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  • 11
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A study has been made of the individual film coefficients of mass transfer for two binary liquid-liquid systems of differing physical properties, namely methyl isobutyl carbinol-water and methylethyl ketone-water, in a 4-in. diam. extraction column operated as a spray column and with 1/2-in. Raschig ring packing. The value of Ht for the dispersed phase was found to be a constant, C1 for a given system in a given column. The Ht values for the continuous phase could be correlated by the equation, \documentclass{article}\pagestyle{empty}\begin{document}$$(H_t )_c = C_2 (V_c /V_d )^n $$\end{document} Values of the constants C1, C2, and n are tabulated along with the values found by earlier investigators for other systems and column packings. The Ht values have been reduced to area base coefficients by the expression for droplet surface area proposed by Gaylor and Pratt (3).Presaturation of either phase was found to have no effect on mass transfer rates. There appears to be relatively little difference in the efficiency of spray and packed columns for systems of low interfacial tension, but for high interfacial-tension systems packed columns are considerably more efficient than spray columns.While no definitive correlations for the effect of physical properties are proposed, there are some indications that n is a function of the viscosity ratio of the two liquid phases and that C2 is a function of the 1/4 power of the groups (dΔργ/μ2c)(μc/μa) and (NS c)c. No correlation was found for the effect of physical properties on (Ht)d.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 74 (1962), S. 83-83 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 13
    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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  • 14
    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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  • 15
    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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  • 16
    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.
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  • 17
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionophores are antibiotics that induce ion transport across natural and artificial membranes. The specific function of a given ionophore depends upon its selectivity and the kinetics of ion capture, transport, and release. Systematic studies of complexed and uncomplexed forms of linear and cyclic ionophores provide insight into molecular mechanisms of ion capture and release and the basis for ion selectivity. The cyclic dodecadepsipeptide valinomycin, cyclo[(L-Val-D-Hyi-D-Val-L-Lac)3-]. transports potassium ions across cellular membrane bilayers selectively. The x-ray crystallographic and nmr spectroscopic data concerning the structures of Na+, K+, and Ba+2 complexes are consistent and provide a rationale for the K+ selectivity of valinomycin. Three significantly different conformations of valinomycin are observed in anhydrous crystals, in hydrated crystals grown from dimethylsulfoxide, and in crystals grown from dioxane. Each of these conformations suggests a different mechanism of ion capture. One of the observed conformations has an elliptical structure stabilized by four 4 ← 1 intramolecular hydrogen bonds and two 5 ← 1 hydrogen bonds. Ion capture could be readily achieved by disruption of the 5 ← 1 hydrogen bonds to permit coordination to a potassium ion entering the cavity. The conformation found in crystals obtained from dimethyl sulfoxide is an open flower shape having three petals and three 4 ← 1 hydrogen bonds. Complexation could proceed by a closing up of the three petals of the flower around the desolvating ion. In the third form, water molecules reside in the central cavity of a bracelet structure having six 4 ← 1 hydrogen bonds. Two of these bracelets stack over one another with their valine-rich faces surrounding a dioxane molecule. The stacked molecules form a channel approximately 20 Å in length, suggesting that under certain circumstances valinomycin might function as a channel. A series of analogues of valinomycin differing in ring composition and size have been synthesized and their transport properties tested. Peptide substitution and chiral variation in the dodecadepsipeptide can result in stabilization or modification of the different conformers. While contraction of the ring size results in loss of ion transport properties, expansion of the ring size permits complexation of larger ions and small positively charged molecules.Gramicidin A is a pentadecapeptide that functions as a transmembrane channel for transporting monovalent cations. Crystal structures of the cesium chloride complex and two uncomplexed forms of gramicidin A have been reported. In all three structures the gramicidin A molecule is a left-handed, antiparallel, double-stranded helical dimer. In the cesium complex the β7.2-helix has 6.4 residues per turn with an internal cavity large enough to accommodate cesium ions. In the uncomplexed structures the channel is 31 Å long and has 5.6 amino acids per turn. Because the helix is too tightly wound to permit ion transport, ion transport would require breaking and reforming of hydrogen bonds. © 1996 John Wiley & Sons, Inc.
    Additional Material: 16 Ill.
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  • 18
    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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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 62 (1996), S. 1167-1177 
    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: Blends of aromatic/aliphatic polyamides of varying compositions were extrusion compounded with an impact modifying reactive elastomer and injection molded. The effect of two different twin-screw blending configurations on the physical and mechanical properties of the blends was evaluated. Effects of processing conditions on blend morphology were also examined. The experimental results indicate that the extrusion sequence affects the extent of polyamide matrix-elastomer reaction as well as the morphology. The relationship between blend morphology, blend components structure and reactivity, and processing conditions with ultimate properties is discussed. © 1996 John Wiley & Sons, Inc.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 223 (1935), S. 1-16 
    ISSN: 0863-1786
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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