Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules
Monodisperse oligomers are important intermediates for studying structure–property relationships in soft materials but are traditionally laborious to synthesize. A semi-automated synthetic system that combines the benefits of telescoped reactions in continuous flow with iterative exponential growth...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2018
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| Online Access: | http://hdl.handle.net/1721.1/117484 https://orcid.org/0000-0002-6366-4627 https://orcid.org/0000-0002-8601-7799 |
| _version_ | 1811070748210495488 |
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| author | Leibfarth, Frank A. Wicker, Amanda Catherine Jamison, Timothy F |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Leibfarth, Frank A. Wicker, Amanda Catherine Jamison, Timothy F |
| author_sort | Leibfarth, Frank A. |
| collection | MIT |
| description | Monodisperse oligomers are important intermediates for studying structure–property relationships in soft materials but are traditionally laborious to synthesize. A semi-automated synthetic system that combines the benefits of telescoped reactions in continuous flow with iterative exponential growth (IEG) greatly expedites this process and makes the rapid synthesis of structurally diverse oligomer libraries practical. Herein, the coupling chemistry in the Flow-IEG system has been upgraded and expanded to include both 1,4- and 1,5-triazole linkages between monomers through an improved copper-catalyzed azide–alkyne cycloaddition (CuAAC) and a newly-optimized ruthenium-catalyzed azide–alkyne cycloaddition (RuAAC), respectively. Improvements to the Flow-IEG framework enabled the library synthesis of monodisperse oligomers with variations in triazole connectivity. These discrete oligomers allowed the systematic evaluation of the consequences of triazole sequence on material properties. The crystallization properties of these macromolecules were highly dependent on both their monomer sequence and triazole substitution pattern. |
| first_indexed | 2024-09-23T08:40:56Z |
| format | Article |
| id | mit-1721.1/117484 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:40:56Z |
| publishDate | 2018 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/1174842022-09-23T13:49:48Z Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules Leibfarth, Frank A. Wicker, Amanda Catherine Jamison, Timothy F Massachusetts Institute of Technology. Department of Chemistry Jamison, Timothy F. Wicker, Amanda Catherine Jamison, Timothy F Monodisperse oligomers are important intermediates for studying structure–property relationships in soft materials but are traditionally laborious to synthesize. A semi-automated synthetic system that combines the benefits of telescoped reactions in continuous flow with iterative exponential growth (IEG) greatly expedites this process and makes the rapid synthesis of structurally diverse oligomer libraries practical. Herein, the coupling chemistry in the Flow-IEG system has been upgraded and expanded to include both 1,4- and 1,5-triazole linkages between monomers through an improved copper-catalyzed azide–alkyne cycloaddition (CuAAC) and a newly-optimized ruthenium-catalyzed azide–alkyne cycloaddition (RuAAC), respectively. Improvements to the Flow-IEG framework enabled the library synthesis of monodisperse oligomers with variations in triazole connectivity. These discrete oligomers allowed the systematic evaluation of the consequences of triazole sequence on material properties. The crystallization properties of these macromolecules were highly dependent on both their monomer sequence and triazole substitution pattern. 2018-08-22T18:41:16Z 2018-08-22T18:41:16Z 2017-09 2017-07 Article http://purl.org/eprint/type/JournalArticle 1759-9954 1759-9962 http://hdl.handle.net/1721.1/117484 Wicker, Amanda C. et al. “Flow-IEG Enables Programmable Thermodynamic Properties in Sequence-Defined Unimolecular Macromolecules.” Polymer Chemistry 8, 37 (2017): 5786–5794 © The Royal Society of Chemistry https://orcid.org/0000-0002-6366-4627 https://orcid.org/0000-0002-8601-7799 en_US http://dx.doi.org/10.1039/C7PY01204G Polymer Chemistry Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Royal Society of Chemistry Prof. Jamison via Erja Kajosalo |
| spellingShingle | Leibfarth, Frank A. Wicker, Amanda Catherine Jamison, Timothy F Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules |
| title | Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules |
| title_full | Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules |
| title_fullStr | Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules |
| title_full_unstemmed | Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules |
| title_short | Flow-IEG enables programmable thermodynamic properties in sequence-defined unimolecular macromolecules |
| title_sort | flow ieg enables programmable thermodynamic properties in sequence defined unimolecular macromolecules |
| url | http://hdl.handle.net/1721.1/117484 https://orcid.org/0000-0002-6366-4627 https://orcid.org/0000-0002-8601-7799 |
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