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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...

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Autores principales: 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.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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.
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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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