Noncovalent Interaction of Uridine 5′-Monophosphate with Adenosine, Cytidine, and Thymidine, as well as Adenosine 5′-Monophosphate and Cytidine 5′-Monophosphate in Aqueous Solution

Abstract

Adduct formation has been studied in the systems of uridine 5′-monophosphate (UMP) with adenosine (Ado), cytidine (Cyd), thymidine (Thd), adenosine 5′-monophosphate (AMP), and cytidine 5′-monophosphate (CMP) by the potentiometric method with computer analysis of the data and 13C and 31P NMR spectroscopic measurements. It has been established that in the complexes identified, ion–dipole and dipole–dipole interactions occur with the positive reaction centers being protonated nitrogen atoms N(3) of UMP or Thd, and at low pH values, endocyclic nitrogen atoms of the other nucleosides and nucleotides, as e.g., in (UMP)H2(Ado). The negative reaction centers are the high-electron density atoms N(1) and N(7) from Ado or AMP and N(3) from Cyd or CMP, and the phosphate group of the nucleotides studied, which already undergo partial deprotonation at low pH values. The NMR results have established the presence of noncovalent stacking-type interactions in certain molecular complexes, e.g., (UMP)H2(AMP). The sites of ion–dipole or dipole–dipole interactions are generated as a result of deprotonation of the nucleosides and nucleotides in the pH range of formation of molecular complexes. Analysis of the equilibrium constants of the reaction allowed a determination of the effectiveness of the phosphate groups and donor atoms of heterocyclic rings in the process of molecular complex formation.