General description of mechanical anisotropy of semicrystalline polymers in relation to orientation of structural units composed of crystalline and noncrystalline materials

A mathematical representation of the transformation of an orientation function between two sets of Cartesian coordinates is discussed in terms of a series expansion of the distribution function in generalized spherical harmonics. A general procedure for calculating the mechanical anisotropy of a single-phase system (a polycrystalline material) from the orientation of its structural units and the intrinsic mechanical anisotropy of the structural unit is discussed in relation to the transformation of the orientation distribution function, i.e., mutual conversion of the coefficients in the expansion of the distribution function between the two sets of Cartesian coordinates. The procedure is extended to a two-phase systems (semicrystalline polymers) containing structural units composed of crystalline and noncrystalline materials in three different geometrical arrangements.     

CHLORPROMAZINE PHOTOSENSITIZATION–II. FAILURE TO DETECT ANY EVIDENCE FOR INVOLVEMENT OF DNA DAMAGE IN THE PHOTODYNAMIC KILLING OF ESCHERICHIA COLI IN THE PRESENCE OF CHLORPROMAZINE

Abstract— When a suspension of Escherichia coli was irradiated with near-UV light in the presence of chlorpromazine (at a concentration below a cytotoxic level), the cells were killed. Efficiency of the photodynamic killing was not influenced by the deficiency of the uvrA gene or the recA gene. Neither phenotypic reversion of E. coli Hs30R (arginine auxotroph) nor induction of lambda prophage in lysogenic bacteria was detected after this treatment.     

Cyclopalladation compounds of the 2-pyridylhydrazone derivatives of p-substituted acetophenones and acetylthiophenes

Cyclopalladation occurs for 2-pyridylhydrazones(HL) of p-methyl-, p-methoxy-, p-chloro-, and p-nitro-acetophenone, and 3-acetyl- and 2-acetyl-thiophene with lithium tetrahalopalladate to give the complexes [PdXL] (X = Cl and Br) and some iodo complexes are prepared by metathesis of the chloro complexes with lithium iodide. These complexes are characterized spectroscopically. The hydrazones are coordinated to palladium through benzene or thiophene ortho-carbon, hydrazone-nitrogen, and pyridine ring-nitrogen atoms forming fused five-membered chelate rings.     

Phase transition in ammonium hexafluorovanadate (III)

Heat capacity of ammonium hexafluorovanadate (NH₄)₃ [VF₆] has been measured with a miniaturized adiabatic calorimeter from 20 to 300 K. A phase transition was found at 280.44 ± 0.05 K with the associated entropy change Δ_trs S = 24.9 ± 0.5 JK^?1 mol^?1. The entropy transition is accounted for by the orientational order-disorder changes of hexafluorovanadate ion and ammonium ion occupying respective octahedral sites, as in the cases of (NH₄)₃AlF₆ and (NH₄)₃FeF₆ crystals. Changes in infrared spectra relative to v₃ vibrational mode of [VF₆]^3? ion can be explained by an orientational disorder of the anions in the high-temperature phase (HTP). The dependence of cubic root of the unit-cell volume of a family of ammonium cryolites on their transition temperatures is discussed in relation to the nature of interactions which induce the phase transition.     

A light-scattering study of deformation of liquid-crystalline spherulites of poly(γ-benzyl-L-glutamate) in an electric field

The deformation of liquid-crystalline spherulites of poly(γ-benzyl-L -glutamate) (PBLG) in an electric field was investigated by light scattering, polarized-light microscopy, and birefringence measurements. Under the polarizing microscope, the deformation was found to be dependent upon the field strength. The spherulites deformed perpendicular to the field. Above 75 V/cm in N,N-dimethylformamide or 120 V/cm in 1,1,2-trichloroethane, the deformed spherulites were transformed to rodlike textures. With increasing voltage, the rods gradually oriented parallel to the electric field. On the basis of the experimental results, models for affine deformation are proposed. With these models, light-scattering patterns are calculated. The calculated and experimental patterns agree semiquantitatively.     

Synthesis of bis(azafulvene)s by dehydration of hydroxymethylpyrrole derivatives

Bis(azafulvene) was isolated in 55% yield by the reaction of 4 equivalents of phenyllithium with 5,5'-diformyl-3,3',4,4'-tetraethyl-2,2'-bipyrrole followed by quenching with acetic anhydride. Unstable bis(azafulvene)s were obtained in much higher yields by dehydrating 5,5'-bis(hydroxymethyl) derivatives of 2,2'-bipyrrole and gem-dimethyl-2,2'-dipyrrylmethane with (Boc)2O-DMAP at room temperature. X-Ray crystallography of two bis(azafulvene)s is reported.     

Decomposition of anthranil. Single pulse shock-tube experiments, potential energy surfaces and multiwell transition-state calculations. The role of intersystem crossing

The thermal decomposition of anthranil diluted in argon was studied behind reflected shock waves in a 2 in. i.d. pressurized driver single-pulse shock tube over the temperature range 825-1000 K and overall densities of approximately 3 x 10(-5) mol/cm(3). Two major products: aniline and cyclopentadiene carbonitrile (accompanied by carbon monoxide) and four minor products resulting from the decomposition were found in the postshock samples. They were, in order of decreasing abundance, pyridine, CH(2)=CHCN, HCN and CHC-CN, and comprised only a few percents of the overall product distribution. Quantum chemical calculations were carried out to determine the sequence of the unimolecular reactions that lead to the formation of cyclopentadiene carbonitrile and of phenylnitrene/phenylimine that are the precursors of aniline. They form aniline by reactions with traces of water impurities. To produce cyclopentadiene carbonitrile, two main processes must take place: CO elimination and ring contraction from a six- to a five-membered ring. It was shown that this can occur via two parallel pathways where CO elimination takes place prior to or following ring contraction. Singlet potential energy surfaces for all the elementary reactions that lead to the formation of cyclopentadiene carbonitrile and phenylnitrene/phenylimine were obtained. Their rate constants were calculated on the basis of the results of the quantum chemical calculations using transition-state theory. A kinetic scheme containing these reactions was constructed and multiwell calculations were performed to evaluate the mole percent of the products as a function of temperature. A very serious disagreement between the experimental results and the results of calculations showed that the singlet PESs could not account for the observed experimental rates. No other singlet PESs that lead to the formation of these products could be found. In view of this observation, attempts to find pathways that lead to the formation of cyclopentadiene carbonitrile and phenylnitrene/phenylimine on triplet surfaces were made. Such surfaces were found, and singlet <--> triplet intersystem crossing probabilities and crossing rate constants were calculated as well as the rate constants of all the elementary steps on the triplet surfaces. A reaction scheme was constructed and multiwell calculations were performed, including also the pathways on the singlet surfaces, to evaluate the mole percent of the products as a function of temperature. The agreement between the experimental results and these calculations was quite satisfactory.     

Conservative numerical schemes for the Ostrovsky equation

The Ostrovsky equation describes gravity waves under the influence of Coriolis force. It is known that solutions of this equation conserve the L² norm and an energy function that is determined non-locally. In this paper we propose four conservative numerical schemes for this equation: a finite difference scheme and a pseudospectral scheme that conserve the norm, and the same types of schemes that conserve the energy. A numerical comparison of these schemes is also provided, which indicates that the energy conservative schemes perform better than the norm conservative schemes.     

Superquadratic convergence of DLASQ for computing matrix singular values

DLASQ is a routine in LAPACK for computing the singular values of a real upper bidiagonal matrix with high accuracy. The basic algorithm, the so-called dqds algorithm, was first presented by Fernando-Parlett, and implemented as the DLASQ routine by Parlett-Marques. DLASQ is now recognized as one of the most efficient routines for computing singular values. In this paper, we prove the asymptotic superquadratic convergence of DLASQ in exact arithmetic.