Understanding the Chloride Affinity of Barbiturates for Anion Receptor Design

Autores
Petelski, Andre Nicolai; Marquez, Josefina; Pamies, Silvana Carina; Sosa, Gladis Laura; Peruchena, Nelida Maria
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. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Marquez, Josefina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; Argentina
Fil: Pamies, Silvana Carina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; Argentina
Fil: Sosa, Gladis Laura. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; Argentina
Fil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Materia
ANIONS
COORDINATION MODES
DENSITY FUNCTIONAL CALCULATIONS
HYDROGEN BONDS
RECEPTORS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/150432
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/150432
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Understanding the Chloride Affinity of Barbiturates for Anion Receptor DesignPetelski, Andre NicolaiMarquez, JosefinaPamies, Silvana CarinaSosa, Gladis LauraPeruchena, Nelida MariaANIONSCOORDINATION MODESDENSITY FUNCTIONAL CALCULATIONSHYDROGEN BONDSRECEPTORShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Due 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. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Marquez, Josefina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; ArgentinaFil: Pamies, Silvana Carina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; ArgentinaFil: Sosa, Gladis Laura. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; ArgentinaFil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaWiley VCH Verlag2021-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/150432Petelski, Andre Nicolai; Marquez, Josefina; Pamies, Silvana Carina; Sosa, Gladis Laura; Peruchena, Nelida Maria; Understanding the Chloride Affinity of Barbiturates for Anion Receptor Design; Wiley VCH Verlag; Chemphyschem; 22; 7; 2-2021; 665-6741439-4235CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/cphc.202100008info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.202100008info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-17T11:45:58Zoai:ri.conicet.gov.ar:11336/150432instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-17 11:45:59.052CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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
Marquez, Josefina
Pamies, Silvana Carina
Sosa, Gladis Laura
Peruchena, Nelida Maria
author Petelski, Andre Nicolai
author_facet Petelski, Andre Nicolai
Marquez, Josefina
Pamies, Silvana Carina
Sosa, Gladis Laura
Peruchena, Nelida Maria
author_role author
author2 Marquez, Josefina
Pamies, Silvana Carina
Sosa, Gladis Laura
Peruchena, Nelida Maria
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
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Marquez, Josefina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; Argentina
Fil: Pamies, Silvana Carina. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; Argentina
Fil: Sosa, Gladis Laura. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Departamento de Ingeniería Química. Laboratorio de Química Teórica y Experimental; Argentina
Fil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
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
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 http://hdl.handle.net/11336/150432
Petelski, Andre Nicolai; Marquez, Josefina; Pamies, Silvana Carina; Sosa, Gladis Laura; Peruchena, Nelida Maria; Understanding the Chloride Affinity of Barbiturates for Anion Receptor Design; Wiley VCH Verlag; Chemphyschem; 22; 7; 2-2021; 665-674
1439-4235
CONICET Digital
CONICET
url http://hdl.handle.net/11336/150432
identifier_str_mv Petelski, Andre Nicolai; Marquez, Josefina; Pamies, Silvana Carina; Sosa, Gladis Laura; Peruchena, Nelida Maria; Understanding the Chloride Affinity of Barbiturates for Anion Receptor Design; Wiley VCH Verlag; Chemphyschem; 22; 7; 2-2021; 665-674
1439-4235
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/cphc.202100008
info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.202100008
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.001348

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