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
Impact of tensile and compressive forces on the hydrolysis of cellulose and chitin.
Hirokazu Kobayashi,Yusuke Suzuki,Takuya Sagawa,Takuya Sagawa,Kyoichi Kuroki,Jun-ya Hasegawa,Atsushi Fukuoka +6 more
TL;DR: In this paper, the authors show how the mechanical forces produced by ball-milling activate the glycosidic bonds of carbohydrate molecules towards hydrolysis, and connect the classical physics of ball milling on a macro scale with molecular activation at a quantum level.
Journal ArticleDOI
On the calculation of internal forces in mechanically stressed polyatomic molecules.
TL;DR: Analysis of internal forces reveals interesting phenomena such as the force multiplication effect, where weak external forces may be used to break strong bonds, and offers insight into the catch-bond phenomenon where chemical reactivity is suppressed through application of a force.
Journal ArticleDOI
Diaryliodonium salts facilitate metal-free mechanoredox free radical polymerizations
TL;DR: In this article , the iodonium-initiated free-radical polymerization of (meth)acrylate monomers under ultrasonic irradiation and ball-milling conditions is presented.
Journal ArticleDOI
Mechanochemistry of Cationic Cobaltocenium Mechanophore.
Yujin Cha,Tianyu Zhu,Ye Sha,Huina Lin,Jihyeon Hwang,Matthew Seraydarian,Stephen L. Craig,Chuanbing Tang +7 more
TL;DR: In this paper, a combination of experimental and computational studies on the mechanochemistry of main-chain cobaltocenium-containing polymers is presented, showing that despite their high bond dissociation energy, cobalt-ocenium mechanophores are found to be selective sites of main chain scission under sonomechanical activation.
Journal ArticleDOI
A modular approach to mechanically gated photoswitching with color-tunable molecular force probes.
Ross Barber,Maxwell J. Robb +1 more
TL;DR: A completely redesigned, highly modular mechanophore platform for mechanically gated photoswitching that offers a robust, accessible synthesis and late stage diversification through Pd-catalyzed cross-coupling reactions to precisely tune the photophysical properties of the masked diarylethene (DAE) photoswitch is reported.
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.
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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.