Post-fabrication reconfiguration of hydrogels through thermodynamic asymmetry in dynamic chemistry
Abstract
Designing soft materials with adaptive properties requires internal chemical processes that enable reconfiguration across multiple system levels. Dynamic covalent chemistry has provided powerful routes to dynamic polymer networks, yet it is typically employed in an equilibrium-based manner where the identity of the dynamic bond remains unchanged. Here, we introduce thermodynamic asymmetry in dynamic covalent chemistry to enable the replacement of network-defining linkages after material formation, rather than their mere bond shuffling. For combinations of hydrazones and oximes, we demonstrate near-quantitative hydrazone-to-oxime exchange under aqueous conditions. Kinetic modeling elucidates that the exchange is dominated by a hydrolytic pathway with a non-trivial concentration dependence. This chemistry enables diverse reconfigurations within hydrogels after their initial synthesis, achieving near-complete replacement at material scale. Treating pre-formed hydrazone gels with functional alkoxyamines enables topological, mechanical, and functional reprogramming without network deconstruction. This work establishes thermodynamically biased dynamic covalent exchange as a generalizable principle for materials, surface functions, or self-assembling systems, illustrating how molecular reaction pathways can be harnessed to deterministically alter structural and functional identity.
Versions
Related
- Chitosan‐Based Hydrogels for Periodontal Therapy: From Drug‐Polymer Chemistry to Smart Multifunctional and Regenerative Systems
- Navigating reconfiguration: case managers in public municipal healthcare - a scoping review protocol.
- Citation Fabrication and Accuracy in AI-Generated Psychiatric Research: A Comparative Evaluation of Four Contemporary Large Language Models
- Intranasal hydrogels for Alzheimer’s disease: from nasal-interface engineering to brain targeting and translational readiness
- Kinetic-driven microphase separation and vitrification of crowded hydrogels with associative bonds
BibTeX
@article{campagna2026postfabrication,
title = {{Post-fabrication reconfiguration of hydrogels through thermodynamic asymmetry in dynamic chemistry}},
author = {Davide Campagna and Diego Ciardi and Weixiang Chen and Andreas Walther},
journal = {Nature Communications},
year = {2026},
month = oct,
doi = {10.1038/s41467-026-78292-4},
url = {https://www.nature.com/articles/s41467-026-78292-4},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Post-fabrication reconfiguration of hydrogels through thermodynamic asymmetry in dynamic chemistry
AU - Davide Campagna
AU - Diego Ciardi
AU - Weixiang Chen
AU - Andreas Walther
PY - 2026
DA - 2026/10/07
JO - Nature Communications
DO - 10.1038/s41467-026-78292-4
UR - https://www.nature.com/articles/s41467-026-78292-4
AB - Designing soft materials with adaptive properties requires internal chemical processes that enable reconfiguration across multiple system levels. Dynamic covalent chemistry has provided powerful routes to dynamic polymer networks, yet it is typically employed in an equilibrium-based manner where the identity of the dynamic bond remains unchanged. Here, we introduce thermodynamic asymmetry in dynamic covalent chemistry to enable the replacement of network-defining linkages after material formation, rather than their mere bond shuffling. For combinations of hydrazones and oximes, we demonstrate near-quantitative hydrazone-to-oxime exchange under aqueous conditions. Kinetic modeling elucidates that the exchange is dominated by a hydrolytic pathway with a non-trivial concentration dependence. This chemistry enables diverse reconfigurations within hydrogels after their initial synthesis, achieving near-complete replacement at material scale. Treating pre-formed hydrazone gels with functional alkoxyamines enables topological, mechanical, and functional reprogramming without network deconstruction. This work establishes thermodynamically biased dynamic covalent exchange as a generalizable principle for materials, surface functions, or self-assembling systems, illustrating how molecular reaction pathways can be harnessed to deterministically alter structural and functional identity.
SN - 2041-1723
ER -