The effect of complementary base pairing on the oxidation potential of a guanosine derivative has been determined by cyclic and differential pulse voltammetry in CHCl3. The formation of the Watson-Crick H-bonded complex lowers the oxidation potential of the free molecule by 0.34 V, which compares well with the value obtained by DFT/B3LYP/6-311++g** computations.
An investigation on the complex formation equilibria between divalent metal ions Me (with Me=Mn, Co, Ni, Cu, Cd, and Pb) and phytic acid (H(12)L) is presented. Experiments were performed through a potentiometric methodology by measuring, at 25 degrees C, the proton and, in some cases (Cu(2+), Cd(2+), and Pb(2+)), also the metal ion activity at equilibrium in solutions containing, besides the metal and the ligand, 3 M NaClO(4) as the ionic medium. Unhydrolyzed solutions of the metal ion at millimolar concentration levels were titrated with solutions of about 10 mM sodium phytate, until the formation of a solid phase took place (always at pH approximately 2.5, except in the case of Cu(2+), which formed soluble complexes up to pH approximately 3.3). Coulometry was employed to produce very dilute solutions of either Cu(2+), Cd(2+), or Pb(2+) of accurately known composition. The emf data were explained by assuming, in the acidity interval explored, the formation of the complexes of general stoichiometry MeH(5)L(5-) and Me(2)H(3)L(5-). Coordination compounds in the solid state were also synthesized and characterized by elemental analysis, thermal analysis, and ICP spectroscopy. The solids had a general stoichiometry Me(6)H (t)LCl (t). x H(2)O, with the following t and x values for each metal investigated: Me ( t; x) = Mn (4; 2); Co (4; 2); Ni (4; 2); Cu (2; 2.5); Zn (2; 1); Sn (6; 6).
The effects of stacking interactions on the oxidation potentials of single strand oligonucleotides containing up to four consecutive adenines, alternated with thymines and cytosines in different sequences and ratios, have been determined by means of differential pulse voltammetry. Voltammetric measurements point toward the establishment in solution of structured oligonucleotide conformations, in which the nucleobases are well stacked altogether. Molecular dynamics simulations confirm that finding, indicating that single strands assume geometrical parameters characteristic of the B-DNA form. The analysis of the voltammetric signals in terms of a simple effective tight binding quantum model leads one to infer a robust set of parameters for treating hole transfer in one-electron-oxidized DNA containing adenines and thymines.
Differential pulse voltammetries of guanine-rich single- and double-stranded oligonucleotides containing up to six consecutive guanines are reported. The observed progressive lowering of the first voltammetric peak potential as the number of adjacent guanines increases unambiguously points toward the establishment of delocalized hole domains; the hole stabilization energy is ca. 0.1 eV per GG step, significantly lower than that observed for AA steps.
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