Substituted 2-Phenyl- and 2-Cyclohexyl-trans-decalins,New Classes of Nematic Liquid Crystals

Versatile procedures for the preparation of the title compounds are described. Representatives of ketones ( 12 and 27 ), hydrocarbons ( 19 and 28 ), acids ( 13 ), esters ( 15 . and 20 ), ethers ( 22 ) and nitriles ( 18 ) possess wide-range nematic phases, provided their terminal chains R² and R³ contain at least three methylene units.     

EFFECTS OF N-PHENYLIMIDE S-23142 AND N-METHYL MESOPORPHYRIN IX ON THE SYNTHESIS OF THE PHYTOCHROME CHROMOPHORE IN PEA EMBRYONIC AXES

Abstract Treatment of imbibed embryonic axes taken from seeds of Pisum sativum with N-phenylimide S-23142, a herbicide that has been suggested to inhibit protoporphyrin synthesis, or with N -methyl mesoporphyrin IX, an inhibitor of the iron chelatase for heme, resulted in a significant decrease in the amount of spectrophotometrically detectable phytochromc in the axes in both cases. However, the amount of immunochemically detectable phytochrome was not affected by either treatment. If S-23142 inhibits the synthesis of protoporphyrin IX in pea, it appears that the conversion of protoporphyrinogen IX to protoporphyrin IX is involved in the biosynthesis of the phytochrome chromophore. The conversion of protoporphyrin IX to heme (Fe-protoporpbyrin) also appears to be a step in the biosynthesis of the chromophore, since N -methyl mesoporphyrin IX prevented the synthesis of spectrophotometrically detectable phytochrome but did not affect the magnesium chelatase activity required for the synthesis of chlorophyll in pea embryonic axes. The results suggest that protoporphyrinogen IX, protoporphyrin IX and heme are intermediates in the biogenesis of the phytochromc chromophore. The pathway to phytochromobilin might become fixed after protoporphyrin IX, being directed toward the Fe branch for heme rather than to the Mg branch for chlorophyll.     

Stereospecific living radical polymerization for simultaneous control of molecular weight and tacticity

The simultaneous control of the molecular weights and the tacticity was attained even during radical polymerization by the judicious combinations of the living/controlled radical polymerizations based on the fast interconversion between the dormant and active species, and the stereospecific radical polymerizations mediated by the added Lewis acids or polar solvents via the coordination to the monomer/polymer terminal substituents. This can be useful for various monomers including not only conjugated monomers, such as acrylamides and methacrylates, but also nonconjugated ones such as vinyl acetate and N‐vinylpyrrolidone. Stereoblock polymers were easily obtained by the addition of the Lewis acids or by change of the solvents during the living radical polymerizations. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6147–6158, 2006     

Atomic absorption spectrometry of traces of tri- and hexavalent chromium

Summary Atomic absorption spectrometry combined with extraction is described for the determination of tri- and hexavalent chromium. The chromium diethyldithiocarbamate chelate was used for chromium (VI), whereas hydroxyquinolate or thenoyltrifluoroacetonate chelate for chromium(III). The method is rapid and precise.

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Zusammenfassung Extraktion und darauffolgende Messung der Atomarabsorption wurden zur Bestimmung von drei- und sechswertigem Chrom verwendet. Die Chelatverbindung mit Diäthyldithiocarbamat wurde für Chrom(VI), der Chelatkomplex mit Hydroxychinolin oder Thenoyltrifluoraceton für Chrom(III) verwendet. Das Verfahren ist rasch und genau.

     

Cross-chiral examinations of molecular enantioselective recognition by fast atom bombardment mass spectrometry: Host–guest complexations between chiral crown ethers and chiral organic ammonium ions

Using fast atom bombardment (FAB) mass spectrometry (MS), cross-chiral relationships were confirmed for the first time for the diasteromeric host-guest complexations between the chiral crown ether host (1) and the chiral organic ammonium ion guest (2) on the basis of the relative peak intensities (RPI). Both host–guest combinations (R, R, R, R) – 1, (R) – 2 and (S, S, S, S) – 1, (S) – 2 obviously provided larger RPI values than the combination of both (R, R, R, R) – 1, (S) – 2 and (S, S, S, S) – 1, (R) – 2 by a factor of 1.6 as an averaged value: 1.87 (n = 4)/1.16 (n = 4) = 1.6. These results are consistent with the expected stabilities of the host-guest complexations by CPK model examinations. Successfully observed cross-chiral examinations strongly suggest a potentially useful FABMS/RPI methodology for rapidly searching newly designed and synthesized crown ether-like host compounds with a higher degree of enantioselectivity.     

Radical-initiated homo- and copolymerization of α-methylene-γ-butyrolactone

The kinetics of α-methylene-γ-butyrolactone (α-MBL) homopolymerization was investigated in N,N-dimethylformamide (DMF) with azobis(isobutyronitrile) as initiator. The rate of polymerization (R_p) was expresed by R_p = k[AIBN]^0.54[α-MBL]^1.1 and the overall activation energy was calculated as 76.1 kJ/mol. Kinetic constants for α-MBL polymerization were obtained as follows: k_p/k_t^1/2 = 0.161 L^1/2 mol^?1/2·s^?1/2; 2fk_d = 2.18 × 10^?5 s^?1. The relative reactivity ratios of α-MBL(M₂) copolymerization with styrene (r₁ = 0.14, r₂ = 0.87) were obtained. Applying the Q–e scheme led to Q = 2.2 and e = 0.65. These Q and e values for α-MBL are higher than those for MMA     

Synthesis of monohalocyclopropane derivatives from olefins by the reaction with trihalomethanes and copper

Fluoro-, chloro-, bromo-, and iodocyclopropane derivatives were obtained in 10–80% yields by the reaction of FCHI₂, ClCHI₂, BrCHI₂, and CHI₃, respectively, with Cu in the presence of olefins. The reaction was electrophilic, and proceeded stereospecifically, i.e., cis and trans olefins afforded cyclopropane derivatives whose configurations with respect to the substituents from original olefins were cis and trans, respectively. Since isomeric olefins were not detected in the reaction mixture which would be expected from the insertion of the corresponding free monohalocarbenes into C—H bonds, the reaction seemed to proceed via organocopper intermediates rather than free monohalocarbenes. With respect to the configuration of the halogen introduced by the new reaction, the cis or endo isomers were generally obtained predominantly over the corresponding trans or exo isomers.     

Grinding-induced equimolar complex formation between thiourea and ethenzamide

We prepared and characterized a grinding-induced equimolar complex of thiourea with ethenzamide. When thiourea and ethenzamide were co-ground at a molar ratio of 3 : 1, new powder X-ray diffraction (PXRD) peaks were observed in addition to PXRD peaks of thiourea crystals. The optimum stoichiometry of the new structure was confirmed as 1 : 1 mol/mol. Effect of grinding time on the thiourea-ethenzamide equimolar complex formation was investigated by using PXRD, differential scanning calorimetry and Fourier transform infrared spectroscopy. The equimolar crystal structure was confirmed by X-ray diffraction measurements of the single crystal which was recrystallized from ethanol. It was found that the intermolecular hydrogen bond formations between thiourea and ethenzamide molecules contributed to the equimolar complex formation. The complex formation was not observed in the cases where benzamide, salicylamide or 3-ethoxybenzamide was co-ground with thiourea. 2-Alcoxyl benzamide structures should be required for the grinding-induced equimolar complex formation with thiourea.     

Study on the thermal stability of a chiral stationary phase coated on capillaries for GC

A chiral stationary phase prepared by bonding L -valine-t-butylamide to XE-60 has been coated on glass and metal capillaries. The performances of the chiral glass and metal columns were equivalent to those of commercial fused silica capillary columns. The thermal stability of the glass column was examined up to 280°C. It was found that no appreciable change in separation factor (α value) was observed up to 230°C. The α values gradually decreased between 240 and 260°C, and enantiomer separation was no longer achieved at 280°C. It was concluded that the allowable upper limit temperature of the chiral stationary phase is between 230 and 240°C in the isothermal mode, and ca 260°C in temperature-programmed mode.     

Ionic conductivity of superionic conducting glasses in the pseudobinary system AgIAg2MoO4

The ionic conductivity was measured in the temperature range 250–300 K as a function of composition of superionic conducting glasses in the pseudobinary system AgIAg₂MoO₄. The conductivity, ranging from 10^?2 to 10^?4 Ω^?1 cm^?1 at room temperature, increases linearly in logarithmic scale with increasing AgI content, while the total silver ion concentration remains nearly constant in the whole glass-forming region of the present system. Such a composition dependence of conductivity is considered to be evidence that only a fraction of the silver ions in glass contributes to the ionic conduction. The conductivity and the activation energy for conduction differ slightly between bulk glasses and pressed pellets of pulverized glasses. The close agreement in bulk glasses and pellets suggests that bulk rather than grain boundary or surface diffusion dominates the conduction process in the present glasses.