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  • 1
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 72 (1968), S. 3105-3110 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 100 (1978), S. 97-100 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 173 (1973), S. 213-220 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The segmental motion of poly(2-vinyl pyridine), in CDCl3 and CD3OD solutions has been studied by 13C spin lattice relaxation time measurements. The relaxation time of carbons is virtually independent of the rel. molecular mass and polymer tacticity. However, it is slightly longer for ring carbons than for chain ones, suggesting a slow rotational oscillation of the rings around the Cα - C5 axis. In the case of the polyelectrolyte [poly(2-vinyl pyridinium ion)], a slight increase of the rigidity of the chain is observed, which may be attributed to the repulsion between the positively charged rings. Additional ESR experiments have shown that the α-protons of the chain are located in the plane of pyridyl rings, thus defining their equilibrium position with respect to the chain.
    Notes: Les mouvements segmentaires de la poly(vinyl-2 pyridine) (PV2P) en solution dans CDCl3 et CD3OD ont été étudiés par mesure du temps de relaxation T1 des carbones-13. Le temps de relaxation de ces carbones est pratiquement indépendant de la masse moléculaire et de la tacticité du polymère. Il est cependant un peu plus long pour les carbones des cycles que pour ceux de la chaîne, ce qui suggère un mouvement lent de libration de ces cycles autour de l'axe Cα - C5. Dans le cas de la forme polyélectrolyte de la PV2P (ion pyridinium) on note un accroissement sensible de la rigidité de la chaîne du fait de la répulsion qui s'exerce entre les cycles chargés positivement. Des expériences complémentaires de R.P.E. indiquent que les protons α de la chaîne se situent dans le plan des cycles pyridyles, ce qui permet de définir la position d'équilibre de ces derniers par rapport à la chaîne.
    Additional Material: 3 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: The preferential orientations of the purine bases in dinucleoside monophosphates such as ApA, ApG, and GpA in 10-2M neutral aqueous solutions have been investigated by proton relaxation at 250 MHz. These orientations are deduced from computer simulations of the magnetization recovery curves following a 180° nonselective pulse. The distances between the H(8) proton of a base and the ribose ring protons which are used in these calculations are obtained by minimization as a function of the glycosyl torsion angle ϒ of the standard deviation between the isotropic reorientation correlation times τR derived from the relaxation rates of these protons. The average H(1′) - H(8) distance obtained by this procedure may be readily verified from the reduction of the H(1′) relaxation rate when H(8) is substituted by a deuteron. The limits of validity of the assumption of a single correlation time τR governing the proton relaxation have been estimated, taking into account several possible internal motions, e.g., the rotation of the base, of the methylene exocyclic group and the N ⇄ S interconversion of the ribose ring. For 10-10 〈 τR 〈 2 × 10-10 sec, it appears that the influence of these motions on the proton relaxation becomes perceptible when the jump rates among equilibrium positions exceed ca. 109 sec-1.The whole of the experimental results show that for the ribose ring N conformer, the orientation of the bases is found in the ranges 60° 〈 ϒ 〈 80° (syn) and 180° 〈 ϒ 〈 210° (anti). For ribose S conformer, it is observed that this orientation is mainly syn with 5° 〈 ϒ 〈 90°. The average H(1′) - H(8) distance provides semiquantitative information on the overall syn or anti orientations of the base in each nucleoside moiety. At 298 K the population of the anti conformer is found to increase in the order A- pG 〈 Ap-G ∼ Gp-A 〈 Ap-A 〈 A-pA 〈 G-pA. A more detailed analysis of relaxation data shows that the maximum possible fraction of the stacked form of dinucleotides, due to the occurrence of N-anti conformers in both nucleoside moieties, is in the order ApG 〈 GpA 〈 ApA, in agreement with previous works, with however smaller values.Lastly the deuteron linewidth in position 8 of the bases indicates a syn-anti transition rate of the order of 109 sec-1 at room temperature, without noticeable effects therefore on the proton relaxation.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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