Effect of pH on the Properties of Hydrogels Cross-Linked via Dynamic Thia-Michael Addition Bonds

dc.creatorFitzSimons, Thomas M.
dc.creatorAnslyn, Eric V.
dc.creatorRosales, Adrienne M.
dc.date.accessioned2024-02-12T19:01:31Z
dc.date.available2024-02-12T19:01:31Z
dc.date.issued2021-12-28
dc.description.abstractHydrogels cross-linked with dynamic covalent bonds exhibit time-dependent properties, making them an advantageous platform for applications ranging from biomaterials to self-healing networks. However, the relationship between the cross-link exchange kinetics, material properties, and stability of these platforms is not fully understood, especially upon addition of external stimuli. In this work, pH was used as a handle to manipulate cross-link exchange kinetics and control the resulting hydrogel mechanics and stability in a physiologically relevant window. Poly(ethylene glycol)-based hydrogels were cross-linked with a reversible thia-Michael addition reaction in aqueous buffer between pH 3 and pH 7. The rate constants of bond exchange and equilibrium constants were determined for each pH value, and these data were correlated with the resulting mechanical profiles of the bulk hydrogels. With increasing pH, both the forward and the reverse rate constants increased, while the equilibrium constant decreased. These changes led to faster stress relaxation and less stiff hydrogels at more basic pH values. The elevated pH values also led to an increased mass loss and a faster rate of release of an encapsulated model bovine serum albumin fluorescent protein. The connection between the kinetics, mechanics, and molecular release profiles provides important insight into the structure−property relationships of dynamic covalent hydrogels, and this system offers a promising platform for controlled release between physiologically relevant pH values.
dc.description.departmentCenter for Dynamics and Control of Materials
dc.description.sponsorshipThis research was supported by the National Science Foundation (NSF MRSEC DMR-1720595, T.M.F., E.V.A., and A.M.R.) and by the National Institutes of Health (R35GM138193, A.M.R.). The authors acknowledge the use of shared research facilities supported in part by the Texas Materials Institute, the Center for Dynamics and Control of Materials: an NSF MRSEC (DMR-1720595), and the NSF National Nanotechnology Coordinated Infrastructure (ECCS- 1542159).
dc.identifier.citationFitzSimons, TM; Anslyn, EV; Rosales, AM. Effect of pH on the Properties of Hydrogels Cross-Linked via Dynamic Thia-Michael Addition Bonds. ACS Polym. Au 2022, 2(2), 129-136. DOI: 10.1021/acspolymersau.1c00049
dc.identifier.doiDOI: 10.1021/acspolymersau.1c00049
dc.identifier.urihttps://hdl.handle.net/2152/123647
dc.identifier.urihttps://doi.org/10.26153/tsw/50441
dc.language.isoen_US
dc.publisherACS Publications
dc.relation.ispartofCenter for Dynamics and Control of Materials Publications
dc.rightsAttribution-NonCommercial-NoDerivs 3.0 United Statesen
dc.rights.restrictionOpen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/us/
dc.subjectThia-Michael
dc.subjecthydrogel
dc.subjectviscoelastic
dc.subjectself-healing
dc.subjectbiomaterial
dc.subjectrelease
dc.subjectdynamic covalent
dc.titleEffect of pH on the Properties of Hydrogels Cross-Linked via Dynamic Thia-Michael Addition Bonds
dc.typeArticle

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