Abstract

Equilibrium constant measurements have been performed potentiometrically at (25±0.1) °C and an ionic strength I=0.1 mol⋅dm−3 KNO3 for the interaction of La(III), Ce(III), Pr(III) and Er(III) with the purine nucleotides adenosine 5′-mono, 5′-di, and 5′-triphosphate and with the biologically relevant secondary ligand zwitterionic buffers 3-(cyclohexyl amino)-1-propanesulfonic acid (CAPS), 3-(cyclohexylamino)-2-hydroxy-1-propane sulfonic acid (CAPSO), N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid (TAPS), 3-[N-bis(hydroxyethyl)amino]-2-hydroxypropanesulfonic acid (DIPSO), N,N-bis(2-hydroxyethyl)glycine (BICINE), and N-(2-acetamido)-2-iminodiacetic acid (ADA) in a 1:1:1 ratio. The formation of various 1:1:1 normal and protonated mixed-ligand complex species was inferred from the potentiometric pH titration curves. The experimental conditions were selected such that self-association of the purine nucleotides and their complexes was negligibly small; that is, the monomeric normal and protonated ternary complexes were studied. Initial estimates of the formation constants of the resulting species and the acid dissociation constants of adenosine 5′-mono-, 5′-di-, and 5′-triphosphate and the zwitterionic buffer secondary ligands were refined with the Superquade computer program. In some Ln(III) mixed-ligand systems, interligand interactions between the coordinating ligands, possibly involving H-bond formation, have been found to be the most important factors in deciding the stability of the mixed-ligand complexes in solutions. The thermodynamic ΔG° values of the monomeric normal and protonated ternary complexes were calculated and discussed.

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