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Mechanically Triggered Release of Functionally Diverse Molecular Payloads from Masked 2-Furylcarbinol Derivatives

Hu, Xiaoran and Zeng, Tian and Husic, Corey C. and Robb, Maxwell J. (2021) Mechanically Triggered Release of Functionally Diverse Molecular Payloads from Masked 2-Furylcarbinol Derivatives. ACS Central Science, 7 (7). pp. 1216-1224. ISSN 2374-7943. PMCID PMC8323246. doi:10.1021/acscentsci.1c00460. https://resolver.caltech.edu/CaltechAUTHORS:20210723-184201152

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Abstract

Polymers that release functional small molecules in response to mechanical force are appealing targets for drug delivery, sensing, catalysis, and many other applications. Mechanically sensitive molecules called mechanophores are uniquely suited to enable molecular release with excellent selectivity and control, but mechanophore designs capable of releasing cargo with diverse chemical functionality are limited. Here, we describe a general and highly modular mechanophore platform based on masked 2-furylcarbinol derivatives that spontaneously decompose under mild conditions upon liberation via a mechanically triggered reaction, resulting in the release of a covalently installed molecular payload. We identify key structure–property relationships for the reactivity of 2-furylcarbinol derivatives that enable the mechanically triggered release of functionally diverse molecular cargo with release kinetics being tunable over several orders of magnitude. In particular, the incorporation of an electron-donating phenoxy group on the furan ring in combination with an α-methyl substituent dramatically lowers the activation barrier for fragmentation, providing a highly active substrate for molecular release. Moreover, we find that phenoxy substitution enhances the thermal stability of the mechanophore without adversely affecting its mechanochemical reactivity. The generality and efficacy of this molecular design platform are demonstrated using ultrasound-induced mechanical force to trigger the efficient release of a broad scope of cargo molecules, including those bearing alcohol, phenol, alkylamine, arylamine, carboxylic acid, and sulfonic acid functional groups.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acscentsci.1c00460DOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8323246PubMed CentralArticle
ORCID:
AuthorORCID
Hu, Xiaoran0000-0001-7598-4516
Zeng, Tian0000-0001-5957-3442
Husic, Corey C.0000-0003-0248-7484
Robb, Maxwell J.0000-0002-0528-9857
Additional Information:© 2021 The Authors. ACS AuthorChoice. Published by American Chemical Society. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) Received: April 13, 2021; Published: July 14, 2021. This research was supported by Caltech and the Arnold and Mabel Beckman Foundation through a Beckman Young Investigator Award. We thank the Center for Catalysis and Chemical Synthesis of the Beckman Institute at Caltech and the CCE Multiuser Mass Spectrometry Laboratory for access to equipment. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:Reaction products, Substituents, Inorganic carbon compounds, Organic compounds, Polymers
Issue or Number:7
PubMed Central ID:PMC8323246
DOI:10.1021/acscentsci.1c00460
Record Number:CaltechAUTHORS:20210723-184201152
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210723-184201152
Official Citation:Mechanically Triggered Release of Functionally Diverse Molecular Payloads from Masked 2-Furylcarbinol Derivatives. Xiaoran Hu, Tian Zeng, Corey C. Husic, and Maxwell J. Robb. ACS Central Science 2021 7 (7), 1216-1224; DOI: 10.1021/acscentsci.1c00460
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110003
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:26 Jul 2021 17:31
Last Modified:04 Aug 2021 19:33

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