Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes
<jats:p> Incorporating dynamic metal-coordination bonds as cross-links into synthetic materials has become attractive not only to improve self-healing and toughness, but also due to the tunability of metal-coordination bonds. However, a priori determination of bond lifetime of met...
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
Proceedings of the National Academy of Sciences
2023
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| Online Access: | https://hdl.handle.net/1721.1/148575 |
| _version_ | 1826199713661059072 |
|---|---|
| author | Khare, Eesha Cazzell, Seth Allen Song, Jake Holten-Andersen, Niels Buehler, Markus J |
| author2 | Massachusetts Institute of Technology. Department of Civil and Environmental Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Khare, Eesha Cazzell, Seth Allen Song, Jake Holten-Andersen, Niels Buehler, Markus J |
| author_sort | Khare, Eesha |
| collection | MIT |
| description | <jats:p>
Incorporating dynamic metal-coordination bonds as cross-links into synthetic materials has become attractive not only to improve self-healing and toughness, but also due to the tunability of metal-coordination bonds. However, a priori determination of bond lifetime of metal-coordination complexes, especially important in the rational design of metal-coordinated materials with prescribed properties, is missing. We report an empirical relationship between the energy landscape of metal-coordination bonds, simulated via metadynamics, and the resulting macroscopic relaxation time in ideal metal-coordinated hydrogels. Importantly, we expand the Arrhenius relationship between the macroscopic hydrogel relaxation time and metal-coordinate bond activation energy to include width and landscape ruggedness identified in the simulated energy landscapes. Using biologically relevant Ni
<jats:sup>2+</jats:sup>
-nitrogen coordination complexes as a model case, we demonstrate that the quantitative relationship developed from histidine-Ni
<jats:sup>2+</jats:sup>
and imidazole-Ni
<jats:sup>2+</jats:sup>
complexes can predict the average relaxation times of other Ni
<jats:sup>2+</jats:sup>
-nitrogen coordinated networks. We anticipate the quantitative relationship presented here to be a starting point for the development of more sophisticated models that can predict relaxation timescales of materials with programmable viscoelastic properties.
</jats:p> |
| first_indexed | 2024-09-23T11:24:33Z |
| format | Article |
| id | mit-1721.1/148575 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:24:33Z |
| publishDate | 2023 |
| publisher | Proceedings of the National Academy of Sciences |
| record_format | dspace |
| spelling | mit-1721.1/1485752023-03-17T03:31:53Z Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes Khare, Eesha Cazzell, Seth Allen Song, Jake Holten-Andersen, Niels Buehler, Markus J Massachusetts Institute of Technology. Department of Civil and Environmental Engineering <jats:p> Incorporating dynamic metal-coordination bonds as cross-links into synthetic materials has become attractive not only to improve self-healing and toughness, but also due to the tunability of metal-coordination bonds. However, a priori determination of bond lifetime of metal-coordination complexes, especially important in the rational design of metal-coordinated materials with prescribed properties, is missing. We report an empirical relationship between the energy landscape of metal-coordination bonds, simulated via metadynamics, and the resulting macroscopic relaxation time in ideal metal-coordinated hydrogels. Importantly, we expand the Arrhenius relationship between the macroscopic hydrogel relaxation time and metal-coordinate bond activation energy to include width and landscape ruggedness identified in the simulated energy landscapes. Using biologically relevant Ni <jats:sup>2+</jats:sup> -nitrogen coordination complexes as a model case, we demonstrate that the quantitative relationship developed from histidine-Ni <jats:sup>2+</jats:sup> and imidazole-Ni <jats:sup>2+</jats:sup> complexes can predict the average relaxation times of other Ni <jats:sup>2+</jats:sup> -nitrogen coordinated networks. We anticipate the quantitative relationship presented here to be a starting point for the development of more sophisticated models that can predict relaxation timescales of materials with programmable viscoelastic properties. </jats:p> 2023-03-16T13:34:56Z 2023-03-16T13:34:56Z 2023-01-24 2023-03-16T13:31:28Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/148575 Khare, Eesha, Cazzell, Seth Allen, Song, Jake, Holten-Andersen, Niels and Buehler, Markus J. 2023. "Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes." Proceedings of the National Academy of Sciences, 120 (4). en 10.1073/pnas.2213160120 Proceedings of the National Academy of Sciences Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Proceedings of the National Academy of Sciences PNAS |
| spellingShingle | Khare, Eesha Cazzell, Seth Allen Song, Jake Holten-Andersen, Niels Buehler, Markus J Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes |
| title | Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes |
| title_full | Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes |
| title_fullStr | Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes |
| title_full_unstemmed | Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes |
| title_short | Molecular understanding of Ni2+-nitrogen family metal-coordinated hydrogel relaxation times using free energy landscapes |
| title_sort | molecular understanding of ni2 nitrogen family metal coordinated hydrogel relaxation times using free energy landscapes |
| url | https://hdl.handle.net/1721.1/148575 |
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