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  • 1
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2343-2355 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of two β-chlorinated versions of poly(isopropylidene carboxylate) has been studied by the combined thermogravimetric and gas evolution techniques described previously. Poly(3-chloro-2-methyl-2-hydroxypropionic acid) was found to decompose by a predominantly first-order process which was characterized by kinetic parameters similar to those obtained for poly(isopropylidene carboxylate). These are interpreted in terms of an intramolecular ester-exchange process. As the reaction proceeds intermolecular elimination of hydrogen chloride leads to crosslinking and ultimately to the formation of a carbonaceous char. This process is much more marked in the randomly β-chlorinated analog of poly(isopropylidene carboxylate). With this polymer, drastic deviation from first-order behavior is observed in thermogravimetric results, even in the early stages of reaction. Gas evolution analysis, being more influenced by degradation fragments having an appreciable vapor pressure, yields reasonable first-order data and indicates that the intramolecular interchange mechanism is still an important process. In general, the introduction of β-chlorine atoms is seen to reduce the rate of thermal decomposition of poly-α-esters.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1069-1077 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The various types of polyester degradation known to occur at elevated temperature are briefly summarized with particular reference to features of potential diagnostic value. Although little is known of poly-α-ester degradation in particular, examination of work on other linear polyesters indicates the spectrum of analytical and kinetic information that will be needed to characterize the degradation of poly-α-esters of various structures. On the basis of this review, an apparatus has been designed which enables kinetic information to be simultaneously obtained by thermogravimetry, gas evolution analysis, and rheological studies of the residual polymer melt. In addition a gas sampling procedure enables twin-column gas-liquid chromatographic analysis to be carried out on the degradation products. Samples of the chromatographically separated degradation products are collected in a microcollector cell for infrared and mass spectrometric analysis. Other refinements include in-line filament and Curie-point pyrolysis techniques.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1079-1093 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of poly(isopropylidene carboxylate) has been studied over the temperature range 200-800°C by using the kinetic and analytical techniques described in Part I of this series. Over a wide range of temperature, tetramethyl glycollide, acetone, carbon monoxide, and, to a lesser extent, methacrylic acid are observed when the products are rapidly swept away from the reaction zone. As decomposition temperature is increased, tetramethyl glycollide takes on the role of an intermediate, the more stable products carbon monoxide and acetone being formed from it. At the highest temperature examined, carbon monoxide begins to predominate, and its formation is accompanied by formation of small amounts of a carbonaceous residue. When the reaction products are allowed to remain in the reaction zone, which is possible at the lower end of the temperature range, methacrylic acid becomes the major product. This is interpreted as a dual decomposition route, involving the tetramethyl glycollide intermediate. Kinetic studies have shown that the decomposition is a first-order process and that the first-order rate constant k is related to temperature (T) by the expression: \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 4.1 \times 10^7 e^{{{ - 27,200} \mathord{\left/ {\vphantom {{ - 27,200} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} {\rm sec}^{ - {\rm 1}} $$\end{document} The results are interpreted in terms of an intramolecular ester interchange process involving tetramethyl glycollide as the primary decomposition product.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2031-2043 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Farol-Weissenberg rheogoniometer has been used to follow molecular weight changes during the degradation of certain poly-α-esters in the melt state. By observing the change in melt viscosity at low shear rates it had been shown that the decomposition of the poly(isopropylidene carboxylate) is substantially first-order with respect to the molecular weight of the residual polymer. The derived kinetic parameters are in good agreement with those previously obtained by other techniques. This provides a substantial piece of supporting evidence for the view that degradation takes place predominantly by intramolecular ester interchange involving the formation of 1,1,4,4,-tetramethylglycollide. The introduction of β-chlorine atoms into the polymer structure leads to a more complex degradation pattern. Thus the presence of a single β chlorine atom per repeat unit, as in poly(3-chloro-2-methyl-2-hydroxypropionic acid) leads to a substantially similar dependence on molecular weight with the added complication of progressive crosslinking which becomes more apparent in later stages of the reaction. This crosslinking reaction plays an increasingly important part as the extent of chlorination of the polymer is increased. In addition, the presence of chlorine leads to an increased sensitivity of the degradation reaction to the presence of oxygen.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2045-2056 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of polyglycollide [poly(methylene carboxylate)] has been studied over the temperature range 250-400°C by using the combined kinetic and analytical technique previously described. The results obtained from thermogravimetry and product analysis were in many ways similar to those from previous work involving higher poly-α-esters. Thus the reaction was predominantly first-order and the major degradation product was glycollide monomer. This confirms the observations of Carothers and is best interpreted in terms of an intramolecular ester interchange process. Kinetic studies have shown that the first-order rate constant k is related to temperature T by the expression: \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 2.1 \times 10^8 e^{ - 32,{{600} \mathord{\left/ {\vphantom {{600} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}{\rm sec}^{ - {\rm 1}} } $$\end{document} The results from gas evolution analysis showed consistent and marked deviation from first-order behavior. This is interpreted in terms of the greater sensitivity of this technique to traces of acidic degradation products. Solution viscometry was used to demonstrate the effect of degradation conditions on molecular weight change in both thermogravimetric and gas evolution techniques.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 1229-1237 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Raman spectra of poly-L-lysine hydrochloride and poly-∊-carbobenzoxy-L-lysine in the solid state have been obtained and are consistent with the presence of an α-helical structure. The Raman spectrum of poly-L-lysine in aqueous solution suggests the presence of random coil structures.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 89-106 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Raman spectra of poly-γ-benzyl-L-glutamate, poly-L-leucine, poly-L-valine, and poly-L-serine are reported. For the α-helical polymers, the conformationally sensitive amide I, II, and III modes are observed in the Raman as, well as the infrared. For the β form, the Raman effect, supplies the infrared inactive inphase motion which is useful for the determination of a parallel or antiparallel chain alignment. Modes characteristic of the specific polypeptide are also observed which are insensitive to conformation.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 615-634 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Raman spectra have been obtained of di-, tri-, tetra-, penta-, and hexa-L-alanine in the solid state. Raman spectra of the dimer and trimer in aqueous solution are also reported. The oligomers of alanine exist as zwitterions in the solid state and aqueous solution. Spectral differences between the dipeptide, and other oligomers arise primarily from the conformationally sensitive amide modes. The dipeptide exists as a nonplanar structure in the solid state and the other oligomere as β conformations. Comparison of Raman spectra of tri-L-alanine in the solid state and in aqueous solution suggests a conformational change to a random coil upon dissolution.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 8 (1974), S. 343-347 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: An investigation of metallic intramedullary fixation devices commonly used in orthopedic surgery revealed that the screw threaded portions of these devices were foci for corrosion and fatique fractures. After several design change proposals, a spherical head was developed which could be incorporated onto the intramedullary nails which would eliminate these problems. An extractor impactor was also developed to enable this new design concept to be utilized in surgery. The design and device are described and displayed.
    Additional Material: 2 Ill.
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