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Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism
[Image: see text] Transient polymers rapidly and controllably depolymerize in response to a specific trigger, typically by a chain-end unzipping mechanism. Triggers, such as heat, light, and chemical stimuli, are generally dependent on the chemistry of the polymer backbone or end groups. Single elec...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7047432/ https://www.ncbi.nlm.nih.gov/pubmed/32123745 http://dx.doi.org/10.1021/acscentsci.9b01237 |
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author | Feinberg, Adam M. Davydovich, Oleg Lloyd, Evan M. Ivanoff, Douglas G. Shiang, Bethany Sottos, Nancy R. Moore, Jeffrey S. |
author_facet | Feinberg, Adam M. Davydovich, Oleg Lloyd, Evan M. Ivanoff, Douglas G. Shiang, Bethany Sottos, Nancy R. Moore, Jeffrey S. |
author_sort | Feinberg, Adam M. |
collection | PubMed |
description | [Image: see text] Transient polymers rapidly and controllably depolymerize in response to a specific trigger, typically by a chain-end unzipping mechanism. Triggers, such as heat, light, and chemical stimuli, are generally dependent on the chemistry of the polymer backbone or end groups. Single electron transfer (SET), in contrast to other triggering mechanisms, is achievable by various means including chemical, electrochemical, and photochemical oxidation or reduction. Here, we identify SET and subsequent mesolytic cleavage as the major thermal triggering mechanism of cyclic poly(phthalaldehyde) (cPPA) depolymerization. Multimodal SET triggering is demonstrated by both chemical and photoredox-triggered depolymerization of cPPA. Redox-active small molecules (p-chloranil and 1,3,5-trimethoxybenzene) were used to tune the depolymerization onset temperature of cPPA over the range 105–135 °C. Extending this mechanism to photoredox catalysis, N-methylacridinium hexafluorophosphate (NMAPF(6)) was used to photochemically degrade cPPA in solution and thin films. Finally, we fabricated photodegradable cPPA monoliths with a storage modulus of 1.8 GPa and demonstrated complete depolymerization within 25 min of sunlight exposure. Sunlight-triggered depolymerization of cPPA is demonstrated and potentially useful for the manufacture of transient devices that vanish leaving little or no trace. Most importantly, this new mechanism is likely to inspire other SET-triggered transient polymers, whose development may address the ongoing crisis of plastic pollution. |
format | Online Article Text |
id | pubmed-7047432 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-70474322020-03-02 Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism Feinberg, Adam M. Davydovich, Oleg Lloyd, Evan M. Ivanoff, Douglas G. Shiang, Bethany Sottos, Nancy R. Moore, Jeffrey S. ACS Cent Sci [Image: see text] Transient polymers rapidly and controllably depolymerize in response to a specific trigger, typically by a chain-end unzipping mechanism. Triggers, such as heat, light, and chemical stimuli, are generally dependent on the chemistry of the polymer backbone or end groups. Single electron transfer (SET), in contrast to other triggering mechanisms, is achievable by various means including chemical, electrochemical, and photochemical oxidation or reduction. Here, we identify SET and subsequent mesolytic cleavage as the major thermal triggering mechanism of cyclic poly(phthalaldehyde) (cPPA) depolymerization. Multimodal SET triggering is demonstrated by both chemical and photoredox-triggered depolymerization of cPPA. Redox-active small molecules (p-chloranil and 1,3,5-trimethoxybenzene) were used to tune the depolymerization onset temperature of cPPA over the range 105–135 °C. Extending this mechanism to photoredox catalysis, N-methylacridinium hexafluorophosphate (NMAPF(6)) was used to photochemically degrade cPPA in solution and thin films. Finally, we fabricated photodegradable cPPA monoliths with a storage modulus of 1.8 GPa and demonstrated complete depolymerization within 25 min of sunlight exposure. Sunlight-triggered depolymerization of cPPA is demonstrated and potentially useful for the manufacture of transient devices that vanish leaving little or no trace. Most importantly, this new mechanism is likely to inspire other SET-triggered transient polymers, whose development may address the ongoing crisis of plastic pollution. American Chemical Society 2020-02-05 2020-02-26 /pmc/articles/PMC7047432/ /pubmed/32123745 http://dx.doi.org/10.1021/acscentsci.9b01237 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Feinberg, Adam M. Davydovich, Oleg Lloyd, Evan M. Ivanoff, Douglas G. Shiang, Bethany Sottos, Nancy R. Moore, Jeffrey S. Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism |
title | Triggered Transience of Plastic Materials by a Single
Electron Transfer Mechanism |
title_full | Triggered Transience of Plastic Materials by a Single
Electron Transfer Mechanism |
title_fullStr | Triggered Transience of Plastic Materials by a Single
Electron Transfer Mechanism |
title_full_unstemmed | Triggered Transience of Plastic Materials by a Single
Electron Transfer Mechanism |
title_short | Triggered Transience of Plastic Materials by a Single
Electron Transfer Mechanism |
title_sort | triggered transience of plastic materials by a single
electron transfer mechanism |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7047432/ https://www.ncbi.nlm.nih.gov/pubmed/32123745 http://dx.doi.org/10.1021/acscentsci.9b01237 |
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