Modular Synthesis and Patterning of High-Stiffness Networks by Postpolymerization Functionalization with Iron–Catechol Complexes
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| Titel: | Modular Synthesis and Patterning of High-Stiffness Networks by Postpolymerization Functionalization with Iron–Catechol Complexes |
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| Autoren: | Declan P. Shannon, Joshua D. Moon, Christopher W. Barney, Nairiti J. Sinha, Kai-Chieh Yang, Seamus D. Jones, Ronnie V. Garcia, Matthew E. Helgeson, Rachel A. Segalman, Megan T. Valentine, Craig J. Hawker |
| Quelle: | Macromolecules Macromolecules, vol 56, iss 6 |
| Verlagsinformationen: | American Chemical Society (ACS), 2023. |
| Publikationsjahr: | 2023 |
| Schlagwörter: | Engineering, Chemical sciences, Polymers, Chemical Sciences, Macromolecular and Materials Chemistry |
| Beschreibung: | Bioinspired iron-catechol cross-links have shown remarkable success in increasing the mechanical properties of polymer networks, in part due to clustering of Fe3+-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 Fe3+-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. |
| Publikationsart: | Article Other literature type |
| Dateibeschreibung: | application/pdf |
| Sprache: | English |
| ISSN: | 1520-5835 0024-9297 |
| DOI: | 10.1021/acs.macromol.2c02561 |
| Zugangs-URL: | https://pubmed.ncbi.nlm.nih.gov/37013083 https://escholarship.org/content/qt4053r2tp/qt4053r2tp.pdf https://escholarship.org/uc/item/4053r2tp |
| Rights: | CC BY URL: http://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 (http://creativecommons.org/licenses/by/4.0/). |
| Dokumentencode: | edsair.doi.dedup.....2641d37cfec19ddfd5ece14275db0ac4 |
| Datenbank: | OpenAIRE |
Nájsť tento článok vo Web of Science | Abstract: | Bioinspired iron-catechol cross-links have shown remarkable success in increasing the mechanical properties of polymer networks, in part due to clustering of Fe3+-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 Fe3+-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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| ISSN: | 15205835 00249297 |
| DOI: | 10.1021/acs.macromol.2c02561 |