A comparison of spin relaxation and local motion between symmetrically and asymmetrically ring-substituted bisphenol units in dissolved polycarbonates

Carbon-13 and proton spin-lattice relaxation times were measured at two field strengths on solutions 10% by weight of two polycarbonates in C₂D₂Cl₄ from ?20 to +120°C. The first polycarbonate is an asymmetrically substituted form with one chlorine on one of the two phenylene aromatic rings of the bisphenol unit, whereas the second polycarbonate is symmetrically substituted with two chlorines on each of the two rings. The nuclear spin relaxation data are interpreted in terms of several local motions likely in these polymers. Segmental motion was described by the Hall–Helfand correlation function. Segmental motion in the monosubstituted polycarbonate is somewhat slower than in unsubstituted polycarbonate, whereas segmental motion in the tetrasubstituted polycarbonate is considerably slower. Phenylene ring rotation is observed in unsubstituted polycarbonate and in the monosubstituted polycarbonate above 40°C. Below 40°C in the monosubstituted species, and at all temperatures in the tetrasubstituted species, ring rotation is replaced by ring libration as the predominant motion contributing to spin lattice relaxation. In addition, the rotational motion of the two types of rings in the asymmetric monosubstituted form are very similar although not identical. The substituted ring is slightly less mobile than the rings of unsubstituted polycarbonate. This indicates a strong coupling of ring motion, although the coupling leads to less than synchronous motion. Methyl group rotation is present in both polymers and is little affected by the various structural modifications.     

Ramsey numbers for graphs with five vertices

The Ramsey numbers r(F¹, F²) are tabulated for essentially all but six pairs of graphs F¹ and F² with five vertices.     

Trimeric liquid crystals containing lateral alkyl chains

The first twelve members of the n-alkyl 2,5-bis-(4'-cyanobiphenyloxybutyloxy)-benozates have been prepared. The compounds are nematogenic; in addition the first three members exhibit a smectic A phase. The nematic-isotropic transition temperatures decrease with little or no alternation on increasing the number of methylene groups in the lateral chain; this is analogous to the behaviour found in monomeric and polymeric mesogens possessing lateral alkyl chains.     

The oxidation of 3,3′-dimethoxy benzidine with potassium bromate in acidic solutions

The kinetics and mechanism of the oxidation of 3,3′-dimethoxybenzidine (oda, o-dianisidine) by potassium bromate in aqueous acidic medium were studied by monitoring the formation rate of the reaction product, 3,3′-dimethoxy 4,4′-diphenoquinone at 447 nm. The reaction is, first order with respect to both the substrate and oxidant, and second order with respect to H⁺. The oda: bromate stoichiometric ratio is 1:1. Plausible mechanism and rate laws are proposed accounting the experimental findings. Computer simulations were done using the proposed mechanism.     

Synthesis of dimethylditritiogermane Me<Subscript>2</Subscript>GeT<Subscript>2</Subscript>

A microsynthetic procedure for preparing tritium-labeled alkyl-substituted germanes is developed. The resulting dimethylditritiogermane can be used as a source of dimethylgermylium ions. The synthesis was performed by the reduction of dibromodimethylgermane with lithium tritide in presence of AlBr₃.     

Spectral and voltammetric studies on titanium substituted Keggin-type heteropolyanions

Bonding and redox properties of mono- and dititanium substituted 12-heteropolytungsto-phosphates and their complexes with bivalent Mn, Co, Ni and Cu are studied by UV-Vis, ESR and cyclicvoltammetric techniques. The heteropoly blue analogue [Ti^IIITi^IVW₁₀PO₄₀]⁸⁻ is unstable and its presence in solution is proved by optical and ESR spectroscopy. ESR results reveal that the odd electron is trapped on the titanium atom at 77 K. The optical electronegativity of Ti(III) in this heteropoly blue is estimated to be 2.4 from the intervalence charge transfer (IVCT) bands. X-ray powder diffraction results show that the complexes K₅M^II[Ti₂W₁₀PO₄₀].xH₂O(M^II = Cu or Mn) are isomorphous with K₇[Ti₂W₁₀PO₄₀].6H₂O. Electronic spectroscopy indicates very high symmetry around the bivalent metal ion M in the K₅M^II[Ti₂W₁₀PO₄₀].xH₂O complexes. This high symmetry is confirmed in K₅Cu[Ti₂W₁₀PO₄₀] by the observation of dynamic Jahn-Teller (JT) distortion at 300 K and static JT distortion at 77 K.     

Magnetic and petrochemical properties of rocks from the Red Sea rift zone

The magnetic and petrochemical properties of basalts dredged from the rift zone at the southern part of the Red Sea at approximately 18° N are studied. The conditions of their formation and evolution are elucidated. The formation of basalts is found to occur in two stages differing in their magma supply rates and redox conditions. Special features of magnetic behavior and the anomalous geomagnetic field in the region were used to determine the sites where the rocks had experienced strong thermodynamic effects (tectonic strain, deformation, heating, etc.). The conditions in which natural remanent magnetization of the basalts was formed are estimated.