Internal Catalysis in Dynamic Hydrogels with Associative Thioester Cross-Links
Name
nihms-2013358.pdf
Description
Accepted version
Size
1000.11 KB
Format
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Checksum (MD5)
de8e8634c27707ef583213cac28900b6
Author(s)
Zhang, Vivian
Ou, Carrie
Kevlishvili, Ilia
Hemmingsen, Christina M
Accardo, Joseph V
Kulik, Heather J
Kalow, Julia A
Date Issued
May 3, 2024
Journal
ACS Macro Letters
Publisher
American Chemical Society
Citation
Internal Catalysis in Dynamic Hydrogels with Associative Thioester Cross-Links. Vivian Zhang, Carrie Ou, Ilia Kevlishvili, Christina M. Hemmingsen, Joseph V. Accardo, Heather J. Kulik, and Julia A. Kalow. ACS Macro Letters 2024 13 (5), 621-626
Version
Author's final manuscript
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-Noncommercial-ShareAlike
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DOI of Published Version
https://doi.org/10.1021/acsmacrolett.4c00245
