Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA

The use of DNA strands as nanowires or electrochemical biosensors requires a deep understanding of charge transfer processes along the strand, as well as of the redox properties. These properties are computationally assessed in detail throughout this study. By applying molecular dynamics and hybrid...

Descripción completa

Detalles Bibliográficos
Autores: Lucía Tamudo, Jesús, Díaz-Tendero Victoria, Sergio, Nogueira, Juan J.
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/709978
Acceso en línea:http://hdl.handle.net/10486/709978
https://dx.doi.org/10.1039/d3cp00884c
Access Level:acceso abierto
Palabra clave:Química
id ES_8794b21bc0650ce75b94bd4f2b5caa37
oai_identifier_str oai:repositorio.uam.es:10486/709978
network_acronym_str ES
network_name_str España
repository_id_str
spelling Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNALucía Tamudo, JesúsDíaz-Tendero Victoria, SergioNogueira, Juan J.QuímicaThe use of DNA strands as nanowires or electrochemical biosensors requires a deep understanding of charge transfer processes along the strand, as well as of the redox properties. These properties are computationally assessed in detail throughout this study. By applying molecular dynamics and hybrid QM/continuum and QM/QM/continuum schemes, the vertical ionization energies, adiabatic ionization energies, vertical attachment energies, one-electron oxidation potentials, and delocalization of the hole generated upon oxidation have been determined for nucleobases in their free form and as part of a pure single-stranded DNA. We show that the reducer ability of the isolated nucleobases is explained by the intramolecular delocalization of the positively charged hole, while the enhancement of the reducer character when going from aqueous solution to the strand correlates very well with the intermolecular hole delocalization. Our simulations suggest that the redox properties of DNA strands can be tuned by playing with the balance between intramolecular and intermolecular charge delocalizationThis work was partially supported by the MICINN – Spanish Ministry of Science and Innovation – Projects PID2019-110091GB-I00 and PID2020-117806GA-I00 funded by MCIN/AEI/10.13039/501100011033, and the ‘María de Maeztu’ (CEX2018-000805-M) Program for Centers of Excellence in R & D. J. J. N. acknowledge the Comunidad de Madrid for funding through the Attraction of Talent Program (Grant ref.2018-T1/BMD-10261). J. L. T. acknowledges the FPU19/02292 grant from the Spanish Ministry of UniversityRSCDepartamento de QuímicaFacultad de Ciencias20232023-05-09research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/709978https://dx.doi.org/10.1039/d3cp00884creponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7099782026-06-23T12:46:27Z
dc.title.none.fl_str_mv Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
title Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
spellingShingle Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
Lucía Tamudo, Jesús
Química
title_short Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
title_full Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
title_fullStr Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
title_full_unstemmed Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
title_sort Intramolecular and intermolecular hole delocalization rules the reducer character of isolated nucleobases and homogeneous single-stranded DNA
dc.creator.none.fl_str_mv Lucía Tamudo, Jesús
Díaz-Tendero Victoria, Sergio
Nogueira, Juan J.
author Lucía Tamudo, Jesús
author_facet Lucía Tamudo, Jesús
Díaz-Tendero Victoria, Sergio
Nogueira, Juan J.
author_role author
author2 Díaz-Tendero Victoria, Sergio
Nogueira, Juan J.
author2_role author
author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
dc.subject.none.fl_str_mv Química
topic Química
description The use of DNA strands as nanowires or electrochemical biosensors requires a deep understanding of charge transfer processes along the strand, as well as of the redox properties. These properties are computationally assessed in detail throughout this study. By applying molecular dynamics and hybrid QM/continuum and QM/QM/continuum schemes, the vertical ionization energies, adiabatic ionization energies, vertical attachment energies, one-electron oxidation potentials, and delocalization of the hole generated upon oxidation have been determined for nucleobases in their free form and as part of a pure single-stranded DNA. We show that the reducer ability of the isolated nucleobases is explained by the intramolecular delocalization of the positively charged hole, while the enhancement of the reducer character when going from aqueous solution to the strand correlates very well with the intermolecular hole delocalization. Our simulations suggest that the redox properties of DNA strands can be tuned by playing with the balance between intramolecular and intermolecular charge delocalization
publishDate 2023
dc.date.none.fl_str_mv 2023
2023-05-09
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/709978
https://dx.doi.org/10.1039/d3cp00884c
url http://hdl.handle.net/10486/709978
https://dx.doi.org/10.1039/d3cp00884c
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv RSC
publisher.none.fl_str_mv RSC
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869412472167858176
score 15,301603

Similares en LA Referencia