Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering

Autores
Fernandez Bordin, Santiago Pablo; Rufeil Fiori, Elena; Padró, J. M.; Galván Josa, Víctor Martín; Plivelic, T. S.; Romero, Marcelo Ricardo
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Stimuli-responsive polymers stand out for their ability to respond to small environmental changes. One of the most representative thermo-sensitive materials is poly(N-isopropyl acrylamide) (PNIPAm), which presents reversible phase transitions close to the human body temperature. However, previous studies observed that the copolymerization of NIPAm with small quantities of different monomers like acrylic acid (AAc) results in copolymers with reduced or lost thermo-responsivity. In this study, thermosensitive PNIPAm, pH-sensitive poly(acrylic acid) (PAAc), and various proportions of their copolymers P(NIPAm-co-AAc) were obtained by free radical polymerization and thoroughly characterized. Rheological and structural studies reveal the remaining thermosensitivity of the copolymers manifested at short molecular ranges. These alterations in short-range interactions are observed in all samples containing NIPAm, and they are evidenced by changes in the fractality of their structure and flow index behavior of the Viscosity Ostwald–de Waele Model. Particularly, when the copolymer proportion of NIPAm/AAc is about 40/60, the Beaucage model reveals two structural levels, ~200 and ~10nm. Furthermore, the model exhibits a thermal response of the lower-size substructures, indicating possible segregation of NIPAm-rich regions from copolymer chains. The evidence found in this work could contribute to the development of nanosystems, in which local thermoresponsive effects are sought, such as for active drug targeting.
Fil: Fernandez Bordin, Santiago Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina. Lund University; Suecia
Fil: Rufeil Fiori, Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Padró, J. M.. YPF - Tecnología; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; Argentina
Fil: Galván Josa, Víctor Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Plivelic, T. S.. Lund University; Suecia
Fil: Romero, Marcelo Ricardo. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina
Materia
Beaucage model
Fractality
Ostwald–de Waele model
PNIPAm
PNIPAm copolymers
Small-angle x-ray scattering
Thermo-sensitive polymers
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/250554
Acceder
id CONICETDig_52efbbcc7f6cae9a3c976842580c464c
oai_identifier_str oai:ri.conicet.gov.ar:11336/250554
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray ScatteringFernandez Bordin, Santiago PabloRufeil Fiori, ElenaPadró, J. M.Galván Josa, Víctor MartínPlivelic, T. S.Romero, Marcelo RicardoBeaucage modelFractalityOstwald–de Waele modelPNIPAmPNIPAm copolymersSmall-angle x-ray scatteringThermo-sensitive polymershttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Stimuli-responsive polymers stand out for their ability to respond to small environmental changes. One of the most representative thermo-sensitive materials is poly(N-isopropyl acrylamide) (PNIPAm), which presents reversible phase transitions close to the human body temperature. However, previous studies observed that the copolymerization of NIPAm with small quantities of different monomers like acrylic acid (AAc) results in copolymers with reduced or lost thermo-responsivity. In this study, thermosensitive PNIPAm, pH-sensitive poly(acrylic acid) (PAAc), and various proportions of their copolymers P(NIPAm-co-AAc) were obtained by free radical polymerization and thoroughly characterized. Rheological and structural studies reveal the remaining thermosensitivity of the copolymers manifested at short molecular ranges. These alterations in short-range interactions are observed in all samples containing NIPAm, and they are evidenced by changes in the fractality of their structure and flow index behavior of the Viscosity Ostwald–de Waele Model. Particularly, when the copolymer proportion of NIPAm/AAc is about 40/60, the Beaucage model reveals two structural levels, ~200 and ~10nm. Furthermore, the model exhibits a thermal response of the lower-size substructures, indicating possible segregation of NIPAm-rich regions from copolymer chains. The evidence found in this work could contribute to the development of nanosystems, in which local thermoresponsive effects are sought, such as for active drug targeting.Fil: Fernandez Bordin, Santiago Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina. Lund University; SueciaFil: Rufeil Fiori, Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; ArgentinaFil: Padró, J. M.. YPF - Tecnología; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; ArgentinaFil: Galván Josa, Víctor Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; ArgentinaFil: Plivelic, T. S.. Lund University; SueciaFil: Romero, Marcelo Ricardo. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; ArgentinaJohn Wiley & Sons2024-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/250554Fernandez Bordin, Santiago Pablo; Rufeil Fiori, Elena; Padró, J. M.; Galván Josa, Víctor Martín; Plivelic, T. S.; et al.; Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering; John Wiley & Sons; Journal of Polymer Science; 2024; 11-2024; 1-132642-41502642-4169CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/pol.20240799info:eu-repo/semantics/altIdentifier/doi/10.1002/pol.20240799info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:50:47Zoai:ri.conicet.gov.ar:11336/250554instacron: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:34982025-09-03 09:50:47.551CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
title Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
spellingShingle Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
Fernandez Bordin, Santiago Pablo
Beaucage model
Fractality
Ostwald–de Waele model
PNIPAm
PNIPAm copolymers
Small-angle x-ray scattering
Thermo-sensitive polymers
title_short Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
title_full Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
title_fullStr Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
title_full_unstemmed Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
title_sort Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering
dc.creator.none.fl_str_mv Fernandez Bordin, Santiago Pablo
Rufeil Fiori, Elena
Padró, J. M.
Galván Josa, Víctor Martín
Plivelic, T. S.
Romero, Marcelo Ricardo
author Fernandez Bordin, Santiago Pablo
author_facet Fernandez Bordin, Santiago Pablo
Rufeil Fiori, Elena
Padró, J. M.
Galván Josa, Víctor Martín
Plivelic, T. S.
Romero, Marcelo Ricardo
author_role author
author2 Rufeil Fiori, Elena
Padró, J. M.
Galván Josa, Víctor Martín
Plivelic, T. S.
Romero, Marcelo Ricardo
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Beaucage model
Fractality
Ostwald–de Waele model
PNIPAm
PNIPAm copolymers
Small-angle x-ray scattering
Thermo-sensitive polymers
topic Beaucage model
Fractality
Ostwald–de Waele model
PNIPAm
PNIPAm copolymers
Small-angle x-ray scattering
Thermo-sensitive polymers
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Stimuli-responsive polymers stand out for their ability to respond to small environmental changes. One of the most representative thermo-sensitive materials is poly(N-isopropyl acrylamide) (PNIPAm), which presents reversible phase transitions close to the human body temperature. However, previous studies observed that the copolymerization of NIPAm with small quantities of different monomers like acrylic acid (AAc) results in copolymers with reduced or lost thermo-responsivity. In this study, thermosensitive PNIPAm, pH-sensitive poly(acrylic acid) (PAAc), and various proportions of their copolymers P(NIPAm-co-AAc) were obtained by free radical polymerization and thoroughly characterized. Rheological and structural studies reveal the remaining thermosensitivity of the copolymers manifested at short molecular ranges. These alterations in short-range interactions are observed in all samples containing NIPAm, and they are evidenced by changes in the fractality of their structure and flow index behavior of the Viscosity Ostwald–de Waele Model. Particularly, when the copolymer proportion of NIPAm/AAc is about 40/60, the Beaucage model reveals two structural levels, ~200 and ~10nm. Furthermore, the model exhibits a thermal response of the lower-size substructures, indicating possible segregation of NIPAm-rich regions from copolymer chains. The evidence found in this work could contribute to the development of nanosystems, in which local thermoresponsive effects are sought, such as for active drug targeting.
Fil: Fernandez Bordin, Santiago Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina. Lund University; Suecia
Fil: Rufeil Fiori, Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Padró, J. M.. YPF - Tecnología; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; Argentina
Fil: Galván Josa, Víctor Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Plivelic, T. S.. Lund University; Suecia
Fil: Romero, Marcelo Ricardo. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina
description Stimuli-responsive polymers stand out for their ability to respond to small environmental changes. One of the most representative thermo-sensitive materials is poly(N-isopropyl acrylamide) (PNIPAm), which presents reversible phase transitions close to the human body temperature. However, previous studies observed that the copolymerization of NIPAm with small quantities of different monomers like acrylic acid (AAc) results in copolymers with reduced or lost thermo-responsivity. In this study, thermosensitive PNIPAm, pH-sensitive poly(acrylic acid) (PAAc), and various proportions of their copolymers P(NIPAm-co-AAc) were obtained by free radical polymerization and thoroughly characterized. Rheological and structural studies reveal the remaining thermosensitivity of the copolymers manifested at short molecular ranges. These alterations in short-range interactions are observed in all samples containing NIPAm, and they are evidenced by changes in the fractality of their structure and flow index behavior of the Viscosity Ostwald–de Waele Model. Particularly, when the copolymer proportion of NIPAm/AAc is about 40/60, the Beaucage model reveals two structural levels, ~200 and ~10nm. Furthermore, the model exhibits a thermal response of the lower-size substructures, indicating possible segregation of NIPAm-rich regions from copolymer chains. The evidence found in this work could contribute to the development of nanosystems, in which local thermoresponsive effects are sought, such as for active drug targeting.
publishDate 2024
dc.date.none.fl_str_mv 2024-11
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/11336/250554
Fernandez Bordin, Santiago Pablo; Rufeil Fiori, Elena; Padró, J. M.; Galván Josa, Víctor Martín; Plivelic, T. S.; et al.; Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering; John Wiley & Sons; Journal of Polymer Science; 2024; 11-2024; 1-13
2642-4150
2642-4169
CONICET Digital
CONICET
url http://hdl.handle.net/11336/250554
identifier_str_mv Fernandez Bordin, Santiago Pablo; Rufeil Fiori, Elena; Padró, J. M.; Galván Josa, Víctor Martín; Plivelic, T. S.; et al.; Localized Thermoresponsive Behavior in P( NIPAm ‐ co ‐ AAc ) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering; John Wiley & Sons; Journal of Polymer Science; 2024; 11-2024; 1-13
2642-4150
2642-4169
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://onlinelibrary.wiley.com/doi/10.1002/pol.20240799
info:eu-repo/semantics/altIdentifier/doi/10.1002/pol.20240799
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons
publisher.none.fl_str_mv John Wiley & Sons
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
_version_ 1842269053505241088
score 13.13397

Publicaciones similares