Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation
Nanocomposite tectons (NCTs) are a recently developed building block for polymer-nanoparticle composite synthesis, consisting of nanoparticle cores functionalized with dense monolayers of polymer chains that terminate in supramolecular recognition groups capable of linking NCTs into hierarchical str...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/128770 |
| _version_ | 1826196785657282560 |
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| author | Wang, Yuping Santos, Peter J.(Peter Jeffries) Kubiak, Joshua M Guo, Xinheng Lee, Margaret S. Macfarlane, Robert J |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Wang, Yuping Santos, Peter J.(Peter Jeffries) Kubiak, Joshua M Guo, Xinheng Lee, Margaret S. Macfarlane, Robert J |
| author_sort | Wang, Yuping |
| collection | MIT |
| description | Nanocomposite tectons (NCTs) are a recently developed building block for polymer-nanoparticle composite synthesis, consisting of nanoparticle cores functionalized with dense monolayers of polymer chains that terminate in supramolecular recognition groups capable of linking NCTs into hierarchical structures. In principle, the use of molecular binding to guide particle assembly allows NCTs to be highly modular in design, with independent control over the composition of the particle core and polymer brush. However, a major challenge to realize an array of compositionally and structurally varied NCT-based materials is the development of different supramolecular bonding interactions to control NCT assembly, as well as an understanding of how the organization of multiple supramolecular groups around a nanoparticle scaffold affects their collective binding interactions. Here, we present a suite of rationally designed NCT systems, where multiple types of supramolecular interactions (hydrogen bonding, metal complexation, and dynamic covalent bond formation) are used to tune NCT assembly as a function of multiple external stimuli including temperature, small molecules, pH, and light. Furthermore, the incorporation of multiple orthogonal supramolecular chemistries in a single NCT system makes it possible to dictate the morphologies of the assembled NCTs in a pathway-dependent fashion. Finally, multistimuli responsive NCTs enable the modification of composite properties by postassembly functionalization, where NCTs linked by covalent bonds with significantly enhanced stability are obtained in a fast and efficient manner. The designs presented here therefore provide major advancement for the field of composite synthesis by establishing a framework for synthesizing hierarchically ordered composites capable of complicated assembly behaviors. Copyright ©2019 American Chemical Society. |
| first_indexed | 2024-09-23T10:37:39Z |
| format | Article |
| id | mit-1721.1/128770 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T10:37:39Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1287702022-09-30T21:54:17Z Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation Wang, Yuping Santos, Peter J.(Peter Jeffries) Kubiak, Joshua M Guo, Xinheng Lee, Margaret S. Macfarlane, Robert J Massachusetts Institute of Technology. Department of Materials Science and Engineering Nanocomposite tectons (NCTs) are a recently developed building block for polymer-nanoparticle composite synthesis, consisting of nanoparticle cores functionalized with dense monolayers of polymer chains that terminate in supramolecular recognition groups capable of linking NCTs into hierarchical structures. In principle, the use of molecular binding to guide particle assembly allows NCTs to be highly modular in design, with independent control over the composition of the particle core and polymer brush. However, a major challenge to realize an array of compositionally and structurally varied NCT-based materials is the development of different supramolecular bonding interactions to control NCT assembly, as well as an understanding of how the organization of multiple supramolecular groups around a nanoparticle scaffold affects their collective binding interactions. Here, we present a suite of rationally designed NCT systems, where multiple types of supramolecular interactions (hydrogen bonding, metal complexation, and dynamic covalent bond formation) are used to tune NCT assembly as a function of multiple external stimuli including temperature, small molecules, pH, and light. Furthermore, the incorporation of multiple orthogonal supramolecular chemistries in a single NCT system makes it possible to dictate the morphologies of the assembled NCTs in a pathway-dependent fashion. Finally, multistimuli responsive NCTs enable the modification of composite properties by postassembly functionalization, where NCTs linked by covalent bonds with significantly enhanced stability are obtained in a fast and efficient manner. The designs presented here therefore provide major advancement for the field of composite synthesis by establishing a framework for synthesizing hierarchically ordered composites capable of complicated assembly behaviors. Copyright ©2019 American Chemical Society. U.S. Army Research Office (W911NF-18-1-0197) NSF CAREER Grant (CHE-1653289) NSF (DMR 14-19807) NSF Graduate Research Fellowship Program Grant (1122374) 2020-12-10T01:13:28Z 2020-12-10T01:13:28Z 2019-07 2019-06 2019-09-23T12:35:15Z Article http://purl.org/eprint/type/JournalArticle 1520-5126 https://hdl.handle.net/1721.1/128770 Wang, Yuping et al., "Multistimuli Responsive Nanocomposite Tectons for Pathway Dependent Self-Assembly and Acceleration of Covalent Bond Formation." Journal of the American Chemical Society 141, 33 (August 2019): 13234–43 ©2019 Authors en https://dx.doi.org/10.1021/jacs.9b06695 Journal of the American Chemical Society Creative Commons Attribution 3.0 unported license http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Wang, Yuping Santos, Peter J.(Peter Jeffries) Kubiak, Joshua M Guo, Xinheng Lee, Margaret S. Macfarlane, Robert J Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation |
| title | Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation |
| title_full | Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation |
| title_fullStr | Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation |
| title_full_unstemmed | Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation |
| title_short | Multistimuli responsive nanocomposite tectons for pathway dependent self-assembly and acceleration of covalent bond formation |
| title_sort | multistimuli responsive nanocomposite tectons for pathway dependent self assembly and acceleration of covalent bond formation |
| url | https://hdl.handle.net/1721.1/128770 |
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