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  • Chemistry  (1,869)
  • GENERAL
  • 1975-1979  (1,642)
  • 1950-1954  (243)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 18 (1976), S. 1335-1335 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    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: A study has been made of the structure and properties of alternating equimolar and random copolymers of vinylcyclohexanne and α-methylvinylcyclohexane with acrylonitrile using infrared and 1H-NMR spectroscopy methods, as well as x-ray diffraction and differential thermal analyses. The spectral methods allowed an estimation of the composition and distribution of comonomer units in the copolymer macrochains. The thermal stability of alternating copolymers was found to be higher than that of polyacrylonitrile. Alternating and random copolymers are amorphous products with various dimensions of crystallites. Information on the molecular motion intensity and temperatures of structural transitions in copolymer macrochains was obtained by the spin-probe technique.
    Additional Material: 5 Ill.
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eine thermische (a) und eine reduktive (b) Methode zur Herstellung von Mikanez-Estern wird beschrieben. Bei der ersten gelang der Nachweis des monomeren Vorläufers, 1,3-Butadien-2-carboxylester. (a)trans/cis-Gemische von Methyl resp. Äthyl 2-Brom-1-methylcyclopropancarboxylat (14/15 resp. 16/17), mit Tri-n-butylzinnhydrid aus den entsprechenden 2,2-Dibrom-1-methylcyclopropancarboxylaten 12 resp. 13 hergestellt, wurden bei 480°/1,7 Torr pyrolysiert. Die bei -78° daraus abgefangenen Kondensate bestanden aus den 1,3-Butadien-2-carboxylaten 5 und 6, im Falle des Äthylesters 6 durch seine 1H-NMR.-Signale charakterisiert und als Addukt (19) mit 4-Phenyl-1,2,4-triazolin-3,5-dion (18) abgefangen (55%). Beim Erwärmen der Kondensate dimerisierten die Dienester 5 resp. 6, so dass sich Dimethyl resp. Diäthyl Mikanezat (9 resp. 10) isolieren liess (67 resp. 100%).(b)Behandlung von Methyl 2(E)-2-Methyl-2-butenoat (20) mit 2 Äquivalenten N-Bromsuccinimid gab (25%) Methyl 2(Z)-4-Brom-2-brommethyl-2-butenoat (21). (Mit 3 Äquivalenten entstand ein Stereomerengemisch 2(Z)- und 2(E)-4,4-Dibrom-2-brommethyl-2-butenoat (22 und 23)). Reduktion des Dibromesters 21 mit Zink in Tetrahydrofuran, Methanol oder Eisessig ergab (50%) Dimethyl Mikanezat (9). Von einer Iodolaktonisierung der aus 9 durch Verseifung hergestellten Mikanezsäure (8) erhielt man 4-Iodo-7-oxo-1-vinyl-6-oxabicyclo[3.2.1]octan-4endo-carbonsäure (24), dessen Bildungsleichtigkeit und IR.-Bande bei 1780 cm eine unabhängige Bestätigung dafür liefert, dass Mikanezsäure (8) durch Kopf-zu-Kopf-Diels-Alder-Dimerisierung von 1,3-Butadien-2-carbonsäure (4) entsteht.Aus Methyl (E)-2-Methyl-2-pentenoat (25) wurde auf gleiche Weise, d.h. über Dibromierung zu 27 und Reduktion mit Zink in Äther, Dimethyl 3,2′-Dimethylmikanezat (29) gewonnen. Die Multiplizität des 1H-NMR.-Signals von H—C(3) in 29 bestätigt, wiederum unabhängig, dass die Dimerisierung des Dienesters (in diesem Fall 28) in Kopf-zu-Kopf-Diels-Alder-Weise stattfindet.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 8 (1976), S. 354-356 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 77Se n.m.r. spectra of twenty-six organoselenium compounds, including some with an endocyclic selenium atom, have been recorded. Our measurements complete the scale of chemical shifts previously established by McFarlane. It seems difficult to define a range of chemical shifts which is characteristic of the valency state of selenium or of its endo- or exocyclic position. Some results are discussed qualitatively. In the case of selenolo[2,3-b]thiophene, evidence has been obtained for a 4J[Se, H] coupling across the sulphur atom.
    Notes: La résonance magnétique du 77Se a été observée dans vingt-six composés organiques dont certains contiennent un atome de sélénium endocyclique. Nous avons pu ainsi compléter l'échelle de déplacements chimiques établie par McFarlane. II apparaît difficile de définir une gamme de déplacement chimique du 77Se caractéristique de son état de valence ou de sa position endo- ou exocyclique. Certains résultats sont discutés qualitativement. Dans le cas du sélénolo [2,3-b]thiophène, des arguments en faveur d'un couplage 4J(Se, H) à travers l'atome de soufre ont été découverts.
    Additional Material: 4 Tab.
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  • 5
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A low-energy spectrometer for the X-ray analysis of plutonium and plutonium-containing materials has been built. We use ultra-thin window to maintain different pressures and contamination level in the spectrometers's sample and crystal chambers. Ultra-thin windows are also used on the X-ray tube and detector. Methods have been developed by which the spectrometer can analyze both metal and loose-powder samples. Representative calibration spectra are presented for the fluorine band in polyfluoroethylene, the oxygen band in α-Al2 O3, and the carbon band in graphite. Experimental spectra are presented for the fluorine band in PuF3 and for the oxygen ban in PuO2.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Fire and Materials 1 (1976), S. 85-89 
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The chemical mechanisms for the action of flame retardants are often mentioned in the literature but the physical modes of action are seldom. Discussed. This article presents one way to quantify their efficiency. The technique is based on literature data for the physical and thermal properties of flams retardants for temperatures from 25°C up to 1000°C. The prolongation of the time to ignition by heat absorption by the retardant and the amount of inert gas evolved by the retardant are calculated at a given radiation for a material flame-proofed with a given amount of the flame retardant. The ability to form an insulating surface layer is considered but not quantified. It is assumed that a medium density wood fibre building boards is treated with 2 kg of flame retardant per m2. The flame retardants included are borates, boric acid, phosphates and silicates. The board is assumed to be irradiated with an intensity of 15 k W m-2. Under these conditions an untreated board ignites after 6-7 min. The time to ignition is prolonged by 1-5 min through heat absorption by the different retardants, and the amount of inert gases evolved may be as high as 2.6 m3 per m2 board. The formation of an insulating surface layer is more difficult to quantify. The results confirm the importance of the physical modes of action of flame retardants and the technique could form the basis for evaluating materials in simulated fire situations.
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2491-2506 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Normal vibrational analysis was carried out for DNA molecules in both A and B conformations as well as for A-RNA. A simplified backbone model was examined and expanded to include the backbone phosphate-group and the ribose ring. We applied the new force-constant refinement procedure discussed in the preceeding paper [Van Zandt, L. L., Lu, K.-C. & Prohofsky, E. W. (1977) Biopolymers, 16, 2481-90] to fit some observed frequencies in the Raman spectra for all three nucleic acids with the same set of force constants. The results indicate that the observed frequency shift can be attributed to the conformational change solely. We ignored the second-order differences in force constants for the different geometries. The agreement between the observed and calculated frequencies derived from the final refined set of force constants is good and apparently justifies this assumption. Two modes previously assigned to the symmetric diester O-P-O stretch and the symmetric dioxy O‥P‥O stretch are actually fitted. They are mainly backbone phosphate-group modes. The refined ribose-ring force-constants were transferred to the calculation of the vibrational spectrum of tetrahydrofuran. The overall agreement is again good. We discuss these calculations and the resulting normal modes. We also discuss the application of the Green-function refinement scheme and several strategies adopted to bias the convergence of the procedure.
    Additional Material: 2 Ill.
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  • 8
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermally induced helix-coil transitions of three A-T DNAs, d(A)n·d(T)n, d(A-T)n·d(A-T)n, and d(A-A-T)n·d(A-T-T)n, were studied. Experimental transition curves of the DNAs were analyzed using the loop entropy model of DNA melting. The calculation of the melting curve of d(A-A-T)n·d(A-T-T)n is presented using the integral equation formalism of Goel and Montroll. The aim of this work was to evaluate thermodynamic parameters which govern DNA stability and to test the theoretical model employed in the analysis. Our results show (1) an excellent over-all agreement between theory and experiment, (2) a loop entropy exponent k = 1.55 ± 0.05 provided the best fit to all the polymer transition curves, (3) the evaluated stacking free energies reflect the relative stability of the DNAs, and (4) the stacking energies of the ApA·TpT dimer evaluated from d(A)n·d(T)n and d(A-A-T)n·d(A-T-T)n differ. The last result is consistent with different conformations for the dimer in these two polymers.
    Additional Material: 4 Ill.
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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: An optimized potential function for base-stacking interaction is constructed. Stacking energies between the complementary pairs of a dimer are calculated as a function of the rotational angle and separation distance. Using several different sets of atomic charges, the electrostatic component in the monopole-monopole approximation (MMA) is compared to the more refined segmented multipole-multipole representation (SMMA); the general features of the stacking minima are found to be correctly reproduced with IEHT or CNDO atomic charges. The electrostatic component is observed to control the location of stacking minima. The MMA, in general, is not a reliable approximation of the SMMA in regions away from minima; however, the MMA is reliable in predicting the location and nature of stacking minima. The attractive part of the Lennard-Jones 6-12 potential is compared to and parameterized against the expression for the second-order interaction terms composed of multipole-bond polarizability for the polarization energy and transition-dipole bond polarizabilities for approximation of the dispersion energy. The repulsive part of the Lennard-Jones potential is compared to a Kitaygorodski-type repulsive function; changing the exponent from its usual value of 12 to 11.7 gives significantly better agreement with the more refined repulsive function. Stacking minima calculated with the optimized potential method are compared with various perturbation-type treatments. The optimized potential method yields results that compare as well with melting data as do any of the more recent and expensive perturbation methods.
    Additional Material: 1 Ill.
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  • 10
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of translational diffusion coefficients by quasielastic laser light scattering, sedimentation coefficients, and intrinsic viscosities at zero shear of proteoglycan subunit fraction A1-D1-D1 isolated from bovine nasal septa are reported. Molecular weights and hydrodynamic dimensions are compared with those expected on the basis of structural models previously proposed. Comparison of the concentration dependence of the diffusion coefficient in the presence of NaCl and GdnHCl leads to the conclusion that significant self-association behaviour of subunit occurs in the absence of GdnHCl. In the absence of added salt, anomalous nonlinear concentration dependence of Dt estimated from wide-angle light-scattering experiments is observed. In addition, Dt apparently becomes angle dependent. These results are interpreted in terms of the perturbation of normal translational diffusion of the monomer by strong repulsive intermolecular interactions due to the combined effects of long-range electrostatic forces and macromolecular congestion at higher concentrations. By carrying out experiments at small scattering angles, it is possible to determine Dt0 for proteoglycan subunit in the absence of supporting electrolyte. Titration of a dilute solution of subunit with hyaluronic acid results in a sigmoidal behaviour of the Stokes radius, indicating the formation of complexes of higher molecular weight results from the noncovalent association of proteoglycan subunits with hyaluronate. Observation of Dt appears to provide a useful method for studying the proteoglycan subunit-hyaluronate interactions.
    Additional Material: 14 Ill.
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