Understanding the chloride affinity of barbiturates for anion receptor design

Autores
Petelski, Andre Nicolai; Márquez, María Josefina; Pamies, Silvana Carina; Sosa, Gladis Laura; Peruchena, Nélida María
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C—H bond is as effective as the N—H bond to coordinate chloride. An analysis of the electron charge density at the C—H···Cl— and N—H···Cl— bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C—H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C—H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl.
Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Petelski, André Nicolai. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina.
Fil: Márquez, María Josefina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina.
Fil: Pamies, Silvana Carina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina.
Fil: Sosa, Gladis Laura. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Sosa, Gladis Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina.
Fil: Peruchena, Nélida María. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Fil: Peruchena, Nélida María. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina
Peer Reviewed
Materia
anions
coordination modes
density functional
calculations
hydrogen bonds
receptors
Nivel de accesibilidad
acceso abierto
Condiciones de uso
2023-10-27T21:20:04Z
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/8649
Acceder
id RIAUTN_0522c8efeb7191409024ec90544380c8
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network_acronym_str RIAUTN
repository_id_str a
network_name_str Repositorio Institucional Abierto (UTN)
spelling Understanding the chloride affinity of barbiturates for anion receptor designPetelski, Andre NicolaiMárquez, María JosefinaPamies, Silvana CarinaSosa, Gladis LauraPeruchena, Nélida Maríaanionscoordination modesdensity functionalcalculationshydrogen bondsreceptorsDue to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C—H bond is as effective as the N—H bond to coordinate chloride. An analysis of the electron charge density at the C—H···Cl— and N—H···Cl— bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C—H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C—H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl.Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Petelski, André Nicolai. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina.Fil: Márquez, María Josefina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina.Fil: Pamies, Silvana Carina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina.Fil: Sosa, Gladis Laura. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Sosa, Gladis Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina.Fil: Peruchena, Nélida María. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Fil: Peruchena, Nélida María. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; ArgentinaPeer Reviewed2023-10-27T21:20:04Z2023-10-27T21:20:04Z2021-02-25info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articulopdfapplication/pdf1439-4235http://hdl.handle.net/20.500.12272/8649doi.org/10.1002/cphc.202100008enginfo:eu-repo/semantics/openAccess2023-10-27T21:20:04ZAcceso abiertoreponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica Nacional2026-09-24T12:48:56Zoai:ria.utn.edu.ar:20.500.12272/8649instacron: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 12:48:57.156Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Understanding the chloride affinity of barbiturates for anion receptor design
title Understanding the chloride affinity of barbiturates for anion receptor design
spellingShingle Understanding the chloride affinity of barbiturates for anion receptor design
Petelski, Andre Nicolai
anions
coordination modes
density functional
calculations
hydrogen bonds
receptors
title_short Understanding the chloride affinity of barbiturates for anion receptor design
title_full Understanding the chloride affinity of barbiturates for anion receptor design
title_fullStr Understanding the chloride affinity of barbiturates for anion receptor design
title_full_unstemmed Understanding the chloride affinity of barbiturates for anion receptor design
title_sort Understanding the chloride affinity of barbiturates for anion receptor design
dc.creator.none.fl_str_mv Petelski, Andre Nicolai
Márquez, María Josefina
Pamies, Silvana Carina
Sosa, Gladis Laura
Peruchena, Nélida María
author Petelski, Andre Nicolai
author_facet Petelski, Andre Nicolai
Márquez, María Josefina
Pamies, Silvana Carina
Sosa, Gladis Laura
Peruchena, Nélida María
author_role author
author2 Márquez, María Josefina
Pamies, Silvana Carina
Sosa, Gladis Laura
Peruchena, Nélida María
author2_role author
author
author
author
dc.subject.none.fl_str_mv anions
coordination modes
density functional
calculations
hydrogen bonds
receptors
topic anions
coordination modes
density functional
calculations
hydrogen bonds
receptors
dc.description.none.fl_txt_mv Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C—H bond is as effective as the N—H bond to coordinate chloride. An analysis of the electron charge density at the C—H···Cl— and N—H···Cl— bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C—H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C—H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl.
Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Petelski, André Nicolai. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina.
Fil: Márquez, María Josefina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina.
Fil: Pamies, Silvana Carina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina.
Fil: Sosa, Gladis Laura. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Grupo de Investigación Química Teórica Experimental; Argentina. Fil: Sosa, Gladis Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina.
Fil: Peruchena, Nélida María. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Fil: Peruchena, Nélida María. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina
Peer Reviewed
description Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C—H bond is as effective as the N—H bond to coordinate chloride. An analysis of the electron charge density at the C—H···Cl— and N—H···Cl— bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C—H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C—H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl.
publishDate 2021
dc.date.none.fl_str_mv 2021-02-25
2023-10-27T21:20:04Z
2023-10-27T21:20:04Z
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 1439-4235
http://hdl.handle.net/20.500.12272/8649
doi.org/10.1002/cphc.202100008
identifier_str_mv 1439-4235
doi.org/10.1002/cphc.202100008
url http://hdl.handle.net/20.500.12272/8649
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
2023-10-27T21:20:04Z
Acceso abierto
eu_rights_str_mv openAccess
rights_invalid_str_mv 2023-10-27T21:20:04Z
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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