Populations and Dynamics of Guanine Radicals in DNA strands-Direct versus Indirect Generation.

Evangelos Balanikas,Akos Banyasz,Dimitra Markovitsi,Gérard Baldacchino

doi:10.3390/molecules24132347

Abstract

Guanine radicals, known to be involved in the damage of the genetic code and aging, are studied by nanosecond transient absorption spectroscopy. They are generated in single, double and four-stranded structures (G-quadruplexes) by one and two-photon ionization at 266 nm, corresponding to a photon energy lower than the ionization potential of nucleobases. The quantum yield of the one-photon process determined for telomeric G-quadruplexes (TEL25/Na+) is (5.2 ± 0.3) × 10−3, significantly higher than that found for duplexes containing in their structure GGG and GG sequences, (2.1 ± 0.4) × 10−3. The radical population is quantified in respect of the ejected electrons. Deprotonation of radical cations gives rise to (G-H1)• and (G-H2)• radicals for duplexes and G-quadruplexes, respectively. The lifetimes of deprotonated radicals determined for a given secondary structure strongly depend on the base sequence. The multiscale non-exponential dynamics of these radicals are discussed in terms of inhomogeneity of the reaction space and continuous conformational motions. The deviation from classical kinetic models developed for homogeneous reaction conditions could also be one reason for discrepancies between the results obtained by photoionization and indirect oxidation, involving a bi-molecular reaction between an oxidant and the nucleic acid.

Highlights

Guanine (G) radicals are major actors in the oxidatively generated damage to the genetic code [1].The reason is that G is the nucleobase with the lowest oxidation potential [2]
The second objective of our study is to examine the extent to which the dynamics of G radicals are affected by the base sequence within a given secondary structure
−1 mol L cm−1 at 600 nm, while determined for the monomeric (G-H2) coefficient radicals [10,16], we found that their mono-nucleotide dGMP, at 500 nm molar absorption is practically the same concentration corresponds to of the initial radical concentration

Summary

Introduction

Guanine (G) radicals are major actors in the oxidatively generated damage to the genetic code [1].The reason is that G is the nucleobase with the lowest oxidation potential [2].

Objectives

Methods

Results

Conclusion