Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes

Autores
Gilles, Facundo Matias; Tagliazucchi, Mario Eugenio; Azzaroni, Omar; Szleifer, Igal
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A theoretical methodology is introduced to calculate the low-bias conductance, structure, and composition of long polyelectrolyte-modified nanochannels of arbitrary geometry. This methodology is applied to explore the coupling between acid-base equilibrium and geometry in cylindrical, conical, and trumpet-shaped nanochannels modified by end-grafted layers of poly(2-(methacryloyloxy)ethyl-phosphate) (PMEP), a diprotic polyacid. The ionic conductance and speciation curves (i.e., the fraction of deprotonated, monoprotonated, and diprotonated acid segments) for this system were predicted as a function of the solution pH. The apparent pKa's and widths of the transitions between the different acid-base states determined from the speciation curves depend on the diameter and shape of the nanochannel and the bulk salt concentration. In the limit of wide channels, the apparent pKa's and widths can be estimated by a simplified analytical model derived from the more general molecular theory. Both the general and the simplified theory predicts that, due to charge-regulation effects, the first acid-base transition (0/-1 transition) is wider than the second one (-1/-2), and both transitions are wider than the ideal one expected for an isolated acid-base group in the bulk. It is also shown that the inflection points of the conductance versus pH curves provide a very good estimation of the apparent pKa's of the polyelectrolyte for cylindrical channels, but the quality of the estimation decreases for noncylindrical geometries.
Fil: Gilles, Facundo Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Szleifer, Igal. Northwestern University; Estados Unidos
Materia
Nanochannel
Nernst-Planck
Polyelectrolyte
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:11336/48940
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic BrushesGilles, Facundo MatiasTagliazucchi, Mario EugenioAzzaroni, OmarSzleifer, IgalNanochannelNernst-PlanckPolyelectrolytehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A theoretical methodology is introduced to calculate the low-bias conductance, structure, and composition of long polyelectrolyte-modified nanochannels of arbitrary geometry. This methodology is applied to explore the coupling between acid-base equilibrium and geometry in cylindrical, conical, and trumpet-shaped nanochannels modified by end-grafted layers of poly(2-(methacryloyloxy)ethyl-phosphate) (PMEP), a diprotic polyacid. The ionic conductance and speciation curves (i.e., the fraction of deprotonated, monoprotonated, and diprotonated acid segments) for this system were predicted as a function of the solution pH. The apparent pKa's and widths of the transitions between the different acid-base states determined from the speciation curves depend on the diameter and shape of the nanochannel and the bulk salt concentration. In the limit of wide channels, the apparent pKa's and widths can be estimated by a simplified analytical model derived from the more general molecular theory. Both the general and the simplified theory predicts that, due to charge-regulation effects, the first acid-base transition (0/-1 transition) is wider than the second one (-1/-2), and both transitions are wider than the ideal one expected for an isolated acid-base group in the bulk. It is also shown that the inflection points of the conductance versus pH curves provide a very good estimation of the apparent pKa's of the polyelectrolyte for cylindrical channels, but the quality of the estimation decreases for noncylindrical geometries.Fil: Gilles, Facundo Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Szleifer, Igal. Northwestern University; Estados UnidosAmerican Chemical Society2016-03info: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/11336/48940Gilles, Facundo Matias; Tagliazucchi, Mario Eugenio; Azzaroni, Omar; Szleifer, Igal; Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes; American Chemical Society; Journal of Physical Chemistry C; 120; 9; 3-2016; 4789-47981932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.5b11788info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcc.5b11788info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:12:32Zoai:ri.conicet.gov.ar:11336/48940instacron: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 15:12:32.45CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
title Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
spellingShingle Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
Gilles, Facundo Matias
Nanochannel
Nernst-Planck
Polyelectrolyte
title_short Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
title_full Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
title_fullStr Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
title_full_unstemmed Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
title_sort Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes
dc.creator.none.fl_str_mv Gilles, Facundo Matias
Tagliazucchi, Mario Eugenio
Azzaroni, Omar
Szleifer, Igal
author Gilles, Facundo Matias
author_facet Gilles, Facundo Matias
Tagliazucchi, Mario Eugenio
Azzaroni, Omar
Szleifer, Igal
author_role author
author2 Tagliazucchi, Mario Eugenio
Azzaroni, Omar
Szleifer, Igal
author2_role author
author
author
dc.subject.none.fl_str_mv Nanochannel
Nernst-Planck
Polyelectrolyte
topic Nanochannel
Nernst-Planck
Polyelectrolyte
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A theoretical methodology is introduced to calculate the low-bias conductance, structure, and composition of long polyelectrolyte-modified nanochannels of arbitrary geometry. This methodology is applied to explore the coupling between acid-base equilibrium and geometry in cylindrical, conical, and trumpet-shaped nanochannels modified by end-grafted layers of poly(2-(methacryloyloxy)ethyl-phosphate) (PMEP), a diprotic polyacid. The ionic conductance and speciation curves (i.e., the fraction of deprotonated, monoprotonated, and diprotonated acid segments) for this system were predicted as a function of the solution pH. The apparent pKa's and widths of the transitions between the different acid-base states determined from the speciation curves depend on the diameter and shape of the nanochannel and the bulk salt concentration. In the limit of wide channels, the apparent pKa's and widths can be estimated by a simplified analytical model derived from the more general molecular theory. Both the general and the simplified theory predicts that, due to charge-regulation effects, the first acid-base transition (0/-1 transition) is wider than the second one (-1/-2), and both transitions are wider than the ideal one expected for an isolated acid-base group in the bulk. It is also shown that the inflection points of the conductance versus pH curves provide a very good estimation of the apparent pKa's of the polyelectrolyte for cylindrical channels, but the quality of the estimation decreases for noncylindrical geometries.
Fil: Gilles, Facundo Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Szleifer, Igal. Northwestern University; Estados Unidos
description A theoretical methodology is introduced to calculate the low-bias conductance, structure, and composition of long polyelectrolyte-modified nanochannels of arbitrary geometry. This methodology is applied to explore the coupling between acid-base equilibrium and geometry in cylindrical, conical, and trumpet-shaped nanochannels modified by end-grafted layers of poly(2-(methacryloyloxy)ethyl-phosphate) (PMEP), a diprotic polyacid. The ionic conductance and speciation curves (i.e., the fraction of deprotonated, monoprotonated, and diprotonated acid segments) for this system were predicted as a function of the solution pH. The apparent pKa's and widths of the transitions between the different acid-base states determined from the speciation curves depend on the diameter and shape of the nanochannel and the bulk salt concentration. In the limit of wide channels, the apparent pKa's and widths can be estimated by a simplified analytical model derived from the more general molecular theory. Both the general and the simplified theory predicts that, due to charge-regulation effects, the first acid-base transition (0/-1 transition) is wider than the second one (-1/-2), and both transitions are wider than the ideal one expected for an isolated acid-base group in the bulk. It is also shown that the inflection points of the conductance versus pH curves provide a very good estimation of the apparent pKa's of the polyelectrolyte for cylindrical channels, but the quality of the estimation decreases for noncylindrical geometries.
publishDate 2016
dc.date.none.fl_str_mv 2016-03
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/11336/48940
Gilles, Facundo Matias; Tagliazucchi, Mario Eugenio; Azzaroni, Omar; Szleifer, Igal; Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes; American Chemical Society; Journal of Physical Chemistry C; 120; 9; 3-2016; 4789-4798
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/48940
identifier_str_mv Gilles, Facundo Matias; Tagliazucchi, Mario Eugenio; Azzaroni, Omar; Szleifer, Igal; Ionic Conductance of Polyelectrolyte-Modified Nanochannels: Nanoconfinement Effects on the Coupled Protonation Equilibria of Polyprotic Brushes; American Chemical Society; Journal of Physical Chemistry C; 120; 9; 3-2016; 4789-4798
1932-7447
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/acs.jpcc.5b11788
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcc.5b11788
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 13.221938

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