Oxidation of olefins with alkanesulfoperacids

Alkanesulfonic peracids RSO₄H effectively oxidize olefins to the corresponding epoxides. The kinetics and mechanism of this reaction are studied. It was shown that both the monomer and dimer form of the peracid act as oxidizing agents. The dependence of the weight constant of the reaction of monomer RSO₄H with substituted acyclic olefins on the structure of the latter is described by the Taft equation. A linear correlation is established between log k₂ and the inductive constants of the substituents on the oxygen atom in the peracid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 333–337, February, 1991.     

Research problem

This section appears from time to time. Contributions are invited, and should be submitted to R C. Thompson, Mathematics Department. University of California, Santa Barbara, CA93106-3080, USA.     

Optical properties of F.I.R. metallic grids: Reflection phase shift measurements

Utilization of metallic grids stacks for F.I.R filters needs a good knowledge of optical properties of each grid. We study here an experimental method in order to determine the wave's change of phase by reflection on a wire grid. We use a Perot-Fabry interferometer constituted by these grids.     

Laser vaporization: A versatile method for studying metal clusters

Vaporizing solid samples of metals and semiconductors with a YAG Laser is a method well suited for producing molecules and clusters of those materials. The clusters are examined by either laser-induced fluorescence (LIF) or mass spectroscopic methods. The technique is valuable for both gas phase and matrix studies. The method is described and some applications, studying either the structure of small metal molecules or their reactions, are reviewed, with emphasis on our recent results from the LIF studies of LiBe, Al₂ and the reaction of Al with oxygen, yielding A1₂O. For larger clusters, Ion Cyclotron Resonance is an extremely valuable method, as we demonstrate by its application to the reactions of small charged silicon clusters with strong oxidising agents.     

Deuterium NMR studies of inositol liquid crystals [1]

Deuterium NMR investigations are presented on members of two new mesogenic series derived from the naturally occurring stereoisomers myo- and scW/o-inositol. Tetraethers of these two series exhibit thermotropic columnar phases in which the columns are apparently formed by stacked hydrogen bonded dimers of these molecules which chemically are vicinal diols. Deuterium NMR measurements were performed on the tetraoctyl homologues 2e (a cis diol) and 3e (a trans diol) of these series. We have investigated mixtures of these diols with small amounts of benzene-d₆ as probe molecules as well as samples of the neat diol compounds deuteriated at their hydroxyl groups. The results obtained show that the mesophases of both compounds are uniaxial and align partially in a magnetic field upon slow cooling from their isotropic liquids. The alignment is with the director parallel to the field direction indicating that the anisotropic magnetic susceptibility of this mesophase is positive. The deuterium quadrupole splitting of the benzene-d₆ probe in both systems is temperature dependent and in the trans diol 3e it even changes sign. This is interpreted in terms of a model in which the benzene-d₆ probe equilibrates rapidly between two (or more) solvation sites with quadrupole splittings of opposite signs The deuterium spectra of the neat deuterium labelled cis diol 2e exhibit two different signals due to the two deuterons which are located at the axial and equatorial hydroxyl groups. This indicates that there is no fast intra- or intermolecular exchange of the hydroxyl hydrogens. The overall quadrupole splittings of the hydroxyl deuterons in this compound are highly reduced compared to their static values and this is interpreted in terms of motional modes involving both reorientation of the hydroxyl deuterons about their C-O axis and overall reorientation of the molecules (or pairs of molecules) around the columnar axes. The corresponding spectra of the neat deuteriated trans diol 3e exhibit a single spectrum indicating that both hydroxyl deuterons in this compound are equivalent, or very nearly so. Within the mesophase region the spectrum undergoes gradual changes due to the increase in the molecular mobility, but the overall motional narrowing is less than in the cis isomer 2e. Apparently due to stronger hydrogen bonding in the trans isomer 3e the precession of the hydroxyl groups is hindered and a fast molecular reorientation is only possible at high temperatures.     

Transport properties of a side-chain liquid-crystalline polymer. Poly(4-acryloyloxy biphenyl)

The transport properties of a side-chain liquid-crystalline polymer forming a smectic A phase have been investigated using dichloromethane as a permeant. Samples differing in the isotropization enthaoly were analyzed. A. Correlation between this thermal parameter and sorption has been found, while the diffusion coefficient is substantially the same in all samples. The results obtained can be explained in terms of a biphasis model in which a disordered permeable phase is present within the liquid-crystalline phase, which is impermeable to the diffusant molecules.     

Measurements of the perpendicular width of ionization-produceddouble layers

Measurements of the perpendicular (to B) double-layer widths of ionization-produced (anode) double layers are presented. These widths were determined from measurements of the double-layer charge separations. The variations of the transverse-to-B widths with plasma density and magnetic field strength are given