Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa

Autores
Chamorro, Ester Ramona; Sequeira, Alfredo Fabián; Zalazar, María Fernanda; Peruchena, Nélida María
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Fil: Chamorro, Ester Ramona. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
Fil: Sequeira, Alfredo Fabián. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
Fil: Zalazar, María Fernanda. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina.
Fil: Zalazar, María Fernanda. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
Fil: Peruchena, Nélida María. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina.
Fil: Peruchena, Nélida María. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
In the present work, the distribution of the electronic charge density of the natural sex pheromone, the (Z)-13-hexadecen-11-ynyl acetate, in the female processionary moth, Thaumetopoea pytiocampa, and its nine analogue derivatives was studied within the framework of the Density Functional Theory and the Atoms in Molecules (AIM) Theory at B3LYP/6-31G* //B3LYP/6-31++G** level. Additionally, molecular electrostatic potential (MEP) maps of the previously mentioned compounds were computed and compared. Furthermore, the substitution of hydrogen atoms from the methyl group in the acetate group by electron withdrawing substituents (i.e., halogen atoms) as well as the replacement effect of hydrogen by electron donor substituents (+I effect) as methyl group, were explored. The key feature of the topological distribution of the charge density in analogue compounds, such as the variations of the topological properties encountered in the region formed by neighbouring atoms from the substitution site were presented and discussed. Using topological parameters, such as electronic charge density, Laplacian, kinetic energy density, and potential energy density evaluated at bond critical points (BCP), we provide here a detailed analysis of the nature of the chemical bonding of these molecules. In addition, the atomic properties (population, charge, energy, volume, and dipole moment) were determined on selected atoms. These properties were analyzed at the substitution site (with respect to the natural sex pheromone) and related to the biological activity and to the possible binding site with the pheromone binding protein, (PBP). Moreover, the Laplacian function of the electronic density was used to locate electrophilic regions susceptible to be attacked (by deficient electron atoms or donor hydrogen). Our results indicate that the change in the atomic properties, such as electronic population and atomic volume, are sensitive indicators of the loss of the biological activity in the analogues studied here. The crucial interaction between the acetate group of the natural sex pheromone and the PBP is most likely to be a hydrogen bonding and the substitution of hydrogen atoms by electronegative atoms in the pheromone molecule reduces the hydrogen acceptor capacity. This situation is mirrored by the diminish of the electronic population on carbon and oxygen atoms at the carbonylic group in the halo-acetate group. Additionally, the modified acetate group (with electronegative atoms) shows new charge concentration critical points or regions of concentration of charge density in which an electrophilic attack can also occur. Finally, the use of the topological analysis based in the charge density distribution and its Laplacian function, in conjunction with MEP maps provides valuable information about the steric volume and electronic requirement of the sex pheromone for binding to the PBP.
Fuente
Bioorganic & Medicinal Chemistry, 2008, vol. 16, no. 18, p. 8535–8545.
Materia
Charge density
Laplacian
Molecular electrostatic potential
Sex pheromone
Nivel de accesibilidad
acceso restringido
Condiciones de uso
Repositorio
Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE)
Institución
Universidad Nacional del Nordeste
OAI Identificador
oai:repositorio.unne.edu.ar:123456789/59988
Acceder
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oai_identifier_str oai:repositorio.unne.edu.ar:123456789/59988
network_acronym_str RIUNNE
repository_id_str 4871
network_name_str Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE)
spelling Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampaChamorro, Ester RamonaSequeira, Alfredo FabiánZalazar, María FernandaPeruchena, Nélida MaríaCharge densityLaplacianMolecular electrostatic potentialSex pheromoneFil: Chamorro, Ester Ramona. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.Fil: Sequeira, Alfredo Fabián. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.Fil: Zalazar, María Fernanda. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina.Fil: Zalazar, María Fernanda. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.Fil: Peruchena, Nélida María. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina.Fil: Peruchena, Nélida María. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.In the present work, the distribution of the electronic charge density of the natural sex pheromone, the (Z)-13-hexadecen-11-ynyl acetate, in the female processionary moth, Thaumetopoea pytiocampa, and its nine analogue derivatives was studied within the framework of the Density Functional Theory and the Atoms in Molecules (AIM) Theory at B3LYP/6-31G* //B3LYP/6-31++G** level. Additionally, molecular electrostatic potential (MEP) maps of the previously mentioned compounds were computed and compared. Furthermore, the substitution of hydrogen atoms from the methyl group in the acetate group by electron withdrawing substituents (i.e., halogen atoms) as well as the replacement effect of hydrogen by electron donor substituents (+I effect) as methyl group, were explored. The key feature of the topological distribution of the charge density in analogue compounds, such as the variations of the topological properties encountered in the region formed by neighbouring atoms from the substitution site were presented and discussed. Using topological parameters, such as electronic charge density, Laplacian, kinetic energy density, and potential energy density evaluated at bond critical points (BCP), we provide here a detailed analysis of the nature of the chemical bonding of these molecules. In addition, the atomic properties (population, charge, energy, volume, and dipole moment) were determined on selected atoms. These properties were analyzed at the substitution site (with respect to the natural sex pheromone) and related to the biological activity and to the possible binding site with the pheromone binding protein, (PBP). Moreover, the Laplacian function of the electronic density was used to locate electrophilic regions susceptible to be attacked (by deficient electron atoms or donor hydrogen). Our results indicate that the change in the atomic properties, such as electronic population and atomic volume, are sensitive indicators of the loss of the biological activity in the analogues studied here. The crucial interaction between the acetate group of the natural sex pheromone and the PBP is most likely to be a hydrogen bonding and the substitution of hydrogen atoms by electronegative atoms in the pheromone molecule reduces the hydrogen acceptor capacity. This situation is mirrored by the diminish of the electronic population on carbon and oxygen atoms at the carbonylic group in the halo-acetate group. Additionally, the modified acetate group (with electronegative atoms) shows new charge concentration critical points or regions of concentration of charge density in which an electrophilic attack can also occur. Finally, the use of the topological analysis based in the charge density distribution and its Laplacian function, in conjunction with MEP maps provides valuable information about the steric volume and electronic requirement of the sex pheromone for binding to the PBP.Elsevier2008info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfp. 8535–8545application/pdfChamorro, Ester Ramona, et al., 2008. Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa. Bioorganic & Medicinal Chemistry. Ámsterdam: Elsevier, vol. 16, no. 18, p. 8535-8545. E-ISSN 1464-3391.0968-0896http://repositorio.unne.edu.ar/handle/123456789/59988Bioorganic & Medicinal Chemistry, 2008, vol. 16, no. 18, p. 8535–8545.reponame:Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE)instname:Universidad Nacional del Nordesteenghttps://www.sciencedirect.com/science/article/abs/pii/S0968089608007244info:eu-repo/semantics/restrictedAccess2026-10-01T11:58:10Zoai:repositorio.unne.edu.ar:123456789/59988instacron:UNNEInstitucionalhttp://repositorio.unne.edu.ar/Universidad públicaNo correspondehttp://repositorio.unne.edu.ar/oaiososa@bib.unne.edu.ar;sergio.alegria@unne.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:48712026-10-01 11:58:10.89Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE) - Universidad Nacional del Nordestefalse
dc.title.none.fl_str_mv Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
title Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
spellingShingle Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
Chamorro, Ester Ramona
Charge density
Laplacian
Molecular electrostatic potential
Sex pheromone
title_short Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
title_full Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
title_fullStr Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
title_full_unstemmed Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
title_sort Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa
dc.creator.none.fl_str_mv Chamorro, Ester Ramona
Sequeira, Alfredo Fabián
Zalazar, María Fernanda
Peruchena, Nélida María
author Chamorro, Ester Ramona
author_facet Chamorro, Ester Ramona
Sequeira, Alfredo Fabián
Zalazar, María Fernanda
Peruchena, Nélida María
author_role author
author2 Sequeira, Alfredo Fabián
Zalazar, María Fernanda
Peruchena, Nélida María
author2_role author
author
author
dc.subject.none.fl_str_mv Charge density
Laplacian
Molecular electrostatic potential
Sex pheromone
topic Charge density
Laplacian
Molecular electrostatic potential
Sex pheromone
dc.description.none.fl_txt_mv Fil: Chamorro, Ester Ramona. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
Fil: Sequeira, Alfredo Fabián. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
Fil: Zalazar, María Fernanda. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina.
Fil: Zalazar, María Fernanda. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
Fil: Peruchena, Nélida María. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Laboratorio de Estructura Molecular y Propiedades; Argentina.
Fil: Peruchena, Nélida María. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
In the present work, the distribution of the electronic charge density of the natural sex pheromone, the (Z)-13-hexadecen-11-ynyl acetate, in the female processionary moth, Thaumetopoea pytiocampa, and its nine analogue derivatives was studied within the framework of the Density Functional Theory and the Atoms in Molecules (AIM) Theory at B3LYP/6-31G* //B3LYP/6-31++G** level. Additionally, molecular electrostatic potential (MEP) maps of the previously mentioned compounds were computed and compared. Furthermore, the substitution of hydrogen atoms from the methyl group in the acetate group by electron withdrawing substituents (i.e., halogen atoms) as well as the replacement effect of hydrogen by electron donor substituents (+I effect) as methyl group, were explored. The key feature of the topological distribution of the charge density in analogue compounds, such as the variations of the topological properties encountered in the region formed by neighbouring atoms from the substitution site were presented and discussed. Using topological parameters, such as electronic charge density, Laplacian, kinetic energy density, and potential energy density evaluated at bond critical points (BCP), we provide here a detailed analysis of the nature of the chemical bonding of these molecules. In addition, the atomic properties (population, charge, energy, volume, and dipole moment) were determined on selected atoms. These properties were analyzed at the substitution site (with respect to the natural sex pheromone) and related to the biological activity and to the possible binding site with the pheromone binding protein, (PBP). Moreover, the Laplacian function of the electronic density was used to locate electrophilic regions susceptible to be attacked (by deficient electron atoms or donor hydrogen). Our results indicate that the change in the atomic properties, such as electronic population and atomic volume, are sensitive indicators of the loss of the biological activity in the analogues studied here. The crucial interaction between the acetate group of the natural sex pheromone and the PBP is most likely to be a hydrogen bonding and the substitution of hydrogen atoms by electronegative atoms in the pheromone molecule reduces the hydrogen acceptor capacity. This situation is mirrored by the diminish of the electronic population on carbon and oxygen atoms at the carbonylic group in the halo-acetate group. Additionally, the modified acetate group (with electronegative atoms) shows new charge concentration critical points or regions of concentration of charge density in which an electrophilic attack can also occur. Finally, the use of the topological analysis based in the charge density distribution and its Laplacian function, in conjunction with MEP maps provides valuable information about the steric volume and electronic requirement of the sex pheromone for binding to the PBP.
description Fil: Chamorro, Ester Ramona. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina.
publishDate 2008
dc.date.none.fl_str_mv 2008
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 Chamorro, Ester Ramona, et al., 2008. Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa. Bioorganic & Medicinal Chemistry. Ámsterdam: Elsevier, vol. 16, no. 18, p. 8535-8545. E-ISSN 1464-3391.
0968-0896
http://repositorio.unne.edu.ar/handle/123456789/59988
identifier_str_mv Chamorro, Ester Ramona, et al., 2008. Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa. Bioorganic & Medicinal Chemistry. Ámsterdam: Elsevier, vol. 16, no. 18, p. 8535-8545. E-ISSN 1464-3391.
0968-0896
url http://repositorio.unne.edu.ar/handle/123456789/59988
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv https://www.sciencedirect.com/science/article/abs/pii/S0968089608007244
dc.rights.none.fl_str_mv info:eu-repo/semantics/restrictedAccess
eu_rights_str_mv restrictedAccess
dc.format.none.fl_str_mv application/pdf
p. 8535–8545
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv Bioorganic & Medicinal Chemistry, 2008, vol. 16, no. 18, p. 8535–8545.
reponame:Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE)
instname:Universidad Nacional del Nordeste
reponame_str Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE)
collection Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE)
instname_str Universidad Nacional del Nordeste
repository.name.fl_str_mv Repositorio Institucional de la Universidad Nacional del Nordeste (UNNE) - Universidad Nacional del Nordeste
repository.mail.fl_str_mv ososa@bib.unne.edu.ar;sergio.alegria@unne.edu.ar
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score 12.854657

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