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Molecular orbital calculations on the conformation of nucleic acids and their constituents

VII. Conformation of the sugar ring in β-nucleosides: The pseudorotational representation

Abstract

The conformational properties of the furanose ring of purine- and pyrimidine-β-nucleosides and-nucleotides are studied quantum-mechanically with the help of the PCILO method, using the pseudorotational concept. The computations point to the existence of two stable conformational zones centered around the C(3′)-endo and C(2′)-endo conformations which in the isolated furanose ring are separated by barriers of the order of 4 kcal/mole. In nucleosides one of the barriers (the one running through the O(1′)-exo-C(2′)-exo path) becomes very high. A detailed study is made of the relation between the phase angle of pseudorotation, P, and the torsion angle about the glycosyl bond, χ CN. A very satisfactory agreement with the available experimental data is observed.

Zusammenfassung

Die Konformationseigenschaften des Furanoserings in β-Nucleosiden und Nucleotiden von Purin und Pyrimidin werden nach der PCILO-Methode unter Berücksichtigung der pseudorotatorischen Betrachtungsweise studiert. Die Rechnung läßt auf die Existenz zweier stabiler Konformationszonen schließen, die in der Umgebung der C(2′)-endo und der C(3′)-endo Konformationen liegen, und die im isolierten Furanosering durch Energiebarrieren der Größenordnung von 4 kcal/mol voneinander getrennt sind. In Nucleosiden wird eine der Barrieren (die durch den Weg O(1′)-exo-C(2′)-exo gekennzeichnete) sehr hoch. Die Relation zwischen dem Phasenwinkel der Pseudorotation, P, und dem Drehwinkel um die Glycosylbindung, χ CN, wird einer eingehenden Untersuchung unterworfen. Man beobachtet eine sehr zufriedenstellende Übereinstimmung mit den verfügbaren experimentellen Daten.

Résumé

Les propriétés conformationnelles du noyau furanose des β-nucleosides et nucleotides des purines et pyrimidines sont étudiées par la méthode PCILO en faisant appel au concept de la pseudorotation. Les calculs indiquent l'existence de deux zones de conformations stables, centrées autour des conformations C(2′)-endo et C(3′)-endo, qui sont dans le sucre isolé séparées par des barrières de l'ordre de 4 kcal/mole. Dans les nucleosides, l'une de ces barrières (celle qui passe par le chemin O(1′)-exo-C(2′)-exo) devient très élevée. Une étude détaillée est effectuée sur la relation entre l'angle de phase de la pseudorotation P et l'angle de torsion autour de la liaison glycosylique, χ CN. Un excellent accord avec les données expérimentales disponibles est observé.

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This research was supported by the R.C.P. 173 and the A.T.P. A 655-2303 of the C.N.R.S.

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Saran, A., Perahia, D. & Pullman, B. Molecular orbital calculations on the conformation of nucleic acids and their constituents. Theoret. Chim. Acta 30, 31–44 (1973). https://doi.org/10.1007/BF00527633

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  • DOI: https://doi.org/10.1007/BF00527633

Keywords

  • Pyrimidin
  • Purine
  • Nucleoside
  • Phase Angle
  • Torsion Angle