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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 463-472 
    ISSN: 0009-2940
    Keywords: Hypervalent compounds ; Tellurium ; Polycations ; Molecular Orbital Theory ; Band structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Approximate MO and band structure calculation are used to analyze the bonding in the recently synthesized paramagnetic, semiconducting phase [Te15Br4]2+. The [Te15Br4]2+ chains are very similar to those in the tellurium subhalide Te2Br. The electronic structure and bonding within these chains is analysed and the possibility of hypervalency in both [Te15Br4][MoOBr4]2 and Te2Br is discussed. The bonding in the classically hypervalent molecule TeBr42- and a model Te3Br24- is compared to that of the infinite system. Our calculations indicate that both [Te15Br4][MoOBr4]2 and Te2Br contain weakly hypervalent Te atoms and that the interesting electronic properties of [Te15Br4][MoOBr4]2 arise within the distinct sublattices, which do not interact significantly.
    Additional Material: 12 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1105-1124 
    ISSN: 0887-624X
    Keywords: liquid crystalline ; epoxy ; kinetic ; curing ; smectic ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The curing kinetics of a system containing 4,4′-diglycidyloxy-α-methylstilbene (DOMS) and different functionality amines, N-ethylaniline (NEA), aniline, benzenesulfonamide (BSA), and sulfanilamide (SAA), have been studied by differential scanning calorimetry (DSC) under isothermal conditions. The phase transformations during curing of the systems have been monitored by a crosspolarized optical microscope equipped with a hot-stage and photo detector. It has been found that the growth of a nematic liquid crystal structure does not cause a discrepancy from the autocatalytic model for the reactions between aniline and epoxy. There is no liquid crystalline structure formed for the systems containing NEA or BSA, which follow the autocatalytic kinetic models within the temperature range of 120-150°C. For the curing reactions between DOMS and SAA, there is a big deviation from the autocatalytic model when the liquid crystals transfer from a nematic structure to a smectic structure. Unlike the usual decrease of reaction rate resulting from diffusion in a heterogeneous reaction, the reaction rate is enhanced. A modified kinetic model has been constructed for this reaction system by introducing a pseudoconcentration term caused from the liquid crystalline structure formation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1105-1124, 1997
    Additional Material: 14 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1457-1471 
    ISSN: 0887-624X
    Keywords: epoxy ; catalyst ; liquid crystalline ; kinetic ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetraalkylphosphonium-Tetrafluoroborate-Tetrafluoroboric Acid was used as a catalyst in the curing of a liquid crystalline epoxy. Under some conditions the Tetraalkylphosphonium-Tetrafluoroborate-Tetrafluoroboric Acid actually retarded the reaction. An extensive experimental and kinetic analysis is presented anda mechanism for the reaction retardation is proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1457-1471, 1998
    Additional Material: 16 Ill.
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  • 4
    ISSN: 0935-9648
    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
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 50 (1996), S. 222-227 
    ISSN: 0006-3592
    Keywords: γ-poly(glutamate) ; γ-PGA ; Bacillus licheniformis ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bacillus licheniformis ATCC 9945A was grown on Medium E in batch fermentations in which the pH was maintained at 5.5., 6.5, 7.4, and 8.25. The effects of pH on cell growth, carbon source utilization, and γ-polyglutamic acid (γ-PGA) production, molecular weight, and polymer stereochemistry were determined. The γ-PGA yield was highest (15 g/L, 96 h growth time) at pH 6.5. The increase in γ-PGA formation at pH 6.5 corresponded with a relatively high specific production rate at high γ-PGA concentration (0.09 h-1, ∼15 g/L γ-PGA). In contrast, the specific γ-PGA production rates at fermentor pH values of 5.5 and 7.4 decreased significantly for γ-PGA fermentor yields 〉∼5 g/L. Interestingly, alteration of the medium pH had little to no significant effects on the product quality as measured by stereochemical composition and molecular weight. While glutamate and glycerol utilization were similar as a function of pH, citrate consumption increased at pH 6.5, indicating that the formation of γ-PGA from citrate at pH 6.5 was of increased importance. The effect of aeration was evaluated by increasing the agitation speed (250 to 800 rpm) and aeration rate (0.5 to 2.0 L/min) at pH 6.5, the pH of maximal γ-PGA production. Increased aeration resulted in doubling of the cell dry weights (2 to 4 g/L), increasing γ-PGA yields (6.3 to 23 g/L by 48 h) and increasing in the maximum γ-PGA-specific production rate (0.09 to 0.11 h-1). Other effects of increased agitation included a rapid depletion of glutamate and citrate (by 50 h) and a decrease in product molecular weight. Despite the increase in agitation and aeration, oxygen limitation of the culture was not avoided, because the partial pressure decreased to 〈1.0% by 29 h. © 1996 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 6 (1997), S. 931-948 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: There has been a great deal of recent interest in monitoring polymer interdiffusion with fluorescence nonradiative energy transfer (NRET), a typical experiment consisting of polymer chains labeled with a donor chromophore interdiffusing with chains labeled with an acceptor chromophore, causing an increase in energy transfer efficiency, E. A factor nearly always ignored in models of this process is the fact that chromophore interactions are screened out because of intermolecular correlation effects, leading to a lower E than would otherwise be expected. The model of Dhinojwala and Torkelson (Macromolecules 27, 4817 (1994)) has been modified to include correlations in order to explore the impact that ignoring correlations has on the diffusion coefficients calculated in such experiments. When correlations are included in the model, E is proportional to (Dpt)1/2/x for t〈x2/(16Dp) (where x is the thickness of the donor-labeled film and Dp is the polymer diffusion coefficient), similar to when correlations are ignored. Within this linear regime errors in Dp associated with ignoring correlations are typically less than 20% for logically defined systems, which may be insignificant given the uncertainty with which diffusion coefficients are normally reported. However, this study clearly demonstrates that precautions should be used in all experiments of this type to stay in this linear regime, as improperly accounting for or ignoring correlation effects at longer diffusion times can lead to the spurious result that apparent diffusion coefficients decrease with annealing time, by factors of 2 to 5 to as much as an order of magnitude or more at sufficiently long time. Systems designed to minimize correlation effects should have a large Förster radius and a sufficiently high ratio of acceptors to donors; with such a situation and the use of NRET data from the linear regime of E vs. t1/2, it is possible under many experimental circumstances to determine diffusion coefficients within small error even when the effects of correlations are ignored.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 59 (1998), S. 732-746 
    ISSN: 0006-3592
    Keywords: Desulfovibrio vulgaris ; hydrogen cycling ; kinetics ; thermodynamics ; modeling ; anaerobic ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A unified model for the growth of Desulfovibrio vulgaris under different environmental conditions is presented. The model assumes the existence of two electron transport mechanisms functioning simultaneously. One mechanism results in the evolution and consumption of hydrogen, as in the hydrogen-cycling model. The second mechanism assumes a direct transport of electrons from the donor to the acceptor, without the participation of H2. A combination of kinetic and thermodynamic conditions control the flow of electrons through each pathway. The model was calibrated using batch experiments with D. vulgaris grown on lactate, in the presence and absence of sulfate, and was verified using additional batch experiments under different conditions. The model captured the general trends of consumption of substrates and accumulation of products, including the transient accumulation and consumption of H2. Furthermore, the model estimated that 48% of the electrons transported from lactate to sulfate involved H2 production, indicating that hydrogen cycling is a fundamental process in D. vulgaris. The presence of simultaneous electron transport mechanisms might provide D. vulgaris with important ecological advantages, because it facilitates a rapid response to changes in environmental conditions. This model increases our ability to study the microbial ecology of anaerobic environments and the role of Desulfovibrio species in a variety of environments. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 59:732-746, 1998.
    Additional Material: 6 Ill.
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  • 8
    ISSN: 0935-9648
    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
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 40 (1998), S. 104-114 
    ISSN: 0021-9304
    Keywords: HA ; particles ; dissolution ; macrophage ; osteolysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: It is controversial as to whether debris from hydroxyapatite (HA)-coated implants jeopardizes the long-term success of total joint replacements. It has been hypothesized that liberated HA particles are engulfed by macrophages and through normal cellular digestion prevent osteolysis and third-body wear. HA particulates, however, have been observed at the interface and on polyethylene articulating surfaces. There is limited data demonstrating the ability of HA to dissolve at the acidity levels associated with macrophage organelle digestion. The objective of this study was to determine if particulate HA could dissolve at the pH levels found in macrophage organelles. Characterized HA particles were placed into buffered solutions corresponding to phagosomal organelle pH levels: cytoplasmic (pH 7), phagosomal (pH 6), and lysosomal (pH 5). Flasks were under continuous agitation in a shaker chamber at 37°C. Calcium and phosphate ions were measured beyond the maximum life span of an activated macrophage. The data showed that calcium ions rose within the first 24 h and then remained constant throughout the experiment for all pH groups. Phosphate ion concentration showed a similar pattern at the lysosomal pH but remained undetected at the other organelle pH levels. The saturation point was highest at the lysosomal pH level and lowest at the cytoplasmic pH level. The results of this experiment leave the potential for HA particles to dissolve following macrophage digestion. However, caution must be exercised when interpreting the macrophage organelle digestion hypothesis; the size of the HA particle, the length of time required to completely dissolve the particle, and potential cellular toxicity all are factors that have yet to be determined before this hypothesis can be validated. © 1998 John Wiley & Sons, Inc. J Biomed Mater Res, 40, 104-114, 1998.
    Additional Material: 5 Ill.
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  • 10
    ISSN: 0044-8249
    Keywords: Eisenverbindungen ; Komplexe mit Sauerstoffliganden ; Magnetische Eigenschaften ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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