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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 14 (1992), S. 401-408 
    ISSN: 0887-3585
    Keywords: X-ray diffraction ; allosterism ; zinc/phenol interaction ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Hexameric insulin has been crystallized from different conditions ina variety of crystalline modifications. In the presence of ∼1%phenol and at a pH of 8.5, a new rhom-bohedral form is produced, space group R3, a = 79.92 Åand c = 40.39 Å, in whichthe asymmetric unit consists of a dimer. The structur has been solved and refined, using data between 8.0 and 2.5 Å resolution, to a residual of0.157. The two monomers in the asymmetric unit have nearly identical R conformations, that is, residues Bl through B8 are α-helical, producing a continuous α-helix from Bl through B19. A phenol molecule is hydrogen bonded to the carbonyl oxygen of A6 Cys of each monomer. Small differences in conformation and the final (2Fo-Fc) and difference electron density maps suggest that an additional phenol molecule is coordinated to one of the two zinc ions.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 7 (1993), S. 360-362 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The production of carbon clusters (but not fullerenes) from coal-derived material by the use of laser desorption mass spectrometry is described. Benzo(e)pyrene, a standard polynuclear hydrocarbon found in coal tars, also gave carbon clusters despite using low laser power to avoid pyrolysis of target molecules. Positive- and negative-ion spectra of the standard included carbon clusters. These clusters are formed by the laser energy and can be confused with aromatic hydrocarbons of the same nominal masses. They have no relevance for studies of coal structure.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The use of a laser-desorption mass spectrometer to examine a coal liquefaction extract known to contain high-molecular-mass material (from size-exclusion chromatography) has shown the presence of components of molecular mass in excess of 104Da for the first time. The molecules detected differ from each other in molecular mass by a few hundred or a few thousand Da. These preliminary results indicate that the basic coal-structure molecules probably consist of aromatic clusters on a chin, in reasonable agreement with current theories of coal structure.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Molecular masses up to 270 000 u have been observed during matrix-assisted laser desorption mass spectroscopy on a sample of bituminous coal; the major fraction of desorbed ions appeared between m/z values of 800 and 5000. Similar mass distributions have been found in a coal-liquefaction extract and a pyrolysis tar. The highest molecular masses identified in this work far exceed previously reported high molecular masses found in coal-derived products (12 000 u), which were also detected by laser-desorption mass spectrometry.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 303-310 
    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: Pipes of isotactic polybutene-1 (PB) have been exposed to internal water and external air in pressure tests at 105°C. The pipes exposed to different internal pressures exhibited different failure mechanisms, referred to as stages I, II, and III. Samples taken from these pipes have been analyzed by infrared (IR) spectroscopy, wide-angle X-ray scattering (WAXS), size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). IR spectroscopy and WAXS confirmed that thermal oxidation of the amorphous part of the polymer accompanied the onset of stage III. Thermal oxidation led to extensive molar mass reduction and to a significant increase in mass crystallinity and melting peak temperature. Extensive and visible degradation in pipes failing according to stage III was confined to so-called “oxidation spots.” The latter were first formed at the outer wall and propagated inwards, finally constituting approximately 50% of the wall thickness. The antioxidant concentration profiles obtained by DSC were always symmetrical and were successfully adapted to a previously developed model. It was shown that migration of the antioxidant was the dominant loss mechanism, that the diffusion coefficient was constant through the pipe wall, and that the evaporative loss to the external air was marginally greater than the loss to the internal water phase. Chemical consumption of the antioxidant was found to be negligible.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 649-657 
    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: Changes in polymer structure and antioxidant concentration have been systematically studied as functions of temperature, hoop stress, exposure time, and location in pipe wall on pressure tested pipes of medium density polyethylene. The pressure tests have been performed with water as the internal medium and air as the external medium at temperatures in the range 80 to 105°. Infrared spectroscopy shows that oxidation is initiated at the inner wall surface just prior to the onset of the so-called stage III fracture. X-ray diffraction and size exclusion chromatography show that oxidation involves only the amorphous phase and results in a significant molar mass reduction. The near-inner-wall material exhibits a 10% reduction in mass average molar mass before the onset of stage III fracture and thereafter a more dramatic decrease. Oxidation induction time measurements by differential scanning calorimetry show that the antioxidant concentration is almost twice as high in the center of the wall as in the near-inner-wall and outer-wall material of the unexposed pipe, that the loss of antioxidant is anomalously rapid at the beginning of the high temperature exposure, and that the antioxidant concentration profile gradually becomes more skewed towards the outer wall on prolonged exposure. The data presented in this paper are used in a parallel paper for modeling purposes.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 658-667 
    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: This paper is the first in a series of related papers describing the application of a diffusion/reaction model to the loss of antioxidants from polyolefins in hot-water applications. The model, which is derived in detail, describes the time evolution of antioxidant concentration profiles in the exposed material in terms of adjustable parameters. The parameters describe the rates of diffusion, evaporation, extraction, and chemical reaction of antioxidant. Parameter values are determined by least-squares fitting of the calculated concentration profiles to experimental profiles. The model is applied to a commercial medium density polyethylene pipe material, where antioxidant concentration data from thermal analysis is available for water/air (internal/external) exposure at three temperatures. A comparison of parameter values with literature data is undertaken. The temperature dependence of the parameters is considered and activation energies are compared with literature values. The relative importances of the loss mechanisms are discussed. The effect of boundary conditions on parameter values is considered by application of the model to a limited amount of available data for air/air and water/water exposures. The results indicate that for water/air exposure, extraction by the water phase is the dominating loss mechanism.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 441-445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different hexameric forms of insulin have been crystallized from a variety of conditions. In the presence of 1% phenol, 1.0 M sodium chloride, and at a pH of 8.5, a rhombohedral form is produced with two monomers in the asymmetric unit, space group R3, a = 79.92 Å and c = 40.39 Å. The structure has been solved and refined, using data between 8.0 and 2.5 Å resolution, to a residual of 0.157. Each of the monomers adopts an R conformation, that is residues B1-B8 are α-helical. As a result of the T to R transition, an elliptical cavity is created between symmetry-related monomers and is occupied by a phenol molecule. A region of density within bonding distance to one of the zinc ions has been interpreted as an additional phenol molecule.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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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 crystal structure of a synthetic analogue of valinomycin, cyclo [-(D-Val-L-Hyi-L-Val-D-Hyi)2-] (octa-meso-valinomycin) (I) (C40H68N4O12 · 1.5 · C4H8O2, Mr = 937.01 + 88.10), has been determined. Crystals grown from dioxane are monoclinic, space group P21/a, with cell parameters a = 21.487(8), b = 16.836(5), c = 16.089(4) Å, β = 111.70(4), and Z = 4. The atomic coordinates for nonhydrogen atoms were refined in the anisotropic thermal motion approximation. H atom positions were included in the structure factor calculations at their geometrically expected positions. Values of the standard and weighted R factors after refinement are 0.11 and 0.13, respectively. The conformation of the depsipeptide crystallized from dioxane is different from that crystallized from chloroform (II). The molecule adopts a rectangular shape with two type IV β-turns containing a hydrogen bond and possesses pseudorotational symmetry. The side chains are located on the molecular periphery. The orientation of the carbonyl groups of the molecule is not conducive for efficient metal-ion coordination and in the observed conformation cannot behave as an ionophore.In the crystal the molecules form infinite chains parallel to the c axis, and are stabilized by two intermolecular hydrogen bonds that are shorter and have better geometry than the intramolecular hydrogen bonds.A φ/Ψ plot for dodecadepsipeptides with a (DLLD)3 sequence has well-defined areas for Val and Hyi residues only in cases when the crystals have been grown from nonpolar or medium-polar solvents. The Φ/Ψ plot for octadepsipeptides crystallized from chloroform (II) shows this behavior also. There also is a correlation between the polarity of the solvent from which crystals of octa-meso-valinomycin or valinomycin analogues with a (DLLD) sequence of configuration have been grown and the number of the intramolecular hydrogen bonds that are formed. The more polar the solvent the fewer the number of intramolecular hydrogen bonds.Empirical energy calculations on octa-meso-valinomycin indicate that for isolated molecules, the energy of the bracelet form (II) is 4.7 kcal/mole lower than that of the rectangular form (I).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 16 (1990), S. 144-148 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A principal requirement for quantitative AES and XPS is the ability to measure true spectral intensities. In order to achieve this we have developed a fully instrumented electron spectrometer to measure absolute intensities for AES and XPS. The spectra contain no distortion due to the energy dependencies of the analyser transmission or the detector efficiency, and therefore provide the true spectrum n(E) with a known uncertainty. In addition, the intensity scale is known accurately in terms of electrons detected per unit of incident flux. The experimental methods and theoretical basis used in the determination of standard reference spectra are discussed, and results are presented for both Auger electron and x-ray photoelectron spectroscopies. AES or XPS spectra of NPL reference materials taken on any user's instrument, with the appropriate conditions, may be compared with the true spectra derived here to calibrate the energy dependence of that particular instrument's intensity scale. In this way, all instruments may be calibrated absolutely to an accuracy of ±2%.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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