Gel formation in reversibly cross-linking polymers

By means of Langevin dynamics simulations, we investigate the gel formation of randomly functionalized polymers in solution, with the ability to form both intra- and intermolecular reversible bonds. Under highly dilute conditions, these polymers form soft nano-objects (so-called single-chain nanopar...

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Autores: Formanek, Maud, Rovigatti, Lorenzo, Zaccarelli, Emanuela, Sciortino, Francesco, Moreno Segurado, Ángel J.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/258593
Acceso en línea:http://hdl.handle.net/10261/258593
Access Level:acceso abierto
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spelling Gel formation in reversibly cross-linking polymersFormanek, MaudRovigatti, LorenzoZaccarelli, EmanuelaSciortino, FrancescoMoreno Segurado, Ángel J.By means of Langevin dynamics simulations, we investigate the gel formation of randomly functionalized polymers in solution, with the ability to form both intra- and intermolecular reversible bonds. Under highly dilute conditions, these polymers form soft nano-objects (so-called single-chain nanoparticles, SCNPs), resulting from the purely intramolecular cross-linking of the reactive functional groups. Here, we show that the competition between intra- and intermolecular bonds at finite concentration is governed by a delicate balance of various entropic contributions and leads to a density-dependent effective valence. System-spanning networks are formed at relatively low monomer densities and their stability is mediated by just a small number of intermolecular connections per chain. The formation of intermolecular bonds furthermore can induce a nonmonotonic dependence of the polymer size on the density for long bond lifetimes. Concomitantly, the polymers in the percolating cluster adopt an intramolecular structure characteristic for self-avoiding chains, which constitutes a strong contrast to the fractal globular behavior of intramolecularly cross-linked SCNPs in crowded solutions with purely topological interactions (no intermolecular bonds). Finally, we study the dynamics of the system, which displays signatures expected for reversible gel-forming systems. An interesting behavior emerges in the reorganization dynamics of the percolating cluster: the relaxation is mostly mediated by the diffusion over long distances, through breaking and formation of bonds, of chains that do not leave the percolating cluster. Regarding the few chains that are transiently free, the time they spend until they reattach to the cluster is solely governed by the bond strength.We acknowledge support from the projects PGC2018-094548-B-I00 (MCIU/AEI/FEDER, UE) and IT-1175-19 (Basque Government, Spain). M.F. acknowledges travel grants from Materials Physics Center (San Sebastián, Spain).We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).Peer reviewedAmerican Chemical SocietyCSIC - Unidad de Recursos de Información Científica para la Investigación (URICI)Agencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)Donostia International Physics CenterEusko JaurlaritzaEuropean CommissionConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202220222021info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/258593reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-094548-B-I0https://doi.org/10.1021/acs.macromol.0c02670Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2585932026-05-22T06:33:51Z
dc.title.none.fl_str_mv Gel formation in reversibly cross-linking polymers
title Gel formation in reversibly cross-linking polymers
spellingShingle Gel formation in reversibly cross-linking polymers
Formanek, Maud
title_short Gel formation in reversibly cross-linking polymers
title_full Gel formation in reversibly cross-linking polymers
title_fullStr Gel formation in reversibly cross-linking polymers
title_full_unstemmed Gel formation in reversibly cross-linking polymers
title_sort Gel formation in reversibly cross-linking polymers
dc.creator.none.fl_str_mv Formanek, Maud
Rovigatti, Lorenzo
Zaccarelli, Emanuela
Sciortino, Francesco
Moreno Segurado, Ángel J.
author Formanek, Maud
author_facet Formanek, Maud
Rovigatti, Lorenzo
Zaccarelli, Emanuela
Sciortino, Francesco
Moreno Segurado, Ángel J.
author_role author
author2 Rovigatti, Lorenzo
Zaccarelli, Emanuela
Sciortino, Francesco
Moreno Segurado, Ángel J.
author2_role author
author
author
author
dc.contributor.none.fl_str_mv CSIC - Unidad de Recursos de Información Científica para la Investigación (URICI)
Agencia Estatal de Investigación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Donostia International Physics Center
Eusko Jaurlaritza
European Commission
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description By means of Langevin dynamics simulations, we investigate the gel formation of randomly functionalized polymers in solution, with the ability to form both intra- and intermolecular reversible bonds. Under highly dilute conditions, these polymers form soft nano-objects (so-called single-chain nanoparticles, SCNPs), resulting from the purely intramolecular cross-linking of the reactive functional groups. Here, we show that the competition between intra- and intermolecular bonds at finite concentration is governed by a delicate balance of various entropic contributions and leads to a density-dependent effective valence. System-spanning networks are formed at relatively low monomer densities and their stability is mediated by just a small number of intermolecular connections per chain. The formation of intermolecular bonds furthermore can induce a nonmonotonic dependence of the polymer size on the density for long bond lifetimes. Concomitantly, the polymers in the percolating cluster adopt an intramolecular structure characteristic for self-avoiding chains, which constitutes a strong contrast to the fractal globular behavior of intramolecularly cross-linked SCNPs in crowded solutions with purely topological interactions (no intermolecular bonds). Finally, we study the dynamics of the system, which displays signatures expected for reversible gel-forming systems. An interesting behavior emerges in the reorganization dynamics of the percolating cluster: the relaxation is mostly mediated by the diffusion over long distances, through breaking and formation of bonds, of chains that do not leave the percolating cluster. Regarding the few chains that are transiently free, the time they spend until they reattach to the cluster is solely governed by the bond strength.
publishDate 2021
dc.date.none.fl_str_mv 2021
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/258593
url http://hdl.handle.net/10261/258593
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-094548-B-I0
https://doi.org/10.1021/acs.macromol.0c02670
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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