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Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers

Poly(lactide) (PLA) and poly(ethylene glycol) (PEG)-based hydrogels were prepared by mixing phosphate buffer saline (PBS, pH 7.4) solutions of four-arm (PEG-PLA)(2)-R-(PLA-PEG)(2) enantiomerically pure copolymers having the opposite chirality of the poly(lactide) blocks. Dynamic Light Scattering, rh...

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Autores principales: Signori, Francesca, Wennink, Jos W. H., Bronco, Simona, Feijen, Jan, Karperien, Marcel, Bizzarri, Ranieri, Dijkstra, Pieter J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9962659/
https://www.ncbi.nlm.nih.gov/pubmed/36834737
http://dx.doi.org/10.3390/ijms24043327
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author Signori, Francesca
Wennink, Jos W. H.
Bronco, Simona
Feijen, Jan
Karperien, Marcel
Bizzarri, Ranieri
Dijkstra, Pieter J.
author_facet Signori, Francesca
Wennink, Jos W. H.
Bronco, Simona
Feijen, Jan
Karperien, Marcel
Bizzarri, Ranieri
Dijkstra, Pieter J.
author_sort Signori, Francesca
collection PubMed
description Poly(lactide) (PLA) and poly(ethylene glycol) (PEG)-based hydrogels were prepared by mixing phosphate buffer saline (PBS, pH 7.4) solutions of four-arm (PEG-PLA)(2)-R-(PLA-PEG)(2) enantiomerically pure copolymers having the opposite chirality of the poly(lactide) blocks. Dynamic Light Scattering, rheology measurements, and fluorescence spectroscopy suggested that, depending on the nature of the linker R, the gelation process followed rather different mechanisms. In all cases, mixing of equimolar amounts of the enantiomeric copolymers led to micellar aggregates with a stereocomplexed PLA core and a hydrophilic PEG corona. Yet, when R was an aliphatic heptamethylene unit, temperature-dependent reversible gelation was mainly induced by entanglements of PEG chains at concentrations higher than 5 wt.%. When R was a linker containing cationic amine groups, thermo-irreversible hydrogels were promptly generated at concentrations higher than 20 wt.%. In the latter case, stereocomplexation of the PLA blocks randomly distributed in micellar aggregates is proposed as the major determinant of the gelation process.
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spelling pubmed-99626592023-02-26 Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers Signori, Francesca Wennink, Jos W. H. Bronco, Simona Feijen, Jan Karperien, Marcel Bizzarri, Ranieri Dijkstra, Pieter J. Int J Mol Sci Article Poly(lactide) (PLA) and poly(ethylene glycol) (PEG)-based hydrogels were prepared by mixing phosphate buffer saline (PBS, pH 7.4) solutions of four-arm (PEG-PLA)(2)-R-(PLA-PEG)(2) enantiomerically pure copolymers having the opposite chirality of the poly(lactide) blocks. Dynamic Light Scattering, rheology measurements, and fluorescence spectroscopy suggested that, depending on the nature of the linker R, the gelation process followed rather different mechanisms. In all cases, mixing of equimolar amounts of the enantiomeric copolymers led to micellar aggregates with a stereocomplexed PLA core and a hydrophilic PEG corona. Yet, when R was an aliphatic heptamethylene unit, temperature-dependent reversible gelation was mainly induced by entanglements of PEG chains at concentrations higher than 5 wt.%. When R was a linker containing cationic amine groups, thermo-irreversible hydrogels were promptly generated at concentrations higher than 20 wt.%. In the latter case, stereocomplexation of the PLA blocks randomly distributed in micellar aggregates is proposed as the major determinant of the gelation process. MDPI 2023-02-07 /pmc/articles/PMC9962659/ /pubmed/36834737 http://dx.doi.org/10.3390/ijms24043327 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Signori, Francesca
Wennink, Jos W. H.
Bronco, Simona
Feijen, Jan
Karperien, Marcel
Bizzarri, Ranieri
Dijkstra, Pieter J.
Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers
title Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers
title_full Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers
title_fullStr Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers
title_full_unstemmed Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers
title_short Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers
title_sort aggregation and gelation behavior of stereocomplexed four-arm pla-peg copolymers containing neutral or cationic linkers
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9962659/
https://www.ncbi.nlm.nih.gov/pubmed/36834737
http://dx.doi.org/10.3390/ijms24043327
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