Journal ArticleDOI
"Flex-activated" mechanophores: using polymer mechanochemistry to direct bond bending activation.
TLDR
Studies in mechanochemical transduction that probe the activation of bonds orthogonal to an elongated polymer main chain are described, a first step toward mechanophores capable of releasing side-chain functionalities without inherently compromising the overall macromolecular architecture.Abstract:
We describe studies in mechanochemical transduction that probe the activation of bonds orthogonal to an elongated polymer main chain. Compression of mechanophore-cross-linked materials resulted in the release of small molecules via cleavage of covalent bonds that were not integral components of the elongated polymer segments. The reactivity is proposed to arise from the distribution of force through the cross-linking units of the polymer network and subsequent bond bending motions that are consistent with the geometric changes in the overall reaction. This departure from contemporary polymer mechanochemistry, in which activation is achieved primarily by force-induced bond elongation, is a first step toward mechanophores capable of releasing side-chain functionalities without inherently compromising the overall macromolecular architecture.read more
Citations
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Journal ArticleDOI
Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed "Tension Trapped Transition State".
Junpeng Wang,Mitchell T. Ong,Tatiana B. Kouznetsova,Jeremy M. Lenhardt,Todd J. Martínez,Stephen L. Craig +5 more
TL;DR: S-trans, s-trans 1,3-diradicaloid transition states are trapped by tension along the backbone of purely cis-substituted gem-difluorocyclopropanated polybutadiene using the extensional forces generated by pulsed sonication of dilute polymer solutions.
Journal ArticleDOI
Strain-Dependent Kinetics in the Cis-to-Trans Isomerization of Azobenzene in Bulk Elastomers.
TL;DR: In this paper, the cis-to-trans isomerization of azobenzene is accelerated in a bulk PDMS elastomer under uniaxial tension by a single-exponential first-order process.
Journal ArticleDOI
Mechanical activation of a dithioester derivative-based retro RAFT-HDA reaction
TL;DR: In this article, a new mechanophore was synthesized from a dithioester derivative and an open-chain diene by the HDA reaction, which was embedded in the polymer chain by initiating the polymerization of methyl acrylate (MA).
Journal ArticleDOI
Mechanochemically Gated Photoswitching: Expanding the Scope of Polymer Mechanochromism
TL;DR: In this paper, a cyclopentadiene-maleimide Diels-Alder adduct was designed to reveal a latent diarylethene photoswitch following mechanical activation, and UV light converted the colorless diels-alder molecule into the colored isomer via a 6π-electrocyclic ring-closing reaction.
References
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Journal ArticleDOI
Force-induced activation of covalent bonds in mechanoresponsive polymeric materials
Douglas A. Davis,Andrew Hamilton,Jinglei Yang,Jinglei Yang,Lee D. Cremar,Dara Van. Gough,Stephanie L. Potisek,Mitchell T. Ong,Paul V. Braun,Todd J. Martínez,Todd J. Martínez,Scott R. White,Jeffrey S. Moore,Nancy R. Sottos +13 more
TL;DR: It is found that pronounced changes in colour and fluorescence emerge with the accumulation of plastic deformation, indicating that in these polymeric materials the transduction of mechanical force into the ring-opening reaction is an activated process.
Journal ArticleDOI
Mechanically-induced chemical changes in polymeric materials
Mary M. Caruso,Douglas A. Davis,Qilong Shen,Susan A. Odom,Nancy R. Sottos,Scott R. White,Jeffrey S. Moore +6 more
TL;DR: The purpose of this review is to broadly survey the mechanical to chemical relationships between synthetic polymers, and to consider the I-O relationship as an energy transduction process for designing stimuli-responsive materials.
Journal ArticleDOI
Mechanochemistry: the mechanical activation of covalent bonds.
TL;DR: A survey of the classical works in mechanochemistry is given and the key mechanochemical phenomena into perspective with recent results from atomic force microscopy and quantum molecular dynamics simulations are put into perspective.
Journal ArticleDOI
From mechanism to mouse: a tale of two bioorthogonal reactions.
TL;DR: Work in the laboratory led to the development of two bioorthogonal transformations that exploit the azide as a small, abiotic, and bioinert reaction partner: the Staudinger ligation and strain-promoted azide–alkyne cycloaddition.
Journal ArticleDOI
Mechanical processes in biochemistry.
TL;DR: This review provides the conceptual framework to understand the role of mechanical force in biochemistry.