The many flavours of mechanochemistry and its plausible conceptual underpinnings

O’Neill, Robert T.; Boulatov, Roman

doi:10.1038/s41570-020-00249-y

Cited by 231 publications

(231 citation statements)

References 214 publications

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“…To a good approximation, force-dependent activation energies are a sum of two contributions. 3,74 One captures the kinetic effects of strain imposed on the reactive moiety and the other of changes in strain energy of all other molecular degrees of freedom of the molecule and its surroundings (represented by spring in Fig. 5a).…”

Section: Discussionmentioning

confidence: 99%

“…Over the last decade or so, coupled mechanical forces have been used to drive a range of targeted covalent responses in isolated polymers and in bulk polymeric materials (covalent polymer mechanochemistry). [1][2][3] Mechanochemical strategies continue to evolve, including their recent use in biasing and probing reaction pathways, 4,5 the release of small molecules and protons, [6][7][8] stress reporting, [9][10][11][12][13] stress strengthening, [14][15][16] degradable polymers, 17,18 and fundamental studies of polymer behaviour under load. 19 In organic reactions, mechanochemical coupling has been investigated in simple bond dissociation reactions [20][21][22][23][24] and in a wide variety of reaction classes with respect to regiochemistry, [25][26][27][28] orbital symmetry, 25,[29][30][31] stereochemistry, 32,33 supramolecular architecture, 34,35 dynamic effects, 36,37 and the alignment and/or loading of scissile bonds with applied tension.…”

Section: Introductionmentioning

confidence: 99%

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Force-modulated reductive elimination from platinum(ii) diaryl complexes

Wang

et al. 2021

Chem. Sci.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Force-modulated reductive elimination from platinum(ii) diaryl complexes

Wang

et al. 2021

Chem. Sci.

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“…In polymer mechanochemistry, force‐reactive functional molecular motifs (mechanophores) are designed such that they undergo transformations on the molecular level by rearranging or cleaving bonds with reasonable specificity [29–34] . Mechanophore activation can occur not only in bulk material by exposure to mechanical stress and strain but also in solution via the collapse of US‐induced cavitation bubbles generating shear stress [35] .…”

Section: Introductionmentioning

confidence: 99%

Activation of the Catalytic Activity of Thrombin for Fibrin Formation by Ultrasound

et al. 2021

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The regulation of enzyme activity is a method to control biological function. We report two systems enabling the ultrasound‐induced activation of thrombin, which is vital for secondary hemostasis. First, we designed polyaptamers, which can specifically bind to thrombin, inhibiting its catalytic activity. With ultrasound generating inertial cavitation and therapeutic medical focused ultrasound, the interactions between polyaptamer and enzyme are cleaved, restoring the activity to catalyze the conversion of fibrinogen into fibrin. Second, we used split aptamers conjugated to the surface of gold nanoparticles (AuNPs). In the presence of thrombin, these assemble into an aptamer tertiary structure, induce AuNP aggregation, and deactivate the enzyme. By ultrasonication, the AuNP aggregates reversibly disassemble releasing and activating the enzyme. We envision that this approach will be a blueprint to control the function of other proteins by mechanical stimuli in the sonogenetics field.

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“…Mechanochemistry plays a pivotal role in a wide range of industrial processes, from polymer recycling to the production of self-strengthening materials. 1 Of these various applications, lubricant additives are currently the most economically valuable. 2 These compounds are critical to maintaining the efficient and reliable operation of most lubricated machine components.…”

Section: Introductionmentioning

confidence: 99%

Mechanochemistry of Phosphate Esters Confined between Sliding Iron Surfaces

Latorre

Remias

Moore

et al. 2021

Preprint

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Small changes to the molecular structure of lubricant additives affect their adsorption and dissociation behaviour at the nanoscale, as well as their friction and wear performance at the macroscale. Here, we show using nonequilibrium molecular dynamics simulations with a reactive force field that secondary trialkylphosphates dissociate much faster than primary trialkylphosphates between sliding iron surfaces. For both molecules, dissociative chemisorption proceeds through cleavage of the carbon − oxygen bond. The rate increases exponentially with temperature and stress, which is indicative of a stress-augmented thermally activated process. Both molecules show similar activation energy and activation volume. The much higher reactivity of secondary trialkylphosphates is driven mostly by the pre-exponential factor, which is almost an order of magnitude larger than for primary trialkylphosphates. These observations and the associated kinetic parameters are consistent with recent macroscale tribometer experiments of the antiwear additive zinc dialkyldithiophosphate. This study represents a crucial step towards the virtual screening of lubricant additives with different substituents for optimal tribological performance.

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The many flavours of mechanochemistry and its plausible conceptual underpinnings

Cited by 231 publications

References 214 publications

Force-modulated reductive elimination from platinum(ii) diaryl complexes

Force-modulated reductive elimination from platinum(ii) diaryl complexes

Activation of the Catalytic Activity of Thrombin for Fibrin Formation by Ultrasound

Mechanochemistry of Phosphate Esters Confined between Sliding Iron Surfaces

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