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Modular Synthesis and Patterning of High-Stiffness Networks by Postpolymerization Functionalization with Iron–Catechol Complexes
[Image: see text] Bioinspired iron–catechol cross-links have shown remarkable success in increasing the mechanical properties of polymer networks, in part due to clustering of Fe(3+)–catechol domains which act as secondary network reinforcing sites. We report a versatile synthetic procedure to prepa...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10064740/ https://www.ncbi.nlm.nih.gov/pubmed/37013083 http://dx.doi.org/10.1021/acs.macromol.2c02561 |
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author | Shannon, Declan P. Moon, Joshua D. Barney, Christopher W. Sinha, Nairiti J. Yang, Kai-Chieh Jones, Seamus D. Garcia, Ronnie V. Helgeson, Matthew E. Segalman, Rachel A. Valentine, Megan T. Hawker, Craig J. |
author_facet | Shannon, Declan P. Moon, Joshua D. Barney, Christopher W. Sinha, Nairiti J. Yang, Kai-Chieh Jones, Seamus D. Garcia, Ronnie V. Helgeson, Matthew E. Segalman, Rachel A. Valentine, Megan T. Hawker, Craig J. |
author_sort | Shannon, Declan P. |
collection | PubMed |
description | [Image: see text] Bioinspired iron–catechol cross-links have shown remarkable success in increasing the mechanical properties of polymer networks, in part due to clustering of Fe(3+)–catechol domains which act as secondary network reinforcing sites. We report a versatile synthetic procedure to prepare modular PEG-acrylate networks with independently tunable covalent bis(acrylate) and supramolecular Fe(3+)–catechol cross-linking. Initial control of network structure is achieved through radical polymerization and cross-linking, followed by postpolymerization incorporation of catechol units via quantitative active ester chemistry and subsequent complexation with iron salts. By tuning the ratio of each building block, dual cross-linked networks reinforced by clustered iron–catechol domains are prepared and exhibit a wide range of properties (Young’s moduli up to ∼245 MPa), well beyond the values achieved through purely covalent cross-linking. This stepwise approach to mixed covalent and metal–ligand cross-linked networks also permits local patterning of PEG-based films through masking techniques forming distinct hard, soft, and gradient regions. |
format | Online Article Text |
id | pubmed-10064740 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-100647402023-04-01 Modular Synthesis and Patterning of High-Stiffness Networks by Postpolymerization Functionalization with Iron–Catechol Complexes Shannon, Declan P. Moon, Joshua D. Barney, Christopher W. Sinha, Nairiti J. Yang, Kai-Chieh Jones, Seamus D. Garcia, Ronnie V. Helgeson, Matthew E. Segalman, Rachel A. Valentine, Megan T. Hawker, Craig J. Macromolecules [Image: see text] Bioinspired iron–catechol cross-links have shown remarkable success in increasing the mechanical properties of polymer networks, in part due to clustering of Fe(3+)–catechol domains which act as secondary network reinforcing sites. We report a versatile synthetic procedure to prepare modular PEG-acrylate networks with independently tunable covalent bis(acrylate) and supramolecular Fe(3+)–catechol cross-linking. Initial control of network structure is achieved through radical polymerization and cross-linking, followed by postpolymerization incorporation of catechol units via quantitative active ester chemistry and subsequent complexation with iron salts. By tuning the ratio of each building block, dual cross-linked networks reinforced by clustered iron–catechol domains are prepared and exhibit a wide range of properties (Young’s moduli up to ∼245 MPa), well beyond the values achieved through purely covalent cross-linking. This stepwise approach to mixed covalent and metal–ligand cross-linked networks also permits local patterning of PEG-based films through masking techniques forming distinct hard, soft, and gradient regions. American Chemical Society 2023-03-15 /pmc/articles/PMC10064740/ /pubmed/37013083 http://dx.doi.org/10.1021/acs.macromol.2c02561 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Shannon, Declan P. Moon, Joshua D. Barney, Christopher W. Sinha, Nairiti J. Yang, Kai-Chieh Jones, Seamus D. Garcia, Ronnie V. Helgeson, Matthew E. Segalman, Rachel A. Valentine, Megan T. Hawker, Craig J. Modular Synthesis and Patterning of High-Stiffness Networks by Postpolymerization Functionalization with Iron–Catechol Complexes |
title | Modular Synthesis
and Patterning of High-Stiffness
Networks by Postpolymerization Functionalization with Iron–Catechol
Complexes |
title_full | Modular Synthesis
and Patterning of High-Stiffness
Networks by Postpolymerization Functionalization with Iron–Catechol
Complexes |
title_fullStr | Modular Synthesis
and Patterning of High-Stiffness
Networks by Postpolymerization Functionalization with Iron–Catechol
Complexes |
title_full_unstemmed | Modular Synthesis
and Patterning of High-Stiffness
Networks by Postpolymerization Functionalization with Iron–Catechol
Complexes |
title_short | Modular Synthesis
and Patterning of High-Stiffness
Networks by Postpolymerization Functionalization with Iron–Catechol
Complexes |
title_sort | modular synthesis
and patterning of high-stiffness
networks by postpolymerization functionalization with iron–catechol
complexes |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10064740/ https://www.ncbi.nlm.nih.gov/pubmed/37013083 http://dx.doi.org/10.1021/acs.macromol.2c02561 |
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