Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks

In this work, a set of well-defined linear triblock copolymers and star block copolymers (3 and 4-arms) with semi-crystalline blocks consisting of poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL), synthesized by combining ring-opening polymerization and organic catalyst switch strategy, wer...

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Autores: Centeno, E., Peñas, Mario I., Zhan, P., Mercado-Rico, J., Matxinandiarena, E., Zubitur, M., Mugica, A., Hadjichristidis, N., Müller, A. J., Hernández, Rebeca
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/342631
Acceso en línea:http://hdl.handle.net/10261/342631
Access Level:acceso abierto
Palabra clave:Hydrogels
Amphiphilic triblock copolymers
Star block copolymers
3D direct ink printing
Biomaterial inks
Crystallinity
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spelling Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocksCenteno, E.Peñas, Mario I.Zhan, P.Mercado-Rico, J.Matxinandiarena, E.Zubitur, M.Mugica, A.Hadjichristidis, N.Müller, A. J.Hernández, RebecaHydrogelsAmphiphilic triblock copolymersStar block copolymers3D direct ink printingBiomaterial inksCrystallinityIn this work, a set of well-defined linear triblock copolymers and star block copolymers (3 and 4-arms) with semi-crystalline blocks consisting of poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL), synthesized by combining ring-opening polymerization and organic catalyst switch strategy, were studied as thermosensitive gel-forming biomaterials for applications in 3D extrusion printing. The hydrogels derived from linear copolymers underwent a temperature-dependent sol–gel–sol transition, behaving as a flowing sol at room temperature and transforming into a non-flowing gel upon heating. On the other hand, the hydrogels derived from 4-arm star block copolymers experienced a gel-sol transition and did not flow at room temperature. This behavior allowed them to be used as 3D printing inks at room temperature. 3D printing results revealed that the semi-crystalline hydrogels of the 4-arm star block copolymers could not only be extruded and printed with high shape fidelity, but they also exhibited a favorable dissolution profile for their use as sacrificial biomaterial inks. Additionally, we thoroughly investigated the crystalline organization of the PCL and the PEO blocks within the hydrogels through comparison with the results obtained in bulk. The results demonstrated evident structural ordering in the hydrogels associated with the crystallization of the PCL blocks. Unexpectedly, DSC results combined with SAXS experiments revealed the presence of PEO block crystals within the 30 % w/v hydrogels from 4-arm star block copolymers, in addition to the PCL block crystals. Hence, remarkable double crystalline hydrogels have been obtained for the first time.This research was financially supported by the projects PID2020- 113045GB-C21 and PID2020-113045GB-C22 funded by MCIN/ AEI /10.13039/501100011033 and by the Basque Government through grant IT1503-22. M.I.P. acknowledges funding through an FPI contract (PRE2018-086104) to develop a PhD thesis. The support of the ALBA (2022086944 and 2022086957 proposals) synchrotron facility is gratefully acknowledged. R.H. is a member of the CSIC Interdisciplinary Thematic Platform (PTI+) Interdisciplinary Platform for Sustainable Plastics towards a Circular Economy+ (PTI-SusPlast+) and the PTI CSIC FAB3D. The authors would also like to thank Alejandro Hernandez-Sosa for assistance regarding 3D printing experiments. P.Z., V.L., and N.H. gratefully acknowledge the support of the King Abdullah University of Science and Technology (KAUST).ElsevierMinisterio de Ciencia, Innovación y Universidades (España)King Abdullah University of Science and TechnologyEusko JaurlaritzaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2024202420232024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/342631reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113045GB-C21info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113045GB-C22http://dx.doi.org/10.1016/j.eurpolymj.2023.112526Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3426312026-05-22T06:33:51Z
dc.title.none.fl_str_mv Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
title Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
spellingShingle Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
Centeno, E.
Hydrogels
Amphiphilic triblock copolymers
Star block copolymers
3D direct ink printing
Biomaterial inks
Crystallinity
title_short Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
title_full Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
title_fullStr Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
title_full_unstemmed Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
title_sort Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks
dc.creator.none.fl_str_mv Centeno, E.
Peñas, Mario I.
Zhan, P.
Mercado-Rico, J.
Matxinandiarena, E.
Zubitur, M.
Mugica, A.
Hadjichristidis, N.
Müller, A. J.
Hernández, Rebeca
author Centeno, E.
author_facet Centeno, E.
Peñas, Mario I.
Zhan, P.
Mercado-Rico, J.
Matxinandiarena, E.
Zubitur, M.
Mugica, A.
Hadjichristidis, N.
Müller, A. J.
Hernández, Rebeca
author_role author
author2 Peñas, Mario I.
Zhan, P.
Mercado-Rico, J.
Matxinandiarena, E.
Zubitur, M.
Mugica, A.
Hadjichristidis, N.
Müller, A. J.
Hernández, Rebeca
author2_role author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
King Abdullah University of Science and Technology
Eusko Jaurlaritza
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Hydrogels
Amphiphilic triblock copolymers
Star block copolymers
3D direct ink printing
Biomaterial inks
Crystallinity
topic Hydrogels
Amphiphilic triblock copolymers
Star block copolymers
3D direct ink printing
Biomaterial inks
Crystallinity
description In this work, a set of well-defined linear triblock copolymers and star block copolymers (3 and 4-arms) with semi-crystalline blocks consisting of poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL), synthesized by combining ring-opening polymerization and organic catalyst switch strategy, were studied as thermosensitive gel-forming biomaterials for applications in 3D extrusion printing. The hydrogels derived from linear copolymers underwent a temperature-dependent sol–gel–sol transition, behaving as a flowing sol at room temperature and transforming into a non-flowing gel upon heating. On the other hand, the hydrogels derived from 4-arm star block copolymers experienced a gel-sol transition and did not flow at room temperature. This behavior allowed them to be used as 3D printing inks at room temperature. 3D printing results revealed that the semi-crystalline hydrogels of the 4-arm star block copolymers could not only be extruded and printed with high shape fidelity, but they also exhibited a favorable dissolution profile for their use as sacrificial biomaterial inks. Additionally, we thoroughly investigated the crystalline organization of the PCL and the PEO blocks within the hydrogels through comparison with the results obtained in bulk. The results demonstrated evident structural ordering in the hydrogels associated with the crystallization of the PCL blocks. Unexpectedly, DSC results combined with SAXS experiments revealed the presence of PEO block crystals within the 30 % w/v hydrogels from 4-arm star block copolymers, in addition to the PCL block crystals. Hence, remarkable double crystalline hydrogels have been obtained for the first time.
publishDate 2023
dc.date.none.fl_str_mv 2023
2024
2024
2024
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/10261/342631
url http://hdl.handle.net/10261/342631
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113045GB-C21
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113045GB-C22
http://dx.doi.org/10.1016/j.eurpolymj.2023.112526
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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)
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