Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations

Autores
Schulz, Erica Patricia; Piñeiro, Ángel; Miñones, José; Miñones Trillo, José; Frechero, Marisa Alejandra; Pieroni, Olga Inés; Schulz, Pablo Carlos
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Monolayers of n-eicosanephosphonic acid, EPA, were studied using a Langmuir balance and a Brewster angle microscope at different subphase pH values to change the charge of the polar headgroups (Zav) from 0 to -2. Molecular dynamics simulations (MDS) results for |Zav| = 0, 1, and 2 were compared with the experimental ones. EPA monolayers behave as mixtures of mutually miscible species (C20H41-PO3H2, C20H41-PO3H-, and C20H41-PO32-, depending on the subphase pH). The order and compactness of the monolayers decrease when increasing |Zav|, while go from strongly interconnected by phosphonic-phosphonic hydrogen bonds (|Zav| = 0-0.03) through an equilibrium between the total cohesive energy and the electrostatic repulsion between the charged polar groups (0.03 < |Zav| < 1.6) to an entirely ionic monolayer (|Zav| ≈ 2). MDS reveal for |Zav| = 0 that the chains form spiralled nearly rounded structures induced by the hydrogen-bonded network. When |Zav| ≈ 1 fingering domains were identified. When Z ≈ 2, the headgroups are more disordered and distanced, not only in the xy plane but also in the z direction, forming a rough layer and responding to compression with a large plateau in the isotherm. The monolayers collapse behavior is consistent with the structures and domains founds in the different ionization states and their consequent in-plane rigidity: there is a transition from a solid-like response at low pH subphases to a fluid-like response at high pH subphases. The film area in the close-packed state increases relatively slow when the polar headgroups are able to form hydrogen bonds but increases to near twice that this value when |Zav| ≈ 2. Other nanoscopic properties of monolayers were also determined by MDS. The computational results confirm the experimental findings and offer a nanoscopic perspective on the structure and interactions in the phosphonate monolayers.
Fil: Schulz, Erica Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Piñeiro, Ángel. Universidad de Santiago de Compostela; España
Fil: Miñones, José. Universidad de Santiago de Compostela; España
Fil: Miñones Trillo, José. Universidad de Santiago de Compostela; España
Fil: Frechero, Marisa Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Pieroni, Olga Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Schulz, Pablo Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Materia
Ionization
Behavior
Phosphonic Acid
Monolayers
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:11336/39847
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/39847
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network_name_str CONICET Digital (CONICET)
spelling Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulationsSchulz, Erica PatriciaPiñeiro, ÁngelMiñones, JoséMiñones Trillo, JoséFrechero, Marisa AlejandraPieroni, Olga InésSchulz, Pablo CarlosIonizationBehaviorPhosphonic AcidMonolayershttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Monolayers of n-eicosanephosphonic acid, EPA, were studied using a Langmuir balance and a Brewster angle microscope at different subphase pH values to change the charge of the polar headgroups (Zav) from 0 to -2. Molecular dynamics simulations (MDS) results for |Zav| = 0, 1, and 2 were compared with the experimental ones. EPA monolayers behave as mixtures of mutually miscible species (C20H41-PO3H2, C20H41-PO3H-, and C20H41-PO32-, depending on the subphase pH). The order and compactness of the monolayers decrease when increasing |Zav|, while go from strongly interconnected by phosphonic-phosphonic hydrogen bonds (|Zav| = 0-0.03) through an equilibrium between the total cohesive energy and the electrostatic repulsion between the charged polar groups (0.03 < |Zav| < 1.6) to an entirely ionic monolayer (|Zav| ≈ 2). MDS reveal for |Zav| = 0 that the chains form spiralled nearly rounded structures induced by the hydrogen-bonded network. When |Zav| ≈ 1 fingering domains were identified. When Z ≈ 2, the headgroups are more disordered and distanced, not only in the xy plane but also in the z direction, forming a rough layer and responding to compression with a large plateau in the isotherm. The monolayers collapse behavior is consistent with the structures and domains founds in the different ionization states and their consequent in-plane rigidity: there is a transition from a solid-like response at low pH subphases to a fluid-like response at high pH subphases. The film area in the close-packed state increases relatively slow when the polar headgroups are able to form hydrogen bonds but increases to near twice that this value when |Zav| ≈ 2. Other nanoscopic properties of monolayers were also determined by MDS. The computational results confirm the experimental findings and offer a nanoscopic perspective on the structure and interactions in the phosphonate monolayers.Fil: Schulz, Erica Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Piñeiro, Ángel. Universidad de Santiago de Compostela; EspañaFil: Miñones, José. Universidad de Santiago de Compostela; EspañaFil: Miñones Trillo, José. Universidad de Santiago de Compostela; EspañaFil: Frechero, Marisa Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Pieroni, Olga Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Schulz, Pablo Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaAmerican Chemical Society2015-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/39847Schulz, Erica Patricia; Piñeiro, Ángel; Miñones, José; Miñones Trillo, José; Frechero, Marisa Alejandra; et al.; Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations; American Chemical Society; Langmuir; 31; 8; 3-2015; 2269-22800743-7463CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/la5050283info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/la5050283info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:46:22Zoai:ri.conicet.gov.ar:11336/39847instacron: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:34982025-10-15 15:46:23.187CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
title Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
spellingShingle Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
Schulz, Erica Patricia
Ionization
Behavior
Phosphonic Acid
Monolayers
title_short Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
title_full Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
title_fullStr Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
title_full_unstemmed Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
title_sort Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations
dc.creator.none.fl_str_mv Schulz, Erica Patricia
Piñeiro, Ángel
Miñones, José
Miñones Trillo, José
Frechero, Marisa Alejandra
Pieroni, Olga Inés
Schulz, Pablo Carlos
author Schulz, Erica Patricia
author_facet Schulz, Erica Patricia
Piñeiro, Ángel
Miñones, José
Miñones Trillo, José
Frechero, Marisa Alejandra
Pieroni, Olga Inés
Schulz, Pablo Carlos
author_role author
author2 Piñeiro, Ángel
Miñones, José
Miñones Trillo, José
Frechero, Marisa Alejandra
Pieroni, Olga Inés
Schulz, Pablo Carlos
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Ionization
Behavior
Phosphonic Acid
Monolayers
topic Ionization
Behavior
Phosphonic Acid
Monolayers
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Monolayers of n-eicosanephosphonic acid, EPA, were studied using a Langmuir balance and a Brewster angle microscope at different subphase pH values to change the charge of the polar headgroups (Zav) from 0 to -2. Molecular dynamics simulations (MDS) results for |Zav| = 0, 1, and 2 were compared with the experimental ones. EPA monolayers behave as mixtures of mutually miscible species (C20H41-PO3H2, C20H41-PO3H-, and C20H41-PO32-, depending on the subphase pH). The order and compactness of the monolayers decrease when increasing |Zav|, while go from strongly interconnected by phosphonic-phosphonic hydrogen bonds (|Zav| = 0-0.03) through an equilibrium between the total cohesive energy and the electrostatic repulsion between the charged polar groups (0.03 < |Zav| < 1.6) to an entirely ionic monolayer (|Zav| ≈ 2). MDS reveal for |Zav| = 0 that the chains form spiralled nearly rounded structures induced by the hydrogen-bonded network. When |Zav| ≈ 1 fingering domains were identified. When Z ≈ 2, the headgroups are more disordered and distanced, not only in the xy plane but also in the z direction, forming a rough layer and responding to compression with a large plateau in the isotherm. The monolayers collapse behavior is consistent with the structures and domains founds in the different ionization states and their consequent in-plane rigidity: there is a transition from a solid-like response at low pH subphases to a fluid-like response at high pH subphases. The film area in the close-packed state increases relatively slow when the polar headgroups are able to form hydrogen bonds but increases to near twice that this value when |Zav| ≈ 2. Other nanoscopic properties of monolayers were also determined by MDS. The computational results confirm the experimental findings and offer a nanoscopic perspective on the structure and interactions in the phosphonate monolayers.
Fil: Schulz, Erica Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Piñeiro, Ángel. Universidad de Santiago de Compostela; España
Fil: Miñones, José. Universidad de Santiago de Compostela; España
Fil: Miñones Trillo, José. Universidad de Santiago de Compostela; España
Fil: Frechero, Marisa Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Pieroni, Olga Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Schulz, Pablo Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
description Monolayers of n-eicosanephosphonic acid, EPA, were studied using a Langmuir balance and a Brewster angle microscope at different subphase pH values to change the charge of the polar headgroups (Zav) from 0 to -2. Molecular dynamics simulations (MDS) results for |Zav| = 0, 1, and 2 were compared with the experimental ones. EPA monolayers behave as mixtures of mutually miscible species (C20H41-PO3H2, C20H41-PO3H-, and C20H41-PO32-, depending on the subphase pH). The order and compactness of the monolayers decrease when increasing |Zav|, while go from strongly interconnected by phosphonic-phosphonic hydrogen bonds (|Zav| = 0-0.03) through an equilibrium between the total cohesive energy and the electrostatic repulsion between the charged polar groups (0.03 < |Zav| < 1.6) to an entirely ionic monolayer (|Zav| ≈ 2). MDS reveal for |Zav| = 0 that the chains form spiralled nearly rounded structures induced by the hydrogen-bonded network. When |Zav| ≈ 1 fingering domains were identified. When Z ≈ 2, the headgroups are more disordered and distanced, not only in the xy plane but also in the z direction, forming a rough layer and responding to compression with a large plateau in the isotherm. The monolayers collapse behavior is consistent with the structures and domains founds in the different ionization states and their consequent in-plane rigidity: there is a transition from a solid-like response at low pH subphases to a fluid-like response at high pH subphases. The film area in the close-packed state increases relatively slow when the polar headgroups are able to form hydrogen bonds but increases to near twice that this value when |Zav| ≈ 2. Other nanoscopic properties of monolayers were also determined by MDS. The computational results confirm the experimental findings and offer a nanoscopic perspective on the structure and interactions in the phosphonate monolayers.
publishDate 2015
dc.date.none.fl_str_mv 2015-03
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/11336/39847
Schulz, Erica Patricia; Piñeiro, Ángel; Miñones, José; Miñones Trillo, José; Frechero, Marisa Alejandra; et al.; Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations; American Chemical Society; Langmuir; 31; 8; 3-2015; 2269-2280
0743-7463
CONICET Digital
CONICET
url http://hdl.handle.net/11336/39847
identifier_str_mv Schulz, Erica Patricia; Piñeiro, Ángel; Miñones, José; Miñones Trillo, José; Frechero, Marisa Alejandra; et al.; Effect of ionization on the behavior of n-Eicosanephosphonic acid monolayers at the air/water interface. experimental determinations and molecular dynamics simulations; American Chemical Society; Langmuir; 31; 8; 3-2015; 2269-2280
0743-7463
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/la5050283
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/la5050283
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
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 13.22299

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