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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Plant and soil 147 (1992), S. 49-57 
    ISSN: 1573-5036
    Keywords: ammonium ; field ; kiwifruit ; 15N ; nitrogen fertilizer ; recovery ; soil nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The fate of 15N-labelled ammonium fertilizer applied once to six-year-old field-grown kiwifruit (Actinidia deliciosa ‘Hayward’) vines was measured over three years. The three main treatments were nitrogen (N) applied singularly at 100 or 200 kg N ha−1 in early spring (two weeks before bud burst) or split with 100 kg N ha−1 (unlabelled) in early spring and 100 kg N ha−1 (15N-labelled) ten weeks later. All N treatments were applied to vines with a history of either 50 or 200 kg N ha−1 yr−1. For three years after 15n application, components of the vines and soil (0–600 mm depth) were sampled at harvest in late autumn and the N and 15N contents determined. By the first harvest, all plant uptake of 15N had occurred and this represented 48–53% of the 15N applied. There was no significant effect of current N fertilizer treatment or of N history on 15N recovery by vines. Removal of 15N in harvested fruit was small at 5–6% in the first year and 8% over 3 years. After 2–3 years, most plant 15N occurred in the roots and this component declined only slowly over time. In contrast, there was a large temporal decline in 15N in above-ground plant components due to the annual ‘removal’ in leaf fall and pruning. An associated experiment showed that when 15N-labelled prunings and leaves were mulched and returned to the soil, only about 9% was recovered by plants within 2 years. Almost all remaining mulched material had been immobilised into the soil organic N. In all treatments, about 20% of the added 15N remained in soil at the first harvest. This was almost entirely in organic fractions (〈0.4% in inorganic N) and mostly in the surface 150-mm layer. The 15N content in soil changed little over time (from 20 to 17% between the first and third harvests respectively) and indicated that most of the N had been immobilised into stable humus forms.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Plant and soil 147 (1992), S. 59-68 
    ISSN: 1573-5036
    Keywords: kiwifruit ; 15N ; plant uptake ; remobilisation ; temporal changes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Temporal changes in the nitrogen (N) and 15N content of various components of six-year-old kiwifruit (Actinidia deliciosa ‘Hayward’) vines which had received 15N-labelled ammonium fertilizer were measured. The fertilizer was applied singularly at 100 or 200 kg N ha−1 in early spring (two weeks before bud burst) or split with 100 kg N ha−1 (unlabelled) in early spring and 100 kg N ha−1 (15N-labelled) ten weeks later. All treatments were applied to vines with a history of either 50 or 200 kg N ha−1 yr−1. The N concentration of leaf and fruit tissue was generally lower in the 100 kg N ha−1 treatment than in the 200 kg N ha−1 treatments and this effect was greater than that of N fertilizer history. During the first 8 weeks after bud burst there was a rapid accumulation of N in leaves (ca. 80 kg N ha−1). Analysis of xylem sap at 4 weeks after bud burst revealed that about 60% of the N utilised for new growth was from remobilisation of N stored within the vines and about 40% from soil and fertilizer N. This was unaffected by rate of N application. Plant uptake of added 15N was rapid and almost complete within 10 weeks of application in either early spring or early summer. Initially, most 15N was present in the leaf and root components but these subsequently declined due to translocation into other components of the vine. The decline in leaf 15N coincided with an equivalent accumulation of 15N in the fruit. The 15N enrichment of the ‘annual’ components (leaves, fruit and current-season's shoots) was about twice that of the structural components (one-year-old shoots, cordon, stem and structural roots) during the first year after application. By the third year the 15N concentration of the annual components had declined to similar levels to that of the structural components. These changes were used to estimate the annual throughput of N from soil in vines which received no N fertilizer in years 2 and 3 at 50% of total above-ground N and only 7% in roots. This was equivalent to about 120 kg N ha−1 yr−1. Where fertilizer N (200 kg ha−1) was applied in year 2 the annual throughput of N from soil and fertilizer was about 170 kg N ha−1.
    Type of Medium: Electronic Resource
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  • 3
    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 analog of valinomycin, cyclo[-(D-Ile-Lac-Ile-D-Hyi)3-] (C60H102N6O18), has been determined by x-ray diffraction procedures. The crystals are orthorhombic, space group P212121, with cell parameters a = 11.516, b = 15.705, c = 39.310 Å, and Z = 4. The atomic coordinates for the C, N, O atoms were refined in the anisotropic thermal motion approximation and for the H atoms in the isotropic approximation. Values of standard (R) and weighted (Rw) reliability factors after refinement are 0.073 and 0.056, respectively. The structure is completely asymmetric. The cyclic molecular backbone is stabilized by six intramolecular hydrogen bonds N—H…O=C, five bonds being of the 4→1 type and one being of the 5→1 type. The side chains are located on the molecular periphery. The conformational state of isoleucinomycin in the crystal is intermediate between the corresponding crystalline states of valinomycin and meso-valinomycin. The observed conformation suggests that complexation could proceed via entry of the ion at the face possessing the L-Lac residues, the less crowded face.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    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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  • 5
    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.
    Type of Medium: Electronic Resource
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  • 6
    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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  • 7
    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.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 14 (1970), S. 777-787 
    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: The preparation of isotactic and syndiotactic 1,4-polypentadienes with a cis content of at least 70%-75% using i-Bu2AlH/Ti(i-OPr)4 and AlEtCl2/thiophene/Co(acetylacetonate)2 catalysts, respectively, is reported. Physical characterization of the vulcanizates, prepared by a common recipe, involving infrared analysis, DTA, simple stress-strain and swelling measurements, and dynamic mechanical measurements over a frequency range of 2 decades and temperature range of -60°C to +20°C indicated that no isomerization had taken place during vulcanization and that stereoregularity of the polymer chains affected the resultant cure: the isotactic form was found to have a greater crosslink density than the syndiotactic form. Master curves covering an extended frequency range were constructed from the reduced dynamic mechanical data and the calculated quantities - thermal expansion coefficients of free volume and the fractional free volumes at the glass transition temperatures - agree with the accepted values. Glass transition temperatures of the isotactic and syndiotactic polymers are -37°C and -42°C, respectively, and for their vulcanizates, -33°C and -40°C, respectively.
    Additional Material: 9 Ill.
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  • 9
    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 series of prepolymers containing terminal blocked isocyanate groups was prepared by reaction of isocyanate-terminated prepolymers [derived from a poly(propylene oxide) diol (MW = 2000) or a triol (MW = 3000) and different diisocyanates] with various blocking agents. Their curing rates with a polyepoxide crosslinking agent were measured to assess their suitability for a delayed-cure durable-press treatment for wool. The curing rates varied over a wide range, but commonly used blocking groups such as phenols, caprolactam, β-diketones, and alcohols were not sufficiently reactive for the intended application, although others, e.g., oximes and certain blocking agents containing a basic center such as N,N-diethylhydroxylamine, hydroxypyridines, and hydroxyquinolines, had the required reactivity. Blocking by 1,3-dipolar cycloaddition of nitrones was examined, but the reactivities were too low. Prepolymers containing blocked aromatic isocyanates were more reactive than those containing blocked aliphatic isocyanates. Difunctional butanone oxime-blocked pre-polymers cured slightly more slowly than analogous trifunctional prepolymers.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 26 (1981), S. 159-170 
    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: Carbon dioxide sorption isotherms in poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) are reported for pressures up to 20 atm. Temperatures between 35 and 80°C were studied for PMMA and temperatures between 30 and 55°C were studied for PEMA. Typical dual mode sorption isotherms concave to the pressure axis were observed in all cases. The measured Langmuir sorption capacities of both polymers extrapolated to zero at the glass transition (Tg) consistent with the behavior of other glassy polymer/gas systems. Sorption enthalpies for CO2 in the Henry's law mode for PMMA and PEMA are in the same range (-2 to -4 kcal/mole) as has been reported for a variety of other glassy polymers such as poly(ethylene terephthalate), polycarbonate, and polyacrylonitrile. Some of the data suggest that postcasting treatment of the PEMA films left a small amount of residual solvent in the film. the presence of the trace residual solvent during quenching from the rubbery to the glassy state after annealing appears to cause a dilation of the Langmuir capacity and an alteration in the apparent Langmuir affinity constant of the PEMA film. These results suggest the possibility of tailoring physical properties of glassy polymers such as sorptivity, permeability, impact strength, and craze resistance by doping small amounts of selected residuals into polymers prior to quenching to the glassy state from the rubbery state.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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