Structure–Mechanochemical Activity Relationships for Cyclobutane Mechanophores

Kryger, Matthew J.; Munaretto, Alexander M.; Moore, Jeffrey S.

doi:10.1021/ja2086728

Cited by 169 publications

(183 citation statements)

References 48 publications

(67 reference statements)

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“…Those include explicit incorporation of the force term into a PES 21,[106][107][108] (as in Eq. (8)), using constraints to simulate stretching, 1,[109][110][111] numerical integration of Eqs. (3) and (4), 37,46,68,112 and approximations based on Eq.…”

Section: A Which Bond Breaks First?mentioning

confidence: 99%

Perspective: Mechanochemistry of biological and synthetic molecules

Makarov

2016

The Journal of Chemical Physics

116

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Coupling of mechanical forces and chemical transformations is central to the biophysics of molecular machines, polymer chemistry, fracture mechanics, tribology, and other disciplines. As a consequence, the same physical principles and theoretical models should be applicable in all of those fields; in fact, similar models have been invoked (and often repeatedly reinvented) to describe, for example, cell adhesion, dry and wet friction, propagation of cracks, and action of molecular motors. This perspective offers a unified view of these phenomena, described in terms of chemical kinetics with rates of elementary steps that are force dependent. The central question is then to describe how the rate of a chemical transformation (and its other measurable properties such as the transition path) depends on the applied force. I will describe physical models used to answer this question and compare them with experimental measurements, which employ single-molecule force spectroscopy and which become increasingly common. Multidimensionality of the underlying molecular energy landscapes and the ensuing frequent misalignment between chemical and mechanical coordinates result in a number of distinct scenarios, each showing a nontrivial force dependence of the reaction rate. I will discuss these scenarios, their commonness (or its lack), and the prospects for their experimental validation. Finally, I will discuss open issues in the field.

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Section: A Which Bond Breaks First?mentioning

confidence: 99%

Perspective: Mechanochemistry of biological and synthetic molecules

Makarov

2016

The Journal of Chemical Physics

116

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“…Moore and associates found structuremechanochemical activity relationships when cyclobutanes of variable stereochemistry and substitution degree were sonochemically cleaved in a formal [2+2] cycloaddition that produces alkenes. 59 Using the above-mentioned COGEF approach, methyl esters derived from six cis and trans cyclobutanes with two, one or no cyano substituents (DCC/DCT, MCC/MCT and NCC/NCT pairs, respectively) were evaluated (Fig. 8).…”

Section: 53mentioning

confidence: 99%

On the mechanochemical activation by ultrasound

Cravotto

Gaudino

Cintas³

2013

Chem. Soc. Rev.

191

143

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This is an author version of the contribution published on:On the mechanochemical activation by ultrasound Cravotto G.; Calcio Gaudino E. ; Cintas P Chem. Soc. Rev., 2013,42, 7521-7534 The definitive version is available at:On the mechanochemical activation by ultrasound Cravotto G.; Calcio Gaudino E. ; Cintas P. AbstractChemists have discovered, and recently actively exploited, the fact that subjecting certain molecules to ultrasound waves can bring about transformations that give insight into the correlation between classical tribological processes and the mechanical action caused by collapsing microbubbles when sonic waves propagate through a liquid medium. Chemical transformations induced by ultrasound take place in solution via mechanisms that are markedly different from those associated with molecular activation in the solid state. Both fields, however, share some striking similarities and numerous sonochemical reactions can be rationalized in purely mechanical terms. This tutorial review examines the tribochemical interpretation of sonochemical reactivity and how the multifaceted action of cavitational phenomena determines molecular evolution. A series of case studies involving solids, crystals, and polymers illustrate the mechanical properties of sound waves.

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“…Similarly, primarily because of the high inherent ring strain, the selective cleavage of a cyclobutane bond is facile, which makes cyclobutane and its derivatives promising mechanophores as well [98][99][100][101]. …”

Section: Mechanical Activation Of Microcyclesmentioning

confidence: 99%

Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

Sheiko

2015

Topics in Current Chemistry

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Mechanical activation of chemical bonds is usually achieved by applying external forces. However, nearly all molecules exhibit inherent strain of their chemical bonds and angles as a result of constraints imposed by covalent bonding and interactions with the surrounding environment. Particularly strong deformation of bonds and angles is observed in hyperbranched macromolecules caused by steric repulsion of densely grafted polymer branches. In addition to the tension amplification, macromolecular architecture allows for accurate control of strain distribution, which enables focusing of the internal mechanical tension to specific chemical bonds and angles. As such, chemically identical bonds in self-strained macromolecules become physically distinct because the difference in bond tension leads to the corresponding difference in the electronic structure and chemical reactivity of individual bonds within the same macromolecule. In this review, we outline different approaches to the design of strained macromolecules along with physical principles of tension management, including generation, amplification, and focusing of mechanical tension at specific chemical bonds.

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Structure–Mechanochemical Activity Relationships for Cyclobutane Mechanophores

Cited by 169 publications

References 48 publications

Perspective: Mechanochemistry of biological and synthetic molecules

Perspective: Mechanochemistry of biological and synthetic molecules

On the mechanochemical activation by ultrasound

Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

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