Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks

Autores
Petelski, Andre Nicolai; Fonseca Guerra, Célia
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Hydrogen-bonded supramolecular systems are known to obtain extra stabilization from the complexation with ions, like guanine quadruplex (GQ). They experience strong hydrogen bonds due to cooperative effects. To gain deeper understanding of the interplay between ions and hydrogen-bonding cooperativity, relativistic dispersion-cor rected density functional theory (DFT-D) computations were performed on triple layer hydrogen-bonded rosettes of ammeline interacting with alkali metal cations and halides. Our results show that when ions are placed between the stacks, the hydrogen bonds are weakened but, at the same time, the cooperativity is strengthened. This phenomenon can be traced back to the shrinkage of the cavity as the ions pull the monomers closer together and therefore the distance between the monomers becomes smaller. On one hand this results in a larger steric repulsion, but on the other hand, the donor-acceptor interactions are enhanced due to the larger overlap between the donating and accepting orbitals leading to more charge donation and therefore an enhanced electrostatic attraction.
Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Petelski, Andre Nicolai. Universidad Libre de Ámsterdam. Instituto de Ciencias Biológicas y Moleculares de Ámsterdam; Países Bajos.
Fil: Fonseca Guerra, Célia. Universidad Libre de Ámsterdam. Instituto de Ciencias Biológicas y Moleculares de Ámsterdam; Países Bajos.
Peer Reviewed
Materia
Charge transfer
cooperative effects
hydrogen bonds
self-assembly
stacking interactions
Nivel de accesibilidad
acceso abierto
Condiciones de uso
2023-10-30T20:21:43Z
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/8659
Acceder
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oai_identifier_str oai:ria.utn.edu.ar:20.500.12272/8659
network_acronym_str RIAUTN
repository_id_str a
network_name_str Repositorio Institucional Abierto (UTN)
spelling Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacksPetelski, Andre NicolaiFonseca Guerra, CéliaCharge transfercooperative effectshydrogen bondsself-assemblystacking interactionsHydrogen-bonded supramolecular systems are known to obtain extra stabilization from the complexation with ions, like guanine quadruplex (GQ). They experience strong hydrogen bonds due to cooperative effects. To gain deeper understanding of the interplay between ions and hydrogen-bonding cooperativity, relativistic dispersion-cor rected density functional theory (DFT-D) computations were performed on triple layer hydrogen-bonded rosettes of ammeline interacting with alkali metal cations and halides. Our results show that when ions are placed between the stacks, the hydrogen bonds are weakened but, at the same time, the cooperativity is strengthened. This phenomenon can be traced back to the shrinkage of the cavity as the ions pull the monomers closer together and therefore the distance between the monomers becomes smaller. On one hand this results in a larger steric repulsion, but on the other hand, the donor-acceptor interactions are enhanced due to the larger overlap between the donating and accepting orbitals leading to more charge donation and therefore an enhanced electrostatic attraction.Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Petelski, Andre Nicolai. Universidad Libre de Ámsterdam. Instituto de Ciencias Biológicas y Moleculares de Ámsterdam; Países Bajos.Fil: Fonseca Guerra, Célia. Universidad Libre de Ámsterdam. Instituto de Ciencias Biológicas y Moleculares de Ámsterdam; Países Bajos.Peer Reviewed2023-10-30T20:21:43Z2023-10-30T20:21:43Z2022-11-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articulopdfapplication/pdf1861-4728http://hdl.handle.net/20.500.12272/8659doi.org/10.1002/asia.202201010enginfo:eu-repo/semantics/openAccess2023-10-30T20:21:43ZAcceso Abiertoreponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica Nacional2026-09-24T12:46:13Zoai:ria.utn.edu.ar:20.500.12272/8659instacron:UTNInstitucionalhttp://ria.utn.edu.ar/Universidad públicaNo correspondehttp://ria.utn.edu.ar/oaigestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:a2026-09-24 12:46:14.629Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
title Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
spellingShingle Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
Petelski, Andre Nicolai
Charge transfer
cooperative effects
hydrogen bonds
self-assembly
stacking interactions
title_short Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
title_full Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
title_fullStr Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
title_full_unstemmed Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
title_sort Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks
dc.creator.none.fl_str_mv Petelski, Andre Nicolai
Fonseca Guerra, Célia
author Petelski, Andre Nicolai
author_facet Petelski, Andre Nicolai
Fonseca Guerra, Célia
author_role author
author2 Fonseca Guerra, Célia
author2_role author
dc.subject.none.fl_str_mv Charge transfer
cooperative effects
hydrogen bonds
self-assembly
stacking interactions
topic Charge transfer
cooperative effects
hydrogen bonds
self-assembly
stacking interactions
dc.description.none.fl_txt_mv Hydrogen-bonded supramolecular systems are known to obtain extra stabilization from the complexation with ions, like guanine quadruplex (GQ). They experience strong hydrogen bonds due to cooperative effects. To gain deeper understanding of the interplay between ions and hydrogen-bonding cooperativity, relativistic dispersion-cor rected density functional theory (DFT-D) computations were performed on triple layer hydrogen-bonded rosettes of ammeline interacting with alkali metal cations and halides. Our results show that when ions are placed between the stacks, the hydrogen bonds are weakened but, at the same time, the cooperativity is strengthened. This phenomenon can be traced back to the shrinkage of the cavity as the ions pull the monomers closer together and therefore the distance between the monomers becomes smaller. On one hand this results in a larger steric repulsion, but on the other hand, the donor-acceptor interactions are enhanced due to the larger overlap between the donating and accepting orbitals leading to more charge donation and therefore an enhanced electrostatic attraction.
Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Petelski, Andre Nicolai. Universidad Libre de Ámsterdam. Instituto de Ciencias Biológicas y Moleculares de Ámsterdam; Países Bajos.
Fil: Fonseca Guerra, Célia. Universidad Libre de Ámsterdam. Instituto de Ciencias Biológicas y Moleculares de Ámsterdam; Países Bajos.
Peer Reviewed
description Hydrogen-bonded supramolecular systems are known to obtain extra stabilization from the complexation with ions, like guanine quadruplex (GQ). They experience strong hydrogen bonds due to cooperative effects. To gain deeper understanding of the interplay between ions and hydrogen-bonding cooperativity, relativistic dispersion-cor rected density functional theory (DFT-D) computations were performed on triple layer hydrogen-bonded rosettes of ammeline interacting with alkali metal cations and halides. Our results show that when ions are placed between the stacks, the hydrogen bonds are weakened but, at the same time, the cooperativity is strengthened. This phenomenon can be traced back to the shrinkage of the cavity as the ions pull the monomers closer together and therefore the distance between the monomers becomes smaller. On one hand this results in a larger steric repulsion, but on the other hand, the donor-acceptor interactions are enhanced due to the larger overlap between the donating and accepting orbitals leading to more charge donation and therefore an enhanced electrostatic attraction.
publishDate 2022
dc.date.none.fl_str_mv 2022-11-07
2023-10-30T20:21:43Z
2023-10-30T20:21:43Z
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv 1861-4728
http://hdl.handle.net/20.500.12272/8659
doi.org/10.1002/asia.202201010
identifier_str_mv 1861-4728
doi.org/10.1002/asia.202201010
url http://hdl.handle.net/20.500.12272/8659
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
2023-10-30T20:21:43Z
Acceso Abierto
eu_rights_str_mv openAccess
rights_invalid_str_mv 2023-10-30T20:21:43Z
Acceso Abierto
dc.format.none.fl_str_mv pdf
application/pdf
dc.source.none.fl_str_mv reponame:Repositorio Institucional Abierto (UTN)
instname:Universidad Tecnológica Nacional
reponame_str Repositorio Institucional Abierto (UTN)
collection Repositorio Institucional Abierto (UTN)
instname_str Universidad Tecnológica Nacional
repository.name.fl_str_mv Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacional
repository.mail.fl_str_mv gestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.ar
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score 13.265058

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