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  • Chemistry  (1,374)
  • Organic Chemistry  (122)
  • 1995-1999  (1,112)
  • 1955-1959  (266)
  • 1
    ISSN: 1057-9257
    Keywords: phospholipid analogue crystals ; synthesis ; molecular structure ; X-ray analysis ; electrophysical properties ; conjugated ionic-hydrogen bond systems ; molecular wires ; molecular electronics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Synthesis and investigation of the structure and electrophysical properties of two halogen hydride derivatives of isobutyl analogues of phosphatidylethanol amine (IPE), namely IPE-HCl and IPE-HBr, were performed to offer a new material for ‘molecular wires’ according to the model of molecular electronics developed earlier by Karasev et al. (Adv. Mater. Opt. Electron., 1994, 4, pp. 203-218). X-ray analysis showed that isostructural crystals of the synthesised compounds are monoclinic with the space symmetry group I2/a (C2/c). They have very similar lattice cell parameters, namely a = 21.892(8), b = 4.7747(2), c = 44.63(2) Å, β = 91.83(3)°, Z = 16 for IPE-HCl and a = 22.115(14), b = 4.808(3), c = 44.83(2) Å, β = 91,74(5)°, Z = 16 for IPE-HBr. It was found that the structure of IPE-HCl contains two symmetrically unrelated molecules of IPE. They form two bilayers within the elementary cell each of which includes three zones of hydrogen bonds. The central zone is formed by NH3 groups belonging to IPE and by chloride ions. The other two zones are quasi-one-dimensional systems of HO(SINGLE BOND)P(DOUBLE BOND)O groups generated by translationally related IPE molecules and can be considered as prospective ‘molecular wires’. These two zones are located symmetrically with respect to the central zone. Electrophysical parameters (contuctance γ and complex dielectric permittivity components ε′ and ε″) were determined for polycrystalline samples of IPE-HCl and IPE-HBr in the temperature range from -20 to 70°C. The permittivity ε′ was found to assume abnormally high values (about 106) at low frequency and to decrease monotonically with increasing temperature in the frequency range from 50 Hz to 10 MHz. Possible mechanisms of polarisation of the synthesised IPE derivatives are analysed. The conductance of the crystals was shown to have an activation character with the activation energy equal to 0.7-1.3 eV for IPE-HCl and 0.4-0.6 eV for IPE-HBr. A hopping mechanism was proposed to explain charge transfer along the systems of HO(SINGLE BOND)P(DOUBLE BOND)O groups involving Cl- and Br- ions.
    Additional Material: 6 Ill.
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  • 2
    ISSN: 1076-5174
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ionization efficiency curves for [M — X]- ions from p-XC6H4N=NC6H5 molecules (X=F, Cl, Br) have been registered in the energy range 0-9 eV with appearance energies 3.3, 4.1 and 3.2 ± 0.2 eV, respectively. The heats of formation of 17 isomeric C12H9N- ions have been estimated using isodesmic reactions. The possible mechanism of isomerization of molecule ions leading to various isomeric [M — X]- ions is represented. The resonance stabilization of both negative and positive ions, questioned for negative ions by some workers, was confirmed by measuring appearance energies of conjugated ions [M — H]- and [M — (CCl2 + CI)]- or [M — Me]+ and [M — CCl3]+ coming from p-MeC6H4O—R (R= or Me) and 4-Methyl-4-trichloromethylcyclohexa-2,5-dienone, respectively.
    Additional Material: 1 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1855-1857 
    ISSN: 1434-1948
    Keywords: Fullerenes ; Titanium ; Complexes ; X-ray analysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first fullerene complex of titanium Cp2Ti(η2-C60) has been synthesized by reaction of the bis(trimethylsilyl)-acetylene complex of titanocene Cp2Ti(η2-Me3SiC2SiMe3) with an equimolar amount of fullerene-60 in toluene at room temperature under argon. An X-ray diffraction study of the complex has shown that it has the structure of a titanacyclopropane derivative.
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  • 4
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1321-1324 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyetherimides (PEI) based on dianhydrides of 3,3′, 4,4′-dipheniloxytetracarboxylic acid and 1,3-bis-(3,4-di-carboxyphenoxy)benzene that contain fragments of such thermoplastic polymers as poly(ether sulfone) or poly(phenylene oxide) have been synthesized. Thermoplastic properties of synthesized PEI were characterized by flow temperature Tf and melt viscosity ηm. The properties obtained are outstanding for the production of PEI as fusible film binders, and composites can be produced without toxic solvents. Carbon fiber reinforced plastics (CFRP) based on PEI films were analyzed using an Acoustic Emission (AE) technique.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0006-3592
    Keywords: α-chymotrypsin ; covalent modification ; enzyme-polyelectrolyte complexes ; enzymatic activity ; denaturation ; water-cosolvent mixtures ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Formation of noncovalent complexes between α-chymotrypsin (CT) and a polyelectrolyte, polybrene (PB), has been shown to produce two major effects on enzymatic reactions in binary mixtures of polar organic cosolvents with water. (i) At moderate concentrations of organic cosolvents (10% to 30% v/v), enzymatic activity of CT is higher than in aqueous solutions, and this activation effect is more significant for CT in complex with PB (5- to 7-fold) than for free enzyme (1.5- to 2.5-fold). (ii) The range of cosolvent concentrations that the enzyme tolerates without complete loss of catalytic activity is much broader. For enhancement of enzyme stability in the complex with the polycation, the number of negatively charged groups in the protein has been artificially increased by using chemical modification with pyromellitic and succinic anhydrides. Additional activation effect at moderate concentrations of ethanol and enhanced resistance of the enzyme toward inactivation at high concentrations of the organic solvent have been observed for the modified preparations of CT in the complex with PB as compared with an analogous complex of the native enzyme. Structural changes behind alterations in enzyme activity in water-ethanol mixtures have been studied by the method of circular dichroism (CD). Protein conformation of all CT preparations has not changed significantly up to 30% v/v of ethanol where activation effects in enzymatic catalysis were most pronounced. At higher concentrations of ethanol, structural changes in the protein have been observed for different forms of CT that were well correlated with a decrease in enzymatic activity. © 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 267-277, 1997.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 24 (1996), S. 469-475 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Boron and germanium δ-doped silicon samples were studied using SIMS depth profiling on a Cameca IMS-4F instrument with O2+, N2+ and Cs+ primary beams at various energies and incidence angles. The depth resolution characteristics were compared. We show that, with experimental conditions being the same, the N2+ primary beam provides for better decay lengths, while the leading edges of the profiles turn out to be significantly broadened because of the beam-induced roughness which develops at an early stage of silicon bombardment by N2+ ions. The influence of ripple-like roughness on the SIMS profile shape is considered within the present simple analytical model. The effect of a modified layer on the SIMS profile depth was experimentally investigated. For profiles obtained with an N2+ primary beam, it was shown that swelling of the modified layer produced by the implantation and trapping of primary particles shifts the profile as a whole toward the surface.
    Additional Material: 10 Ill.
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  • 7
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structural, shrinkage and mechanical characteristics were studied of specimens of ultra-high-molecular polyethylene (UHMPE) and polymerization-filled composites UHMPE-Al and UHMPE-bauxite produced by plunger extrusion of powder material. It is shown that the dependence of the strain-stress characteristics of UHMPE and its composites on the extrusion ratio varies considerably in the presence of a filler. Mechanisms explaining the behavior of the polymer material under study are proposed.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 711-719 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemistry of IrCl62- complex in simple alcohols have been studied using laser-flash photolysis. Single electron transfer from the solvent molecule to the light-excited complex has been shown to be the primary photochemical process. Quantum yields of the photoreduction of IrCl62- complex and the rate constants of its reaction with hydroxyalkyl radicals were determined at 200-330 K. Deviations of the rate constants from Debye-Smoluchowski equation for diffusion-controlled reactions are discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 711-719, 1998
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  • 9
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of competitive binding of two polyanions - DNA and synthetic fluorescence-tagged poly(methacrylate) (PMA*) - with the polycation-quencher poly(N-ethyl-4-vinyl-pyridinium) (PEVP) was studied by fluorescence quenching technique. It was found that ability of DNA to displace PMA *from the water-soluble nonstoichiometric interpolyelectrolyte complex (NPEC) formed by PMA* and PEVP - NPEC(PMA*-PEVP) - and to form water-soluble NPEC(DNA-PEVP) \documentclass{article}\pagestyle{empty}\begin{document}$$ NPEC(PMA^{*}\hbox{-}PEVP) + DNA \Leftrightarrow NPEC(DNA\hbox{-}PEVP) + PMA^{*}$$\end{document} can be determined by the parameter Ψ = PPMA*/PPEVP where PPMA* and PPEVP are the degrees of polymerization of PMA* and PEVP, respectively. In the case of Ψ 〈 1 the decrease of Ψ leads to the shift of the reaction equilibrium to the right, which can be explained by the gain of entropy due to the increase of the total number of polymeric particles in the solution. Introduction of alkali metal cations into the reaction mixture results in the shift of the reaction equilibrium, and according to their ability to shift the equilibrium to the right the cations can be arranged in the series Na+ 〉 K+ 〉 Li+. The substitution of native DNA by denatured DNA practically does not affect the reaction equilibrium in solutions of NaCl and KCl but considerably shifts it to the right in solutions of LiCl. The data obtained are in accordance with the differences in the selectivity of alkali cations binding with competitive polyanions. © 1995 John Wiley & Sons, Inc.
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  • 10
    ISSN: 0006-3525
    Keywords: x-ray crystallography ; ionophore ; valinomycin analogue ; crystal and molecular structure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal and molecular structure of the valinomycin analogue, cyclo [(D-Val-L-Lac-L-Ala-D-Hyi)2 (D-Val-L-Lac-L-Val-D-Hyi)] has been solved by x-ray direct methods using the “Shake and Bake” procedure. The crystals, grown from a mixture of octane/CH2Cl2, belong to space group P21 (Z = 4 ) with cell parameters a = 10.29, b = 32.08, c = 18.73 Å β = 97.05°, and contain two molecules per asymmetric unit. After anisotropic refinement the standard reliability factor was R1 = 0.058. The conformations of both independent molecules is similar to that observed for isoleucinomycin, cyclo [-(D-Ile-L-Lac-L-Ile-D-Hyi)3] [V. Z. Pletnev et al. (1980) Biopolymers, Vol. 19, pp. 1517-1534]. The structure has an asymmetric conformation stabilized by six intramolecular H bonds, five bonds being of the 4 → 1 type and one bond being of the 5 → 1 type. One water molecule is caged in the internal cavity of each cyclodepsipeptide. This conformation could represent an intermediate state between free and complexed forms of valinomycin. © 1997 John Wiley & Sons, Inc. Biopoly 42: 651-658, 1997
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