Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin Polyrotaxanes
Despite hundreds of studies involving slide-ring gels derived from cyclodextrin (CD)-based polyrotaxanes (PRs), their covalent cross-linking kinetics are not well characterized. We employ chemorheology as a tool to measure the gelation kinetics of a model slide-ring organogel derived from α-cyclodex...
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| Format: | Article |
| Language: | English |
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Frontiers Media S.A.
2022-07-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/articles/10.3389/fchem.2022.923775/full |
| _version_ | 1818194292932345856 |
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| author | Karan Dikshit Carson J. Bruns Carson J. Bruns |
| author_facet | Karan Dikshit Carson J. Bruns Carson J. Bruns |
| author_sort | Karan Dikshit |
| collection | DOAJ |
| description | Despite hundreds of studies involving slide-ring gels derived from cyclodextrin (CD)-based polyrotaxanes (PRs), their covalent cross-linking kinetics are not well characterized. We employ chemorheology as a tool to measure the gelation kinetics of a model slide-ring organogel derived from α-cyclodextrin/poly (ethylene glycol) PRs cross-linked with hexamethylenediisocyanate (HMDI) in DMSO. The viscoelastic properties of the gels were monitored in situ by small-amplitude oscillatory shear (SAOS) rheology, enabling us to estimate the activation barrier and rate law for cross-linking while mapping experimental parameters to kinetics and mechanical properties. Gelation time, gel point, and final gel elasticity depend on cross-linker concentration, but polyrotaxane concentration only affects gelation time and elasticity (not gel point), while temperature only affects gelation time and gel point (not final elasticity). These measurements facilitate the rational design of slide-ring networks by simple parameter selection (temperature, cross-linker concentration, PR concentration, reaction time). |
| first_indexed | 2024-12-12T00:59:59Z |
| format | Article |
| id | doaj.art-e1c6c690bc1a41ddad5da697eae9c3a9 |
| institution | Directory Open Access Journal |
| issn | 2296-2646 |
| language | English |
| last_indexed | 2024-12-12T00:59:59Z |
| publishDate | 2022-07-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Chemistry |
| spelling | doaj.art-e1c6c690bc1a41ddad5da697eae9c3a92022-12-22T00:43:46ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462022-07-011010.3389/fchem.2022.923775923775Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin PolyrotaxanesKaran Dikshit 0Carson J. Bruns 1Carson J. Bruns 2Materials Science and Engineering Program, University of Colorado Boulder, Boulder, CO, United StatesPaul M. Rady Mechanical Engineering Department, University of Colorado Boulder, Boulder, CO, United StatesATLAS Institute, University of Colorado Boulder, Boulder, CO, United StatesDespite hundreds of studies involving slide-ring gels derived from cyclodextrin (CD)-based polyrotaxanes (PRs), their covalent cross-linking kinetics are not well characterized. We employ chemorheology as a tool to measure the gelation kinetics of a model slide-ring organogel derived from α-cyclodextrin/poly (ethylene glycol) PRs cross-linked with hexamethylenediisocyanate (HMDI) in DMSO. The viscoelastic properties of the gels were monitored in situ by small-amplitude oscillatory shear (SAOS) rheology, enabling us to estimate the activation barrier and rate law for cross-linking while mapping experimental parameters to kinetics and mechanical properties. Gelation time, gel point, and final gel elasticity depend on cross-linker concentration, but polyrotaxane concentration only affects gelation time and elasticity (not gel point), while temperature only affects gelation time and gel point (not final elasticity). These measurements facilitate the rational design of slide-ring networks by simple parameter selection (temperature, cross-linker concentration, PR concentration, reaction time).https://www.frontiersin.org/articles/10.3389/fchem.2022.923775/fullchemorheologyrheologycyclodextrinsorganogelsslide-ring gelspolyrotaxane |
| spellingShingle | Karan Dikshit Carson J. Bruns Carson J. Bruns Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin Polyrotaxanes Frontiers in Chemistry chemorheology rheology cyclodextrins organogels slide-ring gels polyrotaxane |
| title | Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin Polyrotaxanes |
| title_full | Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin Polyrotaxanes |
| title_fullStr | Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin Polyrotaxanes |
| title_full_unstemmed | Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin Polyrotaxanes |
| title_short | Chemorheological Monitoring of Cross-Linking in Slide-ring Gels Derived From α-cyclodextrin Polyrotaxanes |
| title_sort | chemorheological monitoring of cross linking in slide ring gels derived from α cyclodextrin polyrotaxanes |
| topic | chemorheology rheology cyclodextrins organogels slide-ring gels polyrotaxane |
| url | https://www.frontiersin.org/articles/10.3389/fchem.2022.923775/full |
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