Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

Temperature dependence of the rate constants for reactions of the carbonate radical with organic and inorganic reductants

Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO₃^·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of Fe^II, Mo^IV, and W^IV, the simple inorganic anions SO₃^2?, ClO₂^?, NO₂^?, I^?, and SCN^?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 10⁵ to 3 × 10⁹ M^?1 s^?1, the activation energies ranged from ?11.4 to 18.8 kJ mol^?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.     

The inclusion of electrostatic and dispersion interactions into potentials of mean torque for solutes dissolved in uniaxial liquid crystal solvents

A potential of mean torque is derived for a solute at infinite dilution in a uniaxial liquid crystal solvent, which contains terms originating from the dispersion interaction, and the electrostatic interaction between quadrupole moments on both molecules. It is shown that the electrostatic term is non-zero only if the solute-solvent vectors are distributed with lower than spherical symmetry. If this distribution has cylindrical symmetry then both the electrostatic and dispersion terms in the potential of mean torque are shown to depend on order parameters for the orientational distribution of the solute-solvent vectors, as well as on the order parameters of the solvent molecules.     

Dielectric relaxation of a short molecule in a liquid-crystalline solvent

Dielectric relaxation measurements of 5 mole % 4-n-hexyloxycyanobenzene (I) dissolved in 4-n-pentyloxyphenyl-trans-4-n-octylcyclohexylcarboxylate (II) were carried out from 1 kHz to 10 MHz in the nematic, smectic A and smectic B phases. The relaxation frequency of I parallel to the director is about 05 MHz in the S_Bphase and increases rapidly at the transition from S_B to S_A.     

Effect of dynamic loading on the structure of amorphous alloy Fe66Ni12Si20B2

Transmission- and depth-selective-conversion-electron Mössbauer spectroscopy (DCEMS) were applied to study variation of structural state in the bulk and in the surface layer (500, 1000, 1500 Å thick) of amorphous alloy under certain optimum conditions of the dynamic loading. The alloy structure remains amorphous. However, a certain variation of the short range order. An amorphous oxide Fe₂O₃ is formed on the amorphous alloy surface.     

Total surface areas of Group IVA organometallic compounds: Predictors of toxicity to algae and bacteria

There is a high correlation between molecular surface area (TSA) of triorganotin and triorganolead compounds and their toxicity towards a bacterium (Escherichia coli) and an alga (Selenastrum capricornutum). Parallel attempts to correlate other Group IVA organometals incorporating silicon or germanium were unsuccessful. It was further demonstrated, however, that a high correlation was obtainable between certain series of compounds with the same organic substituent but different metal centers involving all Group IVA elements. In both instances, the inability to obtain a quantitative structure-activity relationship (QSAR) for all systems studied appears to be a function of the solubility of the compounds. While organotin TSA values have been found to correlate well with their toxicities toward various organisms, this study clearly suggests that this type of QSAR can be readily extended to include other organometal systems, provided that there is no solubility problem and the toxicity is a function of the hydrophobicity of the organometal compounds.     

Estimation of the exchange constants in the Fe sublattice of the Y2Fe17 and Y2Fe17N3−δ compounds from the analysis of Mössbauer measurements

From the analysis of Mössbauer data for Y₂Fe₁₇ and Y₂Fe₁₇N_3−δ at various temperatures the hyperfine fields for 4f, 6g, 12j, 12k iron sites were estimated as a function of temperature. The reduced magnetizations calculated from the values of the hyperfine fields are fitted with a mean field model for four interacting sublattices using a computer program. The estimated exchange interaction from the fitting procedure between the 4f sites is found strongly negative (antiferromagnetic) in Y₂Fe₁₇ whereas in Y₂Fe₁₇N_3−δ it increases and becomes weak negative following a modified Slater-Néel curve. The rest of the exchange interactions are found positive or weak negative depending on the distances between the Fe atoms.