Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network

Autores
Gruber, Alexandra; Navarro, Lucila; Klinger, Daniel
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Amphiphilic nanogels (NGs) combine a soft, water-swollen hydrogel matrix with internal hydrophobic domains. While these domains can encapsulate hydrophobic cargoes, the amphiphilic particle surface can reduce colloidal stability and/or limit biological half-life. Therefore, a functional hydrophilic shell is needed to shield the amphiphilic network and tune interactions with biological systems. To adjust core and shell properties independently, we developed a synthetic strategy that uses preformed dual-reactive nanogels. In a first step, emulsion copolymerization of pentafluorophenyl methacrylate (PFPMA) and a reduction-cleavable crosslinker produced precursor particles for subsequent network modification. Orthogonal shell reactivity was installed by using an amphiphilic block copolymer (BCP) surfactant during this particle preparation step. Here, the hydrophilic block poly(polyethylene glycol methyl ether methacrylate) (PPEGMA) contains a reactive alkyne end group for successive functionalization. The hydrophobic block (P(PFPMA-co-MAPMA) contains random methacryl-amido propyl methacrylamide (MAPMA) units to covalently attach the surfactant to the growing PPFPMA network. In the second step, orthogonal modification of the core and shell was demonstrated. Network functionalization with combinations of hydrophilic (acidic, neutral, or basic) and hydrophobic (cholesterol) groups gave a library of pH- and redox-sensitive amphiphilic NGs. Stimuli-responsive properties were demonstrated by pH-dependent swelling and reduction-induced degradation via dynamic light scattering. Subsequently, copper-catalyzed azide-alkyne cycloaddition was used to attach azide-modified rhodamine as model compound to the shell (followed by UV-Vis). Overall, this strategy provides a versatile platform to develop multi-functional amphiphilic nanogels as carriers for hydrophobic cargoes.
Fil: Gruber, Alexandra. Freie Universität Berlin; Alemania
Fil: Navarro, Lucila. Freie Universität Berlin; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Klinger, Daniel. Freie Universität Berlin; Alemania
Materia
Nanogel
Anfifilico
Modificacion quimica
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:11336/215904
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic networkGruber, AlexandraNavarro, LucilaKlinger, DanielNanogelAnfifilicoModificacion quimicahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Amphiphilic nanogels (NGs) combine a soft, water-swollen hydrogel matrix with internal hydrophobic domains. While these domains can encapsulate hydrophobic cargoes, the amphiphilic particle surface can reduce colloidal stability and/or limit biological half-life. Therefore, a functional hydrophilic shell is needed to shield the amphiphilic network and tune interactions with biological systems. To adjust core and shell properties independently, we developed a synthetic strategy that uses preformed dual-reactive nanogels. In a first step, emulsion copolymerization of pentafluorophenyl methacrylate (PFPMA) and a reduction-cleavable crosslinker produced precursor particles for subsequent network modification. Orthogonal shell reactivity was installed by using an amphiphilic block copolymer (BCP) surfactant during this particle preparation step. Here, the hydrophilic block poly(polyethylene glycol methyl ether methacrylate) (PPEGMA) contains a reactive alkyne end group for successive functionalization. The hydrophobic block (P(PFPMA-co-MAPMA) contains random methacryl-amido propyl methacrylamide (MAPMA) units to covalently attach the surfactant to the growing PPFPMA network. In the second step, orthogonal modification of the core and shell was demonstrated. Network functionalization with combinations of hydrophilic (acidic, neutral, or basic) and hydrophobic (cholesterol) groups gave a library of pH- and redox-sensitive amphiphilic NGs. Stimuli-responsive properties were demonstrated by pH-dependent swelling and reduction-induced degradation via dynamic light scattering. Subsequently, copper-catalyzed azide-alkyne cycloaddition was used to attach azide-modified rhodamine as model compound to the shell (followed by UV-Vis). Overall, this strategy provides a versatile platform to develop multi-functional amphiphilic nanogels as carriers for hydrophobic cargoes.Fil: Gruber, Alexandra. Freie Universität Berlin; AlemaniaFil: Navarro, Lucila. Freie Universität Berlin; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Klinger, Daniel. Freie Universität Berlin; AlemaniaRoyal Society of Chemistry2022-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/215904Gruber, Alexandra; Navarro, Lucila; Klinger, Daniel; Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network; Royal Society of Chemistry; Soft Matter; 18; 14; 3-2022; 2858-28711744-683XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/D2SM00116Kinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2022/SM/D2SM00116Kinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:04:07Zoai:ri.conicet.gov.ar:11336/215904instacron: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 15:04:07.47CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
title Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
spellingShingle Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
Gruber, Alexandra
Nanogel
Anfifilico
Modificacion quimica
title_short Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
title_full Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
title_fullStr Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
title_full_unstemmed Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
title_sort Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network
dc.creator.none.fl_str_mv Gruber, Alexandra
Navarro, Lucila
Klinger, Daniel
author Gruber, Alexandra
author_facet Gruber, Alexandra
Navarro, Lucila
Klinger, Daniel
author_role author
author2 Navarro, Lucila
Klinger, Daniel
author2_role author
author
dc.subject.none.fl_str_mv Nanogel
Anfifilico
Modificacion quimica
topic Nanogel
Anfifilico
Modificacion quimica
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Amphiphilic nanogels (NGs) combine a soft, water-swollen hydrogel matrix with internal hydrophobic domains. While these domains can encapsulate hydrophobic cargoes, the amphiphilic particle surface can reduce colloidal stability and/or limit biological half-life. Therefore, a functional hydrophilic shell is needed to shield the amphiphilic network and tune interactions with biological systems. To adjust core and shell properties independently, we developed a synthetic strategy that uses preformed dual-reactive nanogels. In a first step, emulsion copolymerization of pentafluorophenyl methacrylate (PFPMA) and a reduction-cleavable crosslinker produced precursor particles for subsequent network modification. Orthogonal shell reactivity was installed by using an amphiphilic block copolymer (BCP) surfactant during this particle preparation step. Here, the hydrophilic block poly(polyethylene glycol methyl ether methacrylate) (PPEGMA) contains a reactive alkyne end group for successive functionalization. The hydrophobic block (P(PFPMA-co-MAPMA) contains random methacryl-amido propyl methacrylamide (MAPMA) units to covalently attach the surfactant to the growing PPFPMA network. In the second step, orthogonal modification of the core and shell was demonstrated. Network functionalization with combinations of hydrophilic (acidic, neutral, or basic) and hydrophobic (cholesterol) groups gave a library of pH- and redox-sensitive amphiphilic NGs. Stimuli-responsive properties were demonstrated by pH-dependent swelling and reduction-induced degradation via dynamic light scattering. Subsequently, copper-catalyzed azide-alkyne cycloaddition was used to attach azide-modified rhodamine as model compound to the shell (followed by UV-Vis). Overall, this strategy provides a versatile platform to develop multi-functional amphiphilic nanogels as carriers for hydrophobic cargoes.
Fil: Gruber, Alexandra. Freie Universität Berlin; Alemania
Fil: Navarro, Lucila. Freie Universität Berlin; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Klinger, Daniel. Freie Universität Berlin; Alemania
description Amphiphilic nanogels (NGs) combine a soft, water-swollen hydrogel matrix with internal hydrophobic domains. While these domains can encapsulate hydrophobic cargoes, the amphiphilic particle surface can reduce colloidal stability and/or limit biological half-life. Therefore, a functional hydrophilic shell is needed to shield the amphiphilic network and tune interactions with biological systems. To adjust core and shell properties independently, we developed a synthetic strategy that uses preformed dual-reactive nanogels. In a first step, emulsion copolymerization of pentafluorophenyl methacrylate (PFPMA) and a reduction-cleavable crosslinker produced precursor particles for subsequent network modification. Orthogonal shell reactivity was installed by using an amphiphilic block copolymer (BCP) surfactant during this particle preparation step. Here, the hydrophilic block poly(polyethylene glycol methyl ether methacrylate) (PPEGMA) contains a reactive alkyne end group for successive functionalization. The hydrophobic block (P(PFPMA-co-MAPMA) contains random methacryl-amido propyl methacrylamide (MAPMA) units to covalently attach the surfactant to the growing PPFPMA network. In the second step, orthogonal modification of the core and shell was demonstrated. Network functionalization with combinations of hydrophilic (acidic, neutral, or basic) and hydrophobic (cholesterol) groups gave a library of pH- and redox-sensitive amphiphilic NGs. Stimuli-responsive properties were demonstrated by pH-dependent swelling and reduction-induced degradation via dynamic light scattering. Subsequently, copper-catalyzed azide-alkyne cycloaddition was used to attach azide-modified rhodamine as model compound to the shell (followed by UV-Vis). Overall, this strategy provides a versatile platform to develop multi-functional amphiphilic nanogels as carriers for hydrophobic cargoes.
publishDate 2022
dc.date.none.fl_str_mv 2022-03
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/11336/215904
Gruber, Alexandra; Navarro, Lucila; Klinger, Daniel; Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network; Royal Society of Chemistry; Soft Matter; 18; 14; 3-2022; 2858-2871
1744-683X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/215904
identifier_str_mv Gruber, Alexandra; Navarro, Lucila; Klinger, Daniel; Dual-reactive nanogels for orthogonal functionalization of hydrophilic shell and amphiphilic network; Royal Society of Chemistry; Soft Matter; 18; 14; 3-2022; 2858-2871
1744-683X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/D2SM00116K
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2022/SM/D2SM00116K
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
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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score 13.22299

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