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
The rupture mechanism of rubredoxin is more complex than previously thought.
TL;DR: The distribution of strain energy in the central part of rubredoxin is elucidated in real-time with unprecedented detail, giving important insights into the mechanical unfolding pathway of rub redox, and the rupture mechanism is far more complex than previously thought.
Posted ContentDOI
A Two-Step Baro-Mechanical Cycle for Repeated Activation and Deactivation of Mechanophores
TL;DR: This work uses the well-known spiropyran-merocyanine (SP-MC) interconversion to show that repeated activation and deactivation of the SP mechanophore can be achieved by alternating application of mechanical stretching forces and hydrostatic compression.
Journal ArticleDOI
Rapid activation of non-oriented mechanophores via shock loading and spallation
TL;DR: In this article, a large-scale molecular dynamics simulation of a PMMA-spiropyran co-polymer under dynamic mechanical loading was performed and the activation of the mechanophore under various conditions from dynamical compression to tension during unloading.
Dissertation
Quantum Chemical Investigations of Unimolecular and Bimolecular Reaction Barriers under Mechanochemical Conditions
TL;DR: In this paper, the authors used quantum chemical calculations to examine reaction barriers, ΔE, under mechanochemical conditions for a set of unimolecular and bimolecular reactions and found that increasing the sterics of the substituents increases the mechanical work contribution to the reduction in the force-dependent ΔE.
Journal ArticleDOI
Mechanoredox Catalysis Enables a Sustainable and Versatile Reversible Addition‐Fragmentation Chain Transfer Polymerization Process
TL;DR: In this article , an efficient mechanoredox reversible addition-fragmentation chain transfer (RAFT) polymerization process using mechanical stimuli by implementing piezoelectric barium titanate and a diaryliodonium initiator with minimal solvent usage is presented.
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.