Classical and Quantum Mechanical Calculations of the Stacking Interaction of Nd-III Complexes with Regular and Mismatched DNA Sequences

Beltrán-Leiva, María J.; Fuenzalida-Valdivia, Isabel; Cantero-López, Plinio; Bulhões-Figueira, Ana; Alzate-Morales, Jans; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

Abstract

The design of organometallic complexes used as selective intercalators to bind and react at DNA mismatch sites has concentrated efforts in the last few years. In this context, lanthanides have received attention to be employed as active optical centers due to their spectroscopic properties. Despite the fact that there are several experimental data about synthesis and DNA binding of these compounds, theoretical analyses describing their interaction with DNA are scarce. To understand the binding to regular and mismatched DNA sequences as well as to determine the effect of the intercalation on the spectroscopic properties of the complexes, a complete theoretical study going from classical to relativistic quantum mechanics calculations has been performed on some lanthanide complexes with phenanthroline derivatives synthesized and characterized herein, viz. [Nd(NO3)(3)(H2O)-(dppz-R)] with R = H, NO2-, C- and their [Nd(NO3)(3)(H2O)(dpq)] analogue, which was computationally modeled. The results were in correct agreement with the available experimental data showing that dppz complexes have higher binding affinities to DNA than dpq one and supporting the idea that these complexes are not selective to mismatch sites in the sampled time scale. Finally, the spectroscopic analysis evidence an intercalative binding mode and made possible the elucidation of the emission mechanism of these systems. This approach is proposed as a benchmark study to extend this methodology on similar systems and constitutes the first theoretical insight in the interaction between DNA and lanthanide complexes.

Más información

Título según WOS: Classical and Quantum Mechanical Calculations of the Stacking Interaction of Nd-III Complexes with Regular and Mismatched DNA Sequences
Título según SCOPUS: Classical and Quantum Mechanical Calculations of the Stacking Interaction of Nd III Complexes with Regular and Mismatched DNA Sequences
Título de la Revista: JOURNAL OF PHYSICAL CHEMISTRY B
Volumen: 123
Número: 15
Editorial: AMER CHEMICAL SOC
Fecha de publicación: 2019
Página de inicio: 3219
Página final: 3231
Idioma: English
DOI:

10.1021/acs.jpcb.9b00703

Notas: ISI, SCOPUS