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  • 1
    Publication Date: 2017-07-21
    Description: Stretching polymer chains accelerates dissociation of a variety of internal covalent bonds, to an extent that correlates well with the force experienced by the scissile bond. Recent theory has also predicted scenarios in which applied force accelerates dissociation of unloaded bonds and kinetically strengthens strained bonds. We report here unambiguous experimental validation of this hypothesis: Detailed kinetic measurements demonstrate that stretching phosphotriesters accelerates dissociation of the unloaded phosphorus-oxygen bond orthogonal to the pulling axis, whereas stretching organosiloxanes inhibits dissociation of the aligned loaded silicon-oxygen bonds. Qualitatively, the outcome is determined by phosphoester elongation and siloxane contraction along the pulling axis in the respective rate-determining transition states. Quantitatively, the results agree with a simple mechanochemical kinetics model.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
    ISSN: 0375-9474
    Keywords: Nuclear reaction
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0375-9474
    Keywords: Nuclear reaction
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 1-4 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations have been made on the optical rotatory dispersion properties of E. coli ribosomes and their constituent RNA and proteins. The results indicate that (1) no conformational changes are involved in the formation of a 70S particle from the 50S and 308 subunits, (2) the E. coli ribosomal proteins are similar to most globular proteins with little α-helix content, and (3) the conformation of RNA and proteins inside the ribosome is very similar to that in the free state.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 349-355 
    ISSN: 0887-624X
    Keywords: polymer ; polyelectrolyte ; degradation ; aqueous ; decarboxylation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(acrylic acid) (PAA) was decarboxylated in aqueous solution as a function of pH and ionic strength in the temperature range 100-350°C. Degradation kinetics were first order with respect to acid functionality. The rate of decarboxylation at high pH (Eα = 51.1 kcal/mol) was much slower than that at low pH (Eα = 20.3 kcal/mol). At intermediate pH, the reactivity was found to depend on the degree of dissociation of PAA as a functions of ionic strength, pH, and temperature. No monomer was observed in the reaction product. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 25 (1983), S. 2557-2566 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: L-Lysine α-oxidase from Trichoderma viride Y244-2 is immobilized in a gelatin support and fixed on a pO2 sensor. The enzyme electrode obtained is used in a continuous flow system in order to measure the concentration of L-lysine in a fermentor. The sample oxygen-content dependance of the signal is minimized because of the enzyme support properties. The enzyme electrode response is set for lysine concentration from 0.2mM to 4mM. The specificity of lysine is tested with other amino acids. The enzyme membrane for lysine electrode can be used 3000 times or stored six months with good stability.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 811-817 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Results from steady and unsteady, two-dimensional simulations of tertiary current distributions at and below the limiting current density are presented. The simulations are based on dilute-solution theory, with coupling of the concentrations of the ionic species through the electrical field. The electrical field is calculated from the electroneutrality constraint. Results confirm and extend previous theoretical predictions of the electricalmigration enhancement of the limiting current. To demonstrate the potential utility of general current-distribution solvers, measured temporal variations of the rate of copper deposition in the presence of an oscillating shear flow are measured and simulated. Experiments agree well with simulations.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 47 (1996), S. 631-632 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Der Einfluß von Y und Zr auf die Oxidation von NiAl
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 46 (1995), S. 218-222 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Untersuchungen zur Segregation von Y und Zr bei der Oxidation von NiAlKonventionelle, analytische und hochauflösende Transmissionselektronenmikroskopie (TEM) sowie hochauflösende Sekundärionenmassenspektrometrie (SIMS) wurden benutzt, um den Effekt von reaktiven Elementen auf die Oxidation von NiAl zu untersuchen. Polykristalline NiAl-Proben, dotiert mit 0,1 Mas.-% Y oder 0,2 Mas.-% Zr, wurden bei einer Temperatur von 1200°C oxidiert. 18O Tracer-Experimente in Verbindung mit hochauflösenden SIMS-Untersuchungen deuten darauf hin, daß reaktive Elemente die nach außen gerichtete Diffusion von Kationen reduzieren. Energiedispersive Röntgenspektroskopie mit einem dedizierten STEM zeigte, daß die reaktiven Elemente an den Korngrenzen in der Oxidschicht und an der Metall/Oxid-Grenzfläche segregieren. Der Anteil von Y bzw. Zr an den Korngrenzen in der Oxidschicht beträgt 0,2 Monolagen. Demgegenüber wurden an der Metall/Oxid-Grenzfläche 0,15 Monolagen (Zr-dotiert) bzw. 0,07 Monolagen (Y-dotiert) gefunden. In Y-reichen Teilchen im NiAl nahe der Metall/Oxid-Grenzfläche konnte Schwefel nachgewiesen werden.
    Notes: Conventional electron microscopy, analytical electron microscopy, high resolution electron microscopy and high resolution SIMS have been used to investigate the effect of the reactive elements, Yand Zr, on the oxide scale formation on NiAl. Polycrystalline NiAl samples, doped with either 0. 1 wt% Yor 0.2 wt% Zr, were oxidized in air at 1200°C. 18O tracer experiments in conjunction with high resolution SIMS suggest that the reactive elements reduce the outward diffusion of cations. Energy dispersive X-ray spectroscopy on a dedicated STEM showed that the reactive elements segregate to the grain boundaries in the oxide scale and to the metal/oxide interface. The amount at the oxide scale grain boundaries was calculated to be 0.2 monolayers for both Zr and Y doped NiAl. The amounts of segregation were calculated to be 0.15 monolayers (Zr-doped) and 0.07 monolayers (Y-doped) at the metal/oxide interface. The presence of sulfur was detected in Y-rich particles in the NiAl close to the interface.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 1630-1633 
    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: Photosensitive polyamic acid involving substituted 3, 5-diaminobenzamide has been developed for photopatternable polyimidesiloxanes. This precursor, formulated with photosensitizers, was used to develop fine patterns by i-line UV exposure. The curing of polyamic acid was investigated by using FTIR and physical property measurement. The cured film has a high glass transition temperature depending on the siloxane content. It is stable up to 400°C and loses some of the substituted groups on heating to 500°C. The modulus, dielectric constant, and water absorption decreased with higher siloxane content.
    Additional Material: 3 Ill.
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