An ab initio study of phosphorothioate and phosphorodithioate interactions with sodium cation

David E. Volk, Trevor D. Power, David G. Gorenstein, Bruce A. Luxon

    Research output: Contribution to journalArticle

    15 Citations (Scopus)

    Abstract

    The geometries and interaction energies of the sodium-bound nucleic acid backbone analogs Na[(iPrO)(iBuO)PO2], Na[(iPrO)(iBuO)POS(R)], and Na[(iPrO)(iBuO)PS2] have been calculated. The interaction energies are less favorable with increasing sulfur substitution and the destabilizing effect is larger for the second sulfur substitution than it is for the first substitution. The less favorable interaction energies of the phosphorothioate and phosphorodithioate analogs suggest that nucleic acids containing such substitutions should have a lower population of bound cations. This is consistent with widening of the minor groove in B-DNA duplexes containing stereo-regular (R)-phosphorothioate or phosphorodithioate substitutions and increased affinity of sulfur-modified oligonucleotides for proteins.

    Original languageEnglish (US)
    Pages (from-to)4443-4447
    Number of pages5
    JournalTetrahedron Letters
    Volume43
    Issue number25
    DOIs
    StatePublished - Jun 17 2002

    Fingerprint

    Sulfur
    Cations
    Substitution reactions
    Sodium
    Nucleic Acids
    B-Form DNA
    Oligonucleotides
    Population
    phosphorodithioic acid
    Proteins
    Geometry

    Keywords

    • Ab initio calculations
    • BSSE
    • DNA analogs
    • Interaction energies
    • Phosphorodithioate
    • Phosphorothioate

    ASJC Scopus subject areas

    • Biochemistry
    • Organic Chemistry
    • Drug Discovery

    Cite this

    An ab initio study of phosphorothioate and phosphorodithioate interactions with sodium cation. / Volk, David E.; Power, Trevor D.; Gorenstein, David G.; Luxon, Bruce A.

    In: Tetrahedron Letters, Vol. 43, No. 25, 17.06.2002, p. 4443-4447.

    Research output: Contribution to journalArticle

    Volk, David E. ; Power, Trevor D. ; Gorenstein, David G. ; Luxon, Bruce A. / An ab initio study of phosphorothioate and phosphorodithioate interactions with sodium cation. In: Tetrahedron Letters. 2002 ; Vol. 43, No. 25. pp. 4443-4447.
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    AU - Volk, David E.

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    AU - Gorenstein, David G.

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    AB - The geometries and interaction energies of the sodium-bound nucleic acid backbone analogs Na[(iPrO)(iBuO)PO2], Na[(iPrO)(iBuO)POS(R)], and Na[(iPrO)(iBuO)PS2] have been calculated. The interaction energies are less favorable with increasing sulfur substitution and the destabilizing effect is larger for the second sulfur substitution than it is for the first substitution. The less favorable interaction energies of the phosphorothioate and phosphorodithioate analogs suggest that nucleic acids containing such substitutions should have a lower population of bound cations. This is consistent with widening of the minor groove in B-DNA duplexes containing stereo-regular (R)-phosphorothioate or phosphorodithioate substitutions and increased affinity of sulfur-modified oligonucleotides for proteins.

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