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Examining the Impact of Relative Mechanophore Activity on the Selectivity of Ultrasound-Induced Mechanochemical Chain Scission

Overholts, Anna C. and Robb, Maxwell J. (2022) Examining the Impact of Relative Mechanophore Activity on the Selectivity of Ultrasound-Induced Mechanochemical Chain Scission. ACS Macro Letters, 11 (6). pp. 733-738. ISSN 2161-1653. doi:10.1021/acsmacrolett.2c00217. https://resolver.caltech.edu/CaltechAUTHORS:20220519-375169000

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Abstract

Despite recent advances in polymer mechanochemistry, a more complete understanding of the factors that dictate the ultrasound-induced mechanochemical activation efficiency of mechanophores is necessary. Here, we examine how the identity of a mechanophore, and hence its unique force-coupled reactivity, affects the competition between mechanophore activation and nonspecific polymer backbone scission. Polymers incorporating distinct mechanophores but with putatively similar “chain-centeredness” exhibit widely different mechanochemical activation efficiencies. Furthermore, we employ mechanophores that can be orthogonally cleaved following ultrasonication using heat or light to report on the degree of nonspecific backbone scission that occurs for different mechanophore-containing polymers subjected to ultrasound-induced mechanical force. Our results illustrate that the identity of the mechanophore as well as its position in the polymer chain are inextricably important parameters that together control the selectivity of mechanophore activation during ultrasonication.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acsmacrolett.2c00217DOIArticle
ORCID:
AuthorORCID
Overholts, Anna C.0000-0002-0593-6903
Robb, Maxwell J.0000-0002-0528-9857
Additional Information:© 2022 American Chemical Society. Received 6 April 2022. Accepted 16 May 2022. Published online 18 May 2022. Financial support from Caltech is gratefully acknowledged. A.C.O. was supported by an NSF Graduate Research Fellowship (DGE-1745301) and an Institute Fellowship from Caltech. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1745301
CaltechUNSPECIFIED
Subject Keywords:Crystal cleavage, Reactivity, Polymers, Aromatic compounds, Polymer chains
Issue or Number:6
DOI:10.1021/acsmacrolett.2c00217
Record Number:CaltechAUTHORS:20220519-375169000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220519-375169000
Official Citation:Examining the Impact of Relative Mechanophore Activity on the Selectivity of Ultrasound-Induced Mechanochemical Chain Scission. Anna C. Overholts and Maxwell J. Robb. ACS Macro Letters 2022 11 (6), 733-738; DOI: 10.1021/acsmacrolett.2c00217
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114812
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:19 May 2022 21:04
Last Modified:12 Jul 2022 18:19

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