵⁷Fe Mössbauer spectrum recorded from the material of composition Fe_0.25NbTiP₃O₁₂ shows the presence of Fe²⁺ in a distribution of approximately octahedral type I sites within the channels of the NbTiP₃O₁₂ structure. A comparison of the results with those recorded from the material Fe_0.33NbTiP₃O₁₂ demonstrates the existence of an upper limit to the occupation by the Fe²⁺ species of the type I sites. Lattice parameter measurements and⁵⁷Fe Mössbauer spectroscopy show that treatment of Fe_0.25NbTiP₃O₁₂ in air induces the migration of the incorporated iron from the channels to form macroscopic -Fe₂O₃.     

The rate difference between the weak decays of t and in supersymmetry

We find that the CP-violating asymmetry

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at the one-loop order within the minimal supersymmetric extension of the standard model is of the order of few percent for maximal CP violation. It could be measured by considering the rate difference in the one-lepton events.     

Nonlocal forces of inertia in cosmology

This paper reviews the origin of inertia according to Mach's principle and Weber's law of gravitation. The resulting theory is based on simultaneous nonlocal gravitational interactions between particles in the solar system and others in the remote universe beyond the Milky Way galaxy. It explains the precession of the perihelion of Mercury. A most important implication of the Mach-Weber theory of the force of inertia is the necessity for a large amount of uniformly distributed matter in the galactic universe. This matter could be the source of the cosmic background radiation. Nonlocal inertia forces are compatible with a static universe and also with an expanding universe but the latter would demand slow changes in the mass of particles and the gravitational constant.     

Formal orthogonal polynomials revisited. Applications

From some results concerning the formal orthogonal polynomials, already proved in [5], we develop new properties of generalized adjacent polynomials which correspond to a change in the weight function. A new structure of the singular blocks is given. These results have a direct application to Lanczos methods, theG and -algorithms.     

WKB-type approximations for second-order differential equations in -algebras

Rigorous asymptotic approximations of the WKB (or Liouville-Green) type are obtained for a basis of solutions to in the framework of -algebras. Both cases and are included, thus generalizing the classical theory for scalar equations developed by F.W.J. Olver to matrix as well as to infinite-dimensional equations.

     

Synthesis, Structural Characterization, and Oxidation-Reduction Behavior of the gamma-Isomer of the Dodecatungstosilicate Anion

The reaction of tungstate ions with the gamma-10-tungstosilicate in mixed water-ethanol (v/v) yields the corresponding isomer of the 12-tungstosilicate isolated as its tetrabutylammonium salt. It was characterized by means of (183)W NMR, infrared, Raman, and UV spectroscopies and was identified with the isomer resulting from the Keggin structure (alpha-isomer) by rotation of two tritungstic groups by pi/3. Cyclic voltammetry shows that the reducibility increases in the sequence alpha-beta-gamma as the number of rotated tritungstic groups. Whereas the gamma-12-tungstosilicate anion is unstable in pure aqueous solution whatever the pH value, it is stable in mixed aqueous-organic or pure organic solvents, even at boiling temperatures. In contrast, the two- and four-electron-reduced blue species are stable in aqueous media but not the one-electron-reduced blue. Study of the (183)W NMR spectrum of the two-electron-reduced species showed that the two spin-paired electrons are delocalized on all the W atoms on the NMR time scale but have a larger residency time on one group of four atoms.     

Reactions of Substituted Boryl Radicals with Nitroalkanes. EPR, Kinetic, and Product Studies

The radical-initiated reaction of amine-boranes and phosphine-boranes, LBH(3) (L = R(3)N, R(3)P) with aliphatic nitro compounds has been investigated in order to explore the possibility of reducing tertiary nitroalkanes to the corresponding hydrocarbons. In all the examined cases boroxy nitroxides, RN(O(*))OBLH(2), resulting from the addition of ligated boryl radicals, LBH(2)(*), to an oxygen atom of the nitro group were detected and characterized by EPR spectroscopy. This reaction occurs at room temperature with a rate constant of 1.5 x 10(7) M(-)(1) s(-)(1) for LBH(2)(*) = Me(3)NBH(2)(*) and RNO(2) = Me(3)CNO(2). The boroxy nitroxides from tertiary nitroalkanes decay by a fragmentation reaction occurring with cleavage of the nitrogen-oxygen bond, rather than of the carbon-nitrogen bond as would be required for the reduction to the corresponding alkane to take place. The Arrhenius parameters for this fragmentation have been determined in few cases.     

Synthesis of Enantiopure Primary Amines by Stereoselective Ring Opening of Chiral Octahydro-1,3-benzoxazines by Grignard and Organoaluminum Reagents

Chiral 1,3-perhydrobenzoxazines 1, 2, and 9-14, prepared by condensation of 8-(benzylamino)menthol with different aldehydes, react with alkylmagnesium bromides and trimethylaluminum leading to the open amino alcohols 3a-d, 4a-d, and 15-20 in excellent chemical yields and good to excellent diastereomeric excess. The sequential elimination of the menthol appendage by heating with P(2)O(5) and the benzyl group by hydrogenolysis lead to primary amines 7a-d, 8a-d, and 27-30 in excellent chemical yields and ee. The addition of the alkyl group from the Grignard derivatives and the methyl group from the trimethylaluminum occurs from opposite sides of the heterocycle, yielding the final primary amines with the same stereochemistry.