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The influence of metal ion complexation on 31P-NMR parameters of phosphorothioates of guanosine nucleotides

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Rösch,  Paul
Emeritus Group Biophysics, Max Planck Institute for Medical Research, Max Planck Society;

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Goody,  Roger S.
Abt. III: Physikalische Biochemie, Max Planck Institute of Molecular Physiology, Max Planck Society;

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Isakov,  Maria
Max Planck Institute for Medical Research, Max Planck Society;

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Citation

Rösch, P., Goody, R. S., & Isakov, M. (1984). The influence of metal ion complexation on 31P-NMR parameters of phosphorothioates of guanosine nucleotides. Phosphorus Sulfur and Silicon and the Related Elements, 9-16. doi:10.1080/03086648408073121.


Cite as: https://hdl.handle.net/21.11116/0000-0005-DFBB-E
Abstract
An extension of methods already used for the preparation of adenosine phosphorothioates was used to prepare guanosine phosphorothioates in quantities sufficient for extensive 31P-NMR studies. Guanosine phosphorothioates were used to exemplify the influence of Cd2+ and Mg2+ complexation on 31P-NMR parameters as pK-values, chemical shifts, and P[sbnd]O[sbnd]P coupling constants. pKa values decrease in general in the order pK(α-S) a > pK(β-S) a > pK(γ-S) a; the magnitude of the pKa decrease on metal complexation is also in this order. The chemical shifts for the P[sbnd]S resonances are changed downfield on Mg2+ complexation and upfield on Cd2+ complexation. P[sbnd]O[sbnd]P coupling constants are increased by about 7 Hz on sulfur substitution at one of the contributing phosphorus atoms; this difference is at least partially ineffective in the Cd2+ complexes.