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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 197 (1996), S. 2219-2229 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(lactide)s (PLAs) are well known hydrolytically degradable polymers, that are widely used for biomedical applications. However, the intrinsic brittle nature of poly(lactide)s is still poorly understood. The stiffness of a polymer chain, expressed as the characteristic ratio C∞ plays an important role in the deformation mechanism of amorphous polymers. In order to investigate the effect of tacticity, high molecular weight poly(lactide) stereo-copolymers with D-lactide contents in the range 0-50 mol-% were synthesised. These polymers were used in light scattering and differential scanning calorimetry (DSC) experiments for the determination of the characteristic ratio C∞ and glass transition temperature Tg. The results of the light scattering experiments in acetonitrile indicate that the characteristic ratio C∞ for poly(lactide)s depends on the L/D-lactide ratio and increases with the tacticity of the polymer from 9.5 for racemic PDLLA to an estimated 11.8 for isotactic PLLA. These results are consistent with the observed brittle behaviour of poly(lactide) stereo-copolymers and agree well with predictions obtained from group contribution methods. The choice of the relevant bond length used for the calculation of the characteristic ratio from the scattering data is not as obvious as it may seem and remains a point of discussion. The tacticity of poly(lactide)s also influences the glass transition temperature, which varies from 54°C for racemic to 63°C for isotactic poly-(lactide).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nach der neuen, von Kögl, SALEMINK, SCHOUTEN und JELLINEK sichergestellten Formel besitzt Muscarin (I) drei asymmetrische Kohlenstoffatome, so daß bei der Synthese vier Racemate zu erwarten sind, falls man von inaktivem Material ausgeht und bei den angewandten Methoden alle theoretisch möglichen Stereoisomeren entstehen. Bei der in der vorliegenden Mitteilung beschriebenen Synthese, für welche α-Acetyl-δ-chlor-γ-valerolacton als Ausgangsmaterial diente, entstand ein Gemisch von Stereoisomeren, dessen pharmakologische Aktivität am Froschherz etwa ein Drittel von der des natürlichen Alkaloids betrug.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Rapid Communications 14 (1993), S. 155-161 
    ISSN: 0173-2803
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the relative orientation and electronegativity of substituents on the magnitude of 3J(aa), 3J(ae) and 3J(ee) is well predicated by a simple set of additivity constants, valid for pyranose rings in carbohydrates. The proposed set of parameters is used to calculate 327 coupling constants [3J(HH)] in a variety of pyranosides and related compounds. A comparison with experimental values taken from the literature shows that couplings in molecules which are conformationally pure and underformed can be predicted with a surprising accuracy. An overall root-mean-square agreement of 0.29 Hz is attained for a selected group of 305 coupling values. A statistical breakdown of ΔJ(aa) and ΔJ(ae) [ΔJ=J(exp)-J(calc)] along each carbon-carbon bond in the pyranose systems reveals an unexpected degree of geometrical homogeneity.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 22 (1984), S. 793-794 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C NMR chemical shifts are assigned for some quaternary morphinan derivatives, including the ‘minor isomer’ of the thebaine N-oxides. In quaternary morphinan alkaloids having an 8.14-double bond, electric field effects cause unusual 13C NMR shifts.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 31 (1993), S. 590-595 
    ISSN: 0749-1581
    Keywords: Sesquiterpene ether ; MM2 ; Pseudo-rotational analysis ; 3D structure ; Seven-membered ring ; Five-membered ring ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational characteristics of kessane were investigated by means of 600 MHz 1H NMR spectroscopy and molecular mechanics (MM2) calculations. Accurate vicinal 1H—1H coupling constants were obtained by means of extensive computer simulations. These experimental values were compared with coupling constants calculated by the combined use of MM2 calculations and the generalized Karplus equation. It is shown that kessane adopts a single conformation in solution which is only slightly different from the conformation predicted by the MM2 calculations. The cyclopentane ring of kessane is characterized by a pure 1E conformation. The cycloheptane ring adopts a conformation which is situated precisely between the twist-chair TC9 and the chair C5 conformation on the pseudo-rotational pathway of the seven-membered ring.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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