Dynamic behavior of chemically tunable mechano-responsive hydrogels
Abstract
Here, using theory and simulation, we model the mechanical behavior of gels that encompass loops and dangling chain ends. If the loops remain folded and dangling ends are chemically inert, then these topological features just serve as defects. If, however, the loops unfold to expose the hidden (“cryptic”) binding sites and the ends of the dangling chains are reactive, these moieties can form bonds that improve the gel's mechanical properties. For gels with a lower critical solubility temperature (LCST), we systematically switch on the possible unfolding and binding events. To quantify the resulting effects, we derive equations for the gel's equilibrium and dynamic elastic moduli. We also use a finite element approach to simulate the gel's response to deformation and validate the analytic calculations. Herein, we show that the equilibrium moduli are highly sensitive to the presence of unfolding and binding transitions. The dynamical moduli are sensitive not only to these structural changes, but also to the frequency of deformation. For example, when reactive ends bind to exposed cryptic sites at T = 29 °C and relatively high frequency, the storage shear modulus is 119% greater than the corresponding equilibrium value, while the storage Young's modulus is 109% greater thanmore »
- Publication Date:
- Research Org.:
- Univ. of Pittsburgh, PA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); US Army Research Office (ARO)
- OSTI Identifier:
- 1978826
- Alternate Identifier(s):
- OSTI ID: 1830248
- Grant/Contract Number:
- FG02-02ER45998; W911NF1910388
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Soft Matter
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 47; Journal ID: ISSN 1744-683X
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Materials Science; Physics; Polymer Science
Citation Formats
Biswas, Santidan, Yashin, Victor V., and Balazs, Anna C. Dynamic behavior of chemically tunable mechano-responsive hydrogels. United States: N. p., 2021.
Web. doi:10.1039/d1sm01188j.
Biswas, Santidan, Yashin, Victor V., & Balazs, Anna C. Dynamic behavior of chemically tunable mechano-responsive hydrogels. United States. https://doi.org/10.1039/d1sm01188j
Biswas, Santidan, Yashin, Victor V., and Balazs, Anna C. Wed .
"Dynamic behavior of chemically tunable mechano-responsive hydrogels". United States. https://doi.org/10.1039/d1sm01188j. https://www.osti.gov/servlets/purl/1978826.
@article{osti_1978826,
title = {Dynamic behavior of chemically tunable mechano-responsive hydrogels},
author = {Biswas, Santidan and Yashin, Victor V. and Balazs, Anna C.},
abstractNote = {Here, using theory and simulation, we model the mechanical behavior of gels that encompass loops and dangling chain ends. If the loops remain folded and dangling ends are chemically inert, then these topological features just serve as defects. If, however, the loops unfold to expose the hidden (“cryptic”) binding sites and the ends of the dangling chains are reactive, these moieties can form bonds that improve the gel's mechanical properties. For gels with a lower critical solubility temperature (LCST), we systematically switch on the possible unfolding and binding events. To quantify the resulting effects, we derive equations for the gel's equilibrium and dynamic elastic moduli. We also use a finite element approach to simulate the gel's response to deformation and validate the analytic calculations. Herein, we show that the equilibrium moduli are highly sensitive to the presence of unfolding and binding transitions. The dynamical moduli are sensitive not only to these structural changes, but also to the frequency of deformation. For example, when reactive ends bind to exposed cryptic sites at T = 29 °C and relatively high frequency, the storage shear modulus is 119% greater than the corresponding equilibrium value, while the storage Young's modulus is 109% greater than at equilibrium. These findings provide guidelines for tuning the chemical reactivity of loops and dangling ends and the frequency of deformation to tailor the mechano-responsive behavior of polymer networks.},
doi = {10.1039/d1sm01188j},
journal = {Soft Matter},
number = 47,
volume = 17,
place = {United States},
year = {Wed Nov 03 00:00:00 EDT 2021},
month = {Wed Nov 03 00:00:00 EDT 2021}
}
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