Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin

Autores
Giussi, Juan Martín; Velasco, Manuel Isaac; Longo, Gabriel Sebastian; Acosta, Rodolfo Hector; Azzaroni, Omar
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In the traditional view of temperature-driven volume phase transitions in PNIPAm-based microgelsolutions, a monotonic and sharp decrease in particle size occurs upon heating the solution abovethe volume phase transition temperature (VPTT). However, at sufficiently high microgelconcentrations and low salt conditions, our dynamic light scattering experiments reveal anunexpected non-monotonic evolution of particle size when increasing the solution temperature.These findings show that poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA))microgels swell upon heating the solution in the temperature range where NIPAM is water-soluble(i.e., below the VPPT). Further heating the microgel solution leads to microgel collapse as typicallyobserved at temperatures above the VPTT. This novel behavior depends on particle and saltconcentration. We have observed the expected monotonic temperature-response of P(NIPAm-co-MAA) microgel solutions at low particle density and high salt concentration. To gain insights intothe molecular origin of the unusual behavior of these microgel solutions, we have combined nuclearmagnetic resonance studies and molecular-level theoretical calculations of the system. A delicatebalance between inter-particle steric compressions and intra-microgel physical interactions andchemical equilibria determines the size of these microgels. Both steric compression, due to finitedensity, and hydrogen bond formation in the interior of the microgels favor a more compactparticle. On the contrary, at the pH of the experiments the acid-base equilibrium constraints thepolymer charge to increase, which favors particle swelling due to intra-microgel electrostaticrepulsions. This interplay between physical interactions and chemical equilibria occurring at thenanometer length-scale determines the unusual thermal-induced swelling of P(NIPAm-co-MAA)
Fil: Giussi, Juan Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Velasco, Manuel Isaac. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Física "enrique Gaviola"; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Longo, Gabriel Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Acosta, Rodolfo Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Física "enrique Gaviola"; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Materia
POLYMER
NIPAM
NMR
Nivel de accesibilidad
acceso embargado
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:11336/5449
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/5449
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular OriginGiussi, Juan MartínVelasco, Manuel IsaacLongo, Gabriel SebastianAcosta, Rodolfo HectorAzzaroni, OmarPOLYMERNIPAMNMRhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In the traditional view of temperature-driven volume phase transitions in PNIPAm-based microgelsolutions, a monotonic and sharp decrease in particle size occurs upon heating the solution abovethe volume phase transition temperature (VPTT). However, at sufficiently high microgelconcentrations and low salt conditions, our dynamic light scattering experiments reveal anunexpected non-monotonic evolution of particle size when increasing the solution temperature.These findings show that poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA))microgels swell upon heating the solution in the temperature range where NIPAM is water-soluble(i.e., below the VPPT). Further heating the microgel solution leads to microgel collapse as typicallyobserved at temperatures above the VPTT. This novel behavior depends on particle and saltconcentration. We have observed the expected monotonic temperature-response of P(NIPAm-co-MAA) microgel solutions at low particle density and high salt concentration. To gain insights intothe molecular origin of the unusual behavior of these microgel solutions, we have combined nuclearmagnetic resonance studies and molecular-level theoretical calculations of the system. A delicatebalance between inter-particle steric compressions and intra-microgel physical interactions andchemical equilibria determines the size of these microgels. Both steric compression, due to finitedensity, and hydrogen bond formation in the interior of the microgels favor a more compactparticle. On the contrary, at the pH of the experiments the acid-base equilibrium constraints thepolymer charge to increase, which favors particle swelling due to intra-microgel electrostaticrepulsions. This interplay between physical interactions and chemical equilibria occurring at thenanometer length-scale determines the unusual thermal-induced swelling of P(NIPAm-co-MAA)Fil: Giussi, Juan Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Velasco, Manuel Isaac. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Física "enrique Gaviola"; Argentina. Universidad Nacional de Córdoba; ArgentinaFil: Longo, Gabriel Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Acosta, Rodolfo Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Física "enrique Gaviola"; Argentina. Universidad Nacional de Córdoba; ArgentinaFil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaRoyal Society of Chemistry2015-09info:eu-repo/date/embargoEnd/2016-10-03info: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/11336/5449Giussi, Juan Martín; Velasco, Manuel Isaac; Longo, Gabriel Sebastian; Acosta, Rodolfo Hector; Azzaroni, Omar; Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin; Royal Society of Chemistry; Soft Matter; 11; 45; 9-2015; 8879-88861744-683Xenginfo:eu-repo/semantics/altIdentifier/pmid/26400774info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/SM/C5SM01853F#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C5SM01853Finfo:eu-repo/semantics/embargoedAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:34:33Zoai:ri.conicet.gov.ar:11336/5449instacron: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 09:34:34.169CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
title Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
spellingShingle Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
Giussi, Juan Martín
POLYMER
NIPAM
NMR
title_short Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
title_full Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
title_fullStr Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
title_full_unstemmed Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
title_sort Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin
dc.creator.none.fl_str_mv Giussi, Juan Martín
Velasco, Manuel Isaac
Longo, Gabriel Sebastian
Acosta, Rodolfo Hector
Azzaroni, Omar
author Giussi, Juan Martín
author_facet Giussi, Juan Martín
Velasco, Manuel Isaac
Longo, Gabriel Sebastian
Acosta, Rodolfo Hector
Azzaroni, Omar
author_role author
author2 Velasco, Manuel Isaac
Longo, Gabriel Sebastian
Acosta, Rodolfo Hector
Azzaroni, Omar
author2_role author
author
author
author
dc.subject.none.fl_str_mv POLYMER
NIPAM
NMR
topic POLYMER
NIPAM
NMR
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In the traditional view of temperature-driven volume phase transitions in PNIPAm-based microgelsolutions, a monotonic and sharp decrease in particle size occurs upon heating the solution abovethe volume phase transition temperature (VPTT). However, at sufficiently high microgelconcentrations and low salt conditions, our dynamic light scattering experiments reveal anunexpected non-monotonic evolution of particle size when increasing the solution temperature.These findings show that poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA))microgels swell upon heating the solution in the temperature range where NIPAM is water-soluble(i.e., below the VPPT). Further heating the microgel solution leads to microgel collapse as typicallyobserved at temperatures above the VPTT. This novel behavior depends on particle and saltconcentration. We have observed the expected monotonic temperature-response of P(NIPAm-co-MAA) microgel solutions at low particle density and high salt concentration. To gain insights intothe molecular origin of the unusual behavior of these microgel solutions, we have combined nuclearmagnetic resonance studies and molecular-level theoretical calculations of the system. A delicatebalance between inter-particle steric compressions and intra-microgel physical interactions andchemical equilibria determines the size of these microgels. Both steric compression, due to finitedensity, and hydrogen bond formation in the interior of the microgels favor a more compactparticle. On the contrary, at the pH of the experiments the acid-base equilibrium constraints thepolymer charge to increase, which favors particle swelling due to intra-microgel electrostaticrepulsions. This interplay between physical interactions and chemical equilibria occurring at thenanometer length-scale determines the unusual thermal-induced swelling of P(NIPAm-co-MAA)
Fil: Giussi, Juan Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Velasco, Manuel Isaac. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Física "enrique Gaviola"; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Longo, Gabriel Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Acosta, Rodolfo Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Física "enrique Gaviola"; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
description In the traditional view of temperature-driven volume phase transitions in PNIPAm-based microgelsolutions, a monotonic and sharp decrease in particle size occurs upon heating the solution abovethe volume phase transition temperature (VPTT). However, at sufficiently high microgelconcentrations and low salt conditions, our dynamic light scattering experiments reveal anunexpected non-monotonic evolution of particle size when increasing the solution temperature.These findings show that poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA))microgels swell upon heating the solution in the temperature range where NIPAM is water-soluble(i.e., below the VPPT). Further heating the microgel solution leads to microgel collapse as typicallyobserved at temperatures above the VPTT. This novel behavior depends on particle and saltconcentration. We have observed the expected monotonic temperature-response of P(NIPAm-co-MAA) microgel solutions at low particle density and high salt concentration. To gain insights intothe molecular origin of the unusual behavior of these microgel solutions, we have combined nuclearmagnetic resonance studies and molecular-level theoretical calculations of the system. A delicatebalance between inter-particle steric compressions and intra-microgel physical interactions andchemical equilibria determines the size of these microgels. Both steric compression, due to finitedensity, and hydrogen bond formation in the interior of the microgels favor a more compactparticle. On the contrary, at the pH of the experiments the acid-base equilibrium constraints thepolymer charge to increase, which favors particle swelling due to intra-microgel electrostaticrepulsions. This interplay between physical interactions and chemical equilibria occurring at thenanometer length-scale determines the unusual thermal-induced swelling of P(NIPAm-co-MAA)
publishDate 2015
dc.date.none.fl_str_mv 2015-09
info:eu-repo/date/embargoEnd/2016-10-03
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/11336/5449
Giussi, Juan Martín; Velasco, Manuel Isaac; Longo, Gabriel Sebastian; Acosta, Rodolfo Hector; Azzaroni, Omar; Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin; Royal Society of Chemistry; Soft Matter; 11; 45; 9-2015; 8879-8886
1744-683X
url http://hdl.handle.net/11336/5449
identifier_str_mv Giussi, Juan Martín; Velasco, Manuel Isaac; Longo, Gabriel Sebastian; Acosta, Rodolfo Hector; Azzaroni, Omar; Unusual Temperature-Induced Swelling of Ionizable Poly(N-isopropylacrylamide)-Based Microgels: Experimental and Theoretical Insights into its Molecular Origin; Royal Society of Chemistry; Soft Matter; 11; 45; 9-2015; 8879-8886
1744-683X
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/pmid/26400774
info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/SM/C5SM01853F#!divAbstract
info:eu-repo/semantics/altIdentifier/doi/10.1039/C5SM01853F
dc.rights.none.fl_str_mv info:eu-repo/semantics/embargoedAccess
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eu_rights_str_mv embargoedAccess
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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