Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes

Autores
Blanco, Pablo M.; Madurga Díez, Sergio; Narambuena, Claudio Fabian; Mas Pujadas, Francesc; Garcés, Josep L.
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
This work addresses the role of charge regulation (CR) and the associated fluctuations in the conformational and mechanical properties of weak polyelectrolytes. Due to CR, changes in the pH-value modifies the average macromolecular charge and conformational equilibria. A second effect is that, for a given average charge per site, fluctuations can alter the intensity of the interactions by means of correlation between binding sites. We investigate both effects by means of Monte Carlo simulations at constant pH-value, so that the charge is a fluctuating quantity. Once the average charge per site is available, we turn off the fluctuations by assigning the same average charge to every site. A constant charge MC simulation is then performed. We make use of a model which accounts for the main fundamental aspects of a linear flexible polyelectrolyte that is, proton binding, angle internal rotation, bond stretching and bending. Steric excluded volume and differentiated treatment for short-range and long-range interactions are also included. This model can be regarded as a kind of "minimal" in the sense that it contains a minimum number of parameters but still preserving the atomistic detail. It is shown that, if fluctuations are activated, gauche state bond probabilities increase and the persistence length decreases, so that the polymer becomes more folded. Macromolecular stretching is also analyzed in presence of CR (the charge depends on the applied force) and without CR (the charge is fixed to the value at zero force). The analysis of the low force scaling behavior concludes that Pincus exponent becomes pH-dependent. Both, with and without CR, a transition from 1/2 at high pH-values (phantom chain) to 3/5 at low pH-values (Pincus regime) is observed. Finally, the intermediate force stretching regime is investigated. It is found that CR induces a moderate influence in the force-extension curves and persistence length (which in this force regime becomes force-dependent). It is thus concluded that the effect of CR on the stretching curves is mainly due to the changes in the average charge at zero force. It is also found that, for the cases studied, the effect of steric excluded volume is almost irrelevant compared to electrostatic interactions.
Fil: Blanco, Pablo M.. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; España
Fil: Madurga Díez, Sergio. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; España
Fil: Narambuena, Claudio Fabian. Universidad Tecnologica Nacional. Facultad Regional San Rafael; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - San Luis. Instituto de Fisica Aplicada "dr. Jorge Andres Zgrablich". Grupo Vinculado Bionanotecnologia y Sistemas Complejos | Universidad Nacional de San Luis. Facultad de Cs.fisico Matematicas y Naturales. Instituto de Fisica Aplicada "dr. Jorge Andres Zgrablich". Grupo Vinculado Bionanotecnologia y Sistemas Complejos. - Universidad Tecnologica Nacional. Facultad Reg.san Rafael. Grupo Vinculado Bionanotecnologia y Sistemas Complejos.; Argentina
Fil: Mas Pujadas, Francesc. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; España
Fil: Garcés, Josep L.. Lleida University; España
Materia
ANNEALED POLYELECTROLYTE
BINDING EQUILIBRIA
CHARGE FLUCTUATIONS
CHARGE REGULATION
CONFORMATIONAL EQUILIBRIA
CONSTANT PH ENSAMBLE
MONTE CARLO SIMULATION
POLYELECTROLYTES
SCALING LAW
SEMI-GRAND CANONICAL ENSEMBLE
STRETCHING
WEAK 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:11336/183029

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oai_identifier_str oai:ri.conicet.gov.ar:11336/183029
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible PolyelectrolytesBlanco, Pablo M.Madurga Díez, SergioNarambuena, Claudio FabianMas Pujadas, FrancescGarcés, Josep L.ANNEALED POLYELECTROLYTEBINDING EQUILIBRIACHARGE FLUCTUATIONSCHARGE REGULATIONCONFORMATIONAL EQUILIBRIACONSTANT PH ENSAMBLEMONTE CARLO SIMULATIONPOLYELECTROLYTESSCALING LAWSEMI-GRAND CANONICAL ENSEMBLESTRETCHINGWEAK POLYELECTROLYTEhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1This work addresses the role of charge regulation (CR) and the associated fluctuations in the conformational and mechanical properties of weak polyelectrolytes. Due to CR, changes in the pH-value modifies the average macromolecular charge and conformational equilibria. A second effect is that, for a given average charge per site, fluctuations can alter the intensity of the interactions by means of correlation between binding sites. We investigate both effects by means of Monte Carlo simulations at constant pH-value, so that the charge is a fluctuating quantity. Once the average charge per site is available, we turn off the fluctuations by assigning the same average charge to every site. A constant charge MC simulation is then performed. We make use of a model which accounts for the main fundamental aspects of a linear flexible polyelectrolyte that is, proton binding, angle internal rotation, bond stretching and bending. Steric excluded volume and differentiated treatment for short-range and long-range interactions are also included. This model can be regarded as a kind of "minimal" in the sense that it contains a minimum number of parameters but still preserving the atomistic detail. It is shown that, if fluctuations are activated, gauche state bond probabilities increase and the persistence length decreases, so that the polymer becomes more folded. Macromolecular stretching is also analyzed in presence of CR (the charge depends on the applied force) and without CR (the charge is fixed to the value at zero force). The analysis of the low force scaling behavior concludes that Pincus exponent becomes pH-dependent. Both, with and without CR, a transition from 1/2 at high pH-values (phantom chain) to 3/5 at low pH-values (Pincus regime) is observed. Finally, the intermediate force stretching regime is investigated. It is found that CR induces a moderate influence in the force-extension curves and persistence length (which in this force regime becomes force-dependent). It is thus concluded that the effect of CR on the stretching curves is mainly due to the changes in the average charge at zero force. It is also found that, for the cases studied, the effect of steric excluded volume is almost irrelevant compared to electrostatic interactions.Fil: Blanco, Pablo M.. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; EspañaFil: Madurga Díez, Sergio. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; EspañaFil: Narambuena, Claudio Fabian. Universidad Tecnologica Nacional. Facultad Regional San Rafael; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - San Luis. Instituto de Fisica Aplicada "dr. Jorge Andres Zgrablich". Grupo Vinculado Bionanotecnologia y Sistemas Complejos | Universidad Nacional de San Luis. Facultad de Cs.fisico Matematicas y Naturales. Instituto de Fisica Aplicada "dr. Jorge Andres Zgrablich". Grupo Vinculado Bionanotecnologia y Sistemas Complejos. - Universidad Tecnologica Nacional. Facultad Reg.san Rafael. Grupo Vinculado Bionanotecnologia y Sistemas Complejos.; ArgentinaFil: Mas Pujadas, Francesc. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; EspañaFil: Garcés, Josep L.. Lleida University; EspañaMultidisciplinary Digital Publishing Institute2019-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/183029Blanco, Pablo M.; Madurga Díez, Sergio; Narambuena, Claudio Fabian; Mas Pujadas, Francesc; Garcés, Josep L.; Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes; Multidisciplinary Digital Publishing Institute; Polymers; 11; 12; 11-20192073-4360CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2073-4360/11/12/1962info:eu-repo/semantics/altIdentifier/doi/10.3390/polym11121962info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:50:42Zoai:ri.conicet.gov.ar:11336/183029instacron: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:34982025-09-29 09:50:42.559CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
title Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
spellingShingle Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
Blanco, Pablo M.
ANNEALED POLYELECTROLYTE
BINDING EQUILIBRIA
CHARGE FLUCTUATIONS
CHARGE REGULATION
CONFORMATIONAL EQUILIBRIA
CONSTANT PH ENSAMBLE
MONTE CARLO SIMULATION
POLYELECTROLYTES
SCALING LAW
SEMI-GRAND CANONICAL ENSEMBLE
STRETCHING
WEAK POLYELECTROLYTE
title_short Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
title_full Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
title_fullStr Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
title_full_unstemmed Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
title_sort Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
dc.creator.none.fl_str_mv Blanco, Pablo M.
Madurga Díez, Sergio
Narambuena, Claudio Fabian
Mas Pujadas, Francesc
Garcés, Josep L.
author Blanco, Pablo M.
author_facet Blanco, Pablo M.
Madurga Díez, Sergio
Narambuena, Claudio Fabian
Mas Pujadas, Francesc
Garcés, Josep L.
author_role author
author2 Madurga Díez, Sergio
Narambuena, Claudio Fabian
Mas Pujadas, Francesc
Garcés, Josep L.
author2_role author
author
author
author
dc.subject.none.fl_str_mv ANNEALED POLYELECTROLYTE
BINDING EQUILIBRIA
CHARGE FLUCTUATIONS
CHARGE REGULATION
CONFORMATIONAL EQUILIBRIA
CONSTANT PH ENSAMBLE
MONTE CARLO SIMULATION
POLYELECTROLYTES
SCALING LAW
SEMI-GRAND CANONICAL ENSEMBLE
STRETCHING
WEAK POLYELECTROLYTE
topic ANNEALED POLYELECTROLYTE
BINDING EQUILIBRIA
CHARGE FLUCTUATIONS
CHARGE REGULATION
CONFORMATIONAL EQUILIBRIA
CONSTANT PH ENSAMBLE
MONTE CARLO SIMULATION
POLYELECTROLYTES
SCALING LAW
SEMI-GRAND CANONICAL ENSEMBLE
STRETCHING
WEAK POLYELECTROLYTE
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv This work addresses the role of charge regulation (CR) and the associated fluctuations in the conformational and mechanical properties of weak polyelectrolytes. Due to CR, changes in the pH-value modifies the average macromolecular charge and conformational equilibria. A second effect is that, for a given average charge per site, fluctuations can alter the intensity of the interactions by means of correlation between binding sites. We investigate both effects by means of Monte Carlo simulations at constant pH-value, so that the charge is a fluctuating quantity. Once the average charge per site is available, we turn off the fluctuations by assigning the same average charge to every site. A constant charge MC simulation is then performed. We make use of a model which accounts for the main fundamental aspects of a linear flexible polyelectrolyte that is, proton binding, angle internal rotation, bond stretching and bending. Steric excluded volume and differentiated treatment for short-range and long-range interactions are also included. This model can be regarded as a kind of "minimal" in the sense that it contains a minimum number of parameters but still preserving the atomistic detail. It is shown that, if fluctuations are activated, gauche state bond probabilities increase and the persistence length decreases, so that the polymer becomes more folded. Macromolecular stretching is also analyzed in presence of CR (the charge depends on the applied force) and without CR (the charge is fixed to the value at zero force). The analysis of the low force scaling behavior concludes that Pincus exponent becomes pH-dependent. Both, with and without CR, a transition from 1/2 at high pH-values (phantom chain) to 3/5 at low pH-values (Pincus regime) is observed. Finally, the intermediate force stretching regime is investigated. It is found that CR induces a moderate influence in the force-extension curves and persistence length (which in this force regime becomes force-dependent). It is thus concluded that the effect of CR on the stretching curves is mainly due to the changes in the average charge at zero force. It is also found that, for the cases studied, the effect of steric excluded volume is almost irrelevant compared to electrostatic interactions.
Fil: Blanco, Pablo M.. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; España
Fil: Madurga Díez, Sergio. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; España
Fil: Narambuena, Claudio Fabian. Universidad Tecnologica Nacional. Facultad Regional San Rafael; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - San Luis. Instituto de Fisica Aplicada "dr. Jorge Andres Zgrablich". Grupo Vinculado Bionanotecnologia y Sistemas Complejos | Universidad Nacional de San Luis. Facultad de Cs.fisico Matematicas y Naturales. Instituto de Fisica Aplicada "dr. Jorge Andres Zgrablich". Grupo Vinculado Bionanotecnologia y Sistemas Complejos. - Universidad Tecnologica Nacional. Facultad Reg.san Rafael. Grupo Vinculado Bionanotecnologia y Sistemas Complejos.; Argentina
Fil: Mas Pujadas, Francesc. Universidad de Barcelona. Facultad de Quimica. Instituto de Quimica Teorica y Computacional.; España
Fil: Garcés, Josep L.. Lleida University; España
description This work addresses the role of charge regulation (CR) and the associated fluctuations in the conformational and mechanical properties of weak polyelectrolytes. Due to CR, changes in the pH-value modifies the average macromolecular charge and conformational equilibria. A second effect is that, for a given average charge per site, fluctuations can alter the intensity of the interactions by means of correlation between binding sites. We investigate both effects by means of Monte Carlo simulations at constant pH-value, so that the charge is a fluctuating quantity. Once the average charge per site is available, we turn off the fluctuations by assigning the same average charge to every site. A constant charge MC simulation is then performed. We make use of a model which accounts for the main fundamental aspects of a linear flexible polyelectrolyte that is, proton binding, angle internal rotation, bond stretching and bending. Steric excluded volume and differentiated treatment for short-range and long-range interactions are also included. This model can be regarded as a kind of "minimal" in the sense that it contains a minimum number of parameters but still preserving the atomistic detail. It is shown that, if fluctuations are activated, gauche state bond probabilities increase and the persistence length decreases, so that the polymer becomes more folded. Macromolecular stretching is also analyzed in presence of CR (the charge depends on the applied force) and without CR (the charge is fixed to the value at zero force). The analysis of the low force scaling behavior concludes that Pincus exponent becomes pH-dependent. Both, with and without CR, a transition from 1/2 at high pH-values (phantom chain) to 3/5 at low pH-values (Pincus regime) is observed. Finally, the intermediate force stretching regime is investigated. It is found that CR induces a moderate influence in the force-extension curves and persistence length (which in this force regime becomes force-dependent). It is thus concluded that the effect of CR on the stretching curves is mainly due to the changes in the average charge at zero force. It is also found that, for the cases studied, the effect of steric excluded volume is almost irrelevant compared to electrostatic interactions.
publishDate 2019
dc.date.none.fl_str_mv 2019-11
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/11336/183029
Blanco, Pablo M.; Madurga Díez, Sergio; Narambuena, Claudio Fabian; Mas Pujadas, Francesc; Garcés, Josep L.; Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes; Multidisciplinary Digital Publishing Institute; Polymers; 11; 12; 11-2019
2073-4360
CONICET Digital
CONICET
url http://hdl.handle.net/11336/183029
identifier_str_mv Blanco, Pablo M.; Madurga Díez, Sergio; Narambuena, Claudio Fabian; Mas Pujadas, Francesc; Garcés, Josep L.; Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes; Multidisciplinary Digital Publishing Institute; Polymers; 11; 12; 11-2019
2073-4360
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://www.mdpi.com/2073-4360/11/12/1962
info:eu-repo/semantics/altIdentifier/doi/10.3390/polym11121962
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 Multidisciplinary Digital Publishing Institute
publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
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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