Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) Synthesis
Abstract Poly(glycerol sebacate) (PGS) belongs to the hyperbranched polyesters family (HBP), which possesses an extensive variety of applications due to its tunable chemical and mechanical properties, together with its biocompatibility and biodegradability. However, the understanding of PGS synthesi...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2024-02-01
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| Series: | Macromolecular Materials and Engineering |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/mame.202300270 |
| _version_ | 1797305259059576832 |
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| author | Rubén Martín‐Cabezuelo Alicia Naderpour‐Peñalver A Sigen Wenxin Wang Guillermo Vilariño‐Feltrer Ana Vallés‐Lluch |
| author_facet | Rubén Martín‐Cabezuelo Alicia Naderpour‐Peñalver A Sigen Wenxin Wang Guillermo Vilariño‐Feltrer Ana Vallés‐Lluch |
| author_sort | Rubén Martín‐Cabezuelo |
| collection | DOAJ |
| description | Abstract Poly(glycerol sebacate) (PGS) belongs to the hyperbranched polyesters family (HBP), which possesses an extensive variety of applications due to its tunable chemical and mechanical properties, together with its biocompatibility and biodegradability. However, the understanding of PGS synthesis becomes a challenge due to the lack of consistency when determining its synthesis parameters. Understanding these parameters is fundamental to control PGS synthesis and obtain a scalable and reproducible final product for biomedical applications. To unveil their effect on diverging PGS properties, diols are used as glycerol analogs and the reaction is chemically and thermally monitored, suggesting a heterogeneous reactivity of the exposed hydroxyl groups. Also, confinement of the prepolymerization is proven to be fundamental In order to maintain the equimolar ratio of initial monomers during synthesis. Early stages of the polycondensation (first 4 h) tend to linear and less branched oligomers by consuming primary hydroxyls rather than secondary hydroxyls. However, physicochemical characterization determines that a high degree of conversion (40%) is reached during these early stages. Afterward, the oligomers tend to condense through the secondary hydroxyls into a more crosslinked elastomer. This study demonstrates how hydroxyl affinity, water presence, and glycerol loss are crucial for the scalability and reproducibility of its final product. |
| first_indexed | 2024-03-08T00:22:22Z |
| format | Article |
| id | doaj.art-db00255f20df413aa92ad3b336c8911a |
| institution | Directory Open Access Journal |
| issn | 1438-7492 1439-2054 |
| language | English |
| last_indexed | 2024-03-08T00:22:22Z |
| publishDate | 2024-02-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Macromolecular Materials and Engineering |
| spelling | doaj.art-db00255f20df413aa92ad3b336c8911a2024-02-16T04:32:59ZengWiley-VCHMacromolecular Materials and Engineering1438-74921439-20542024-02-013092n/an/a10.1002/mame.202300270Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) SynthesisRubén Martín‐Cabezuelo0Alicia Naderpour‐Peñalver1A Sigen2Wenxin Wang3Guillermo Vilariño‐Feltrer4Ana Vallés‐Lluch5Centre for Biomaterials and Tissue Engineering Technical University of Valencia Valencia 46020 SpainCentre for Biomaterials and Tissue Engineering Technical University of Valencia Valencia 46020 SpainCharles Institute of Dermatology School of Medicine University College Dublin Dublin D04 V1W8 IrelandCharles Institute of Dermatology School of Medicine University College Dublin Dublin D04 V1W8 IrelandCentre for Biomaterials and Tissue Engineering Technical University of Valencia Valencia 46020 SpainCentre for Biomaterials and Tissue Engineering Technical University of Valencia Valencia 46020 SpainAbstract Poly(glycerol sebacate) (PGS) belongs to the hyperbranched polyesters family (HBP), which possesses an extensive variety of applications due to its tunable chemical and mechanical properties, together with its biocompatibility and biodegradability. However, the understanding of PGS synthesis becomes a challenge due to the lack of consistency when determining its synthesis parameters. Understanding these parameters is fundamental to control PGS synthesis and obtain a scalable and reproducible final product for biomedical applications. To unveil their effect on diverging PGS properties, diols are used as glycerol analogs and the reaction is chemically and thermally monitored, suggesting a heterogeneous reactivity of the exposed hydroxyl groups. Also, confinement of the prepolymerization is proven to be fundamental In order to maintain the equimolar ratio of initial monomers during synthesis. Early stages of the polycondensation (first 4 h) tend to linear and less branched oligomers by consuming primary hydroxyls rather than secondary hydroxyls. However, physicochemical characterization determines that a high degree of conversion (40%) is reached during these early stages. Afterward, the oligomers tend to condense through the secondary hydroxyls into a more crosslinked elastomer. This study demonstrates how hydroxyl affinity, water presence, and glycerol loss are crucial for the scalability and reproducibility of its final product.https://doi.org/10.1002/mame.202300270biomaterialsglycerolH‐NMRpoly(glycerol‐sebacate)polymer chemistry |
| spellingShingle | Rubén Martín‐Cabezuelo Alicia Naderpour‐Peñalver A Sigen Wenxin Wang Guillermo Vilariño‐Feltrer Ana Vallés‐Lluch Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) Synthesis Macromolecular Materials and Engineering biomaterials glycerol H‐NMR poly(glycerol‐sebacate) polymer chemistry |
| title | Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) Synthesis |
| title_full | Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) Synthesis |
| title_fullStr | Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) Synthesis |
| title_full_unstemmed | Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) Synthesis |
| title_short | Unveiling the Role of Key Parameters during Molecular Growth for Optimal Poly(glycerol sebacate) Synthesis |
| title_sort | unveiling the role of key parameters during molecular growth for optimal poly glycerol sebacate synthesis |
| topic | biomaterials glycerol H‐NMR poly(glycerol‐sebacate) polymer chemistry |
| url | https://doi.org/10.1002/mame.202300270 |
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