Internal Catalysis in Dynamic Hydrogels with Associative Thioester Cross-Links.
ACS Macro Lett
; 13(5): 621-626, 2024 May 21.
Article
em En
| MEDLINE
| ID: mdl-38700544
ABSTRACT
Thioesters are an essential functional group in biosynthetic pathways, which has motivated their development as reactive handles in probes and peptide assembly. Thioester exchange is typically accelerated by catalysts or elevated pH. Here, we report the use of bifunctional aromatic thioesters as dynamic covalent cross-links in hydrogels, demonstrating that at physiologic pH in aqueous conditions, transthioesterification facilitates stress relaxation on the time scale of hundreds of seconds. We show that intramolecular hydrogen bonding is responsible for accelerated exchange, evident in both molecular kinetics and macromolecular stress relaxation. Drawing from concepts in the vitrimer literature, this system exemplifies how dynamic cross-links that exchange through an associative mechanism enable tunable stress relaxation without altering stiffness.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
ACS Macro Lett
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Estados Unidos