Year: 2024
Type: article
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.
Source: ACS Macro Letters
Language: English
Subfield: Polymers and Plastics
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
Funders: National Science Foundation, Alfred P. Sloan Foundation, Camille and Henry Dreyfus Foundation, Northwestern University, National Institutes of Health, International Institute for Nanotechnology, Northwestern University, National Institute of General Medical Sciences, National Institute of Diabetes and Digestive and Kidney Diseases, Division of Graduate Education, Office of Advanced Cyberinfrastructure, Division of Electrical, Communications and Cyber Systems, Division of Chemistry
Awards: CAREER: Photocontrolled Dynamic Covalent Crosslinkers for Light-Responsive Polymer Networks, G1276186940, G1453181110, Biomechanical Mechanisms Underlying Pathologic Hepatic Stellate Cell Behavior in Liver Fibrosis, G1555197637, Acquisition of a 500 MHz NMR Spectrometer for Chemical Research, G1787346651, Graduate Research Fellowship Program (GRFP), Track 4: Advanced CI Coordination Ecosystem: Monitoring and Measurement Services, G2083676204, Development of Photoreversible 4D Cell Culture Technologies, G2391795087, NSF Center for Sustainable Polymers, G2499401798, G2604586490, G3352712625, G336680401, G338811424, G34258105, NSF Center for the Chemistry of Molecularly Optimized Networks, G3562386289, Track 1: ACCESS Resource Allocations Marketplace and Platform Services (RAMPS), G4010157413, G4275568664, G4393968868, G4660062756, ACO: An Open CI Ecosystem to Advance Scientific Discovery (OpenCI), Track 3: COre National Ecosystem for CyberinfrasTructure (CONECT), G5156331529, G5306386714, G5367127336, G5464919783, NNCI: Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource, G6068553369, G6386240557, G741047408, G7526614437, G7916508619, G8230932042, Track 2: Customized Multi-tier Assistance, Training, and Computational Help (MATCH) for End User ACCESS to CI, G8499740153, G8623325734, G8762281482, G8994211811
OpenAlex ID: W4396610065