Stacking interactions play a major role in DNA oxidation, because they finely modulate the redox potential of DNA nucleobases, in a way which depends on the primary and higher order structures. [1] Indeed, there is experimental evidence that sequences of adjacent guanines (G), the nucleobase with the lowest oxidation potential, are the most easily oxidizable sites in DNA, GGG sequences being still more reactive than GG ones.[2-4]. 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. [5] Here, we present a series of voltammetric measurements -a well suited experimental tool for detecting the effects of inter-base interactions on the oxidation potentials of the nucleobases- [6-7] of oligonucleotides containing adenines in different sequences and ratios, which in physiological conditions exhibit multiple signals, characteristic of  stacked molecular systems, which allow a quantitative determination of the strengths of stacking interactions between two stacked adenine units. We have shown that voltammetry is a powerful method to quantify the strength of stacking interactions in oligonucleotides, providing the necessary physical quantities for understanding the complex landscape of electronic states which controls long range hole transfer

STACKING INTERACTIONS BETWEEN ADENINES IN DNA OLIGONUCLEOTIDES

CAPOBIANCO, AMEDEO;CARUSO, Tonino;PELUSO, Andrea
2013-01-01

Abstract

Stacking interactions play a major role in DNA oxidation, because they finely modulate the redox potential of DNA nucleobases, in a way which depends on the primary and higher order structures. [1] Indeed, there is experimental evidence that sequences of adjacent guanines (G), the nucleobase with the lowest oxidation potential, are the most easily oxidizable sites in DNA, GGG sequences being still more reactive than GG ones.[2-4]. 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. [5] Here, we present a series of voltammetric measurements -a well suited experimental tool for detecting the effects of inter-base interactions on the oxidation potentials of the nucleobases- [6-7] of oligonucleotides containing adenines in different sequences and ratios, which in physiological conditions exhibit multiple signals, characteristic of  stacked molecular systems, which allow a quantitative determination of the strengths of stacking interactions between two stacked adenine units. We have shown that voltammetry is a powerful method to quantify the strength of stacking interactions in oligonucleotides, providing the necessary physical quantities for understanding the complex landscape of electronic states which controls long range hole transfer
2013
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11386/4160253
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