- Force-reactivity property of a single monomer is sufficient to predict the micromechanical behavior of its polymer
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We demonstrate an accurate prediction of the micromechanical behavior of a single chain of cyclopropanated polybutadiene, which is governed by rapid isomerization of the cyclopropane moieties at ~1.2 nN, from the force-rate correlation of this reaction measured in a small series of increasingly strained macrocycles. The data demonstrate that a single physical quantity, force, uniquely defines the dynamics across length scales from >100 to 1 nm and that strain imposed through molecular design and that imposed by micromanipulation techniques have equivalent effects on the kinetics of a chemical reaction. This represents a new method of screening potential monomers for applications in stress-responsive materials that could also facilitate atomistic interpretations of single-molecule force experiments.
- Akbulatov, Sergey,Tian, Yancong,Boulatov, Roman
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supporting information; experimental part
p. 7620 - 7623
(2012/06/30)
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- LES (TRIMETHYLSILYL)BICYCLO-ALCENES, NOUVEAUX SILYLCYCLOPROPANES BICYCLIQUES FONCTIONNELS
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A convenient synthesis of new silylbicyclo-alkenes is reported involving a facile and rapid process and giving both endo and exo monosilyl isomers as well as gem-disilyl derivatives.The behaviour of these species towards acids has been investigated.Both the size of the large ring and the double-bond position play a role in the regiochemistry of the electrophilic attack.These results bring to ligth new perspectives for functionalization of cyclololefins via cyclopropanation.
- Grignon-Dubois, M.,Dunogues, J.,Ahra, M.
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p. 216 - 225
(2007/10/02)
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- trans-Cycloalkenes. Part 11. trans-Cyclonona-1,2,6-triene, a Transient Precursor of 2,3-Divinylcyclopentene
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Three potential precursors of trans-cyclonona-1,2,6-triene (1), namely the allene-dioxolan (7), the allene-oxathiolan (14), and the dichlorocyclopropane (16) have been prepared starting ultimately from cyclo-octa-1,5-diene.Treatment of these precursors with BunLi under conditions appropriate to each case gave 2,3-divinylcyclopentene in moderate to good yields.It is considered that trans-cyclonona-1,2,6-triene is formed as transient intermediate.
- Connel, A. Christopher,Whitham, Gordon H.
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p. 989 - 994
(2007/10/02)
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- Synthesis of Polycyclic Homocyclopropylcarbinols by Reductive Cyclization of Bromocyclopropyl Epoxides
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A new synthetic route to polycyclic homocyclopropylcarbinols has been realized by lithiation of bromocyclopropyl epoxides with n-butyllithium and subsequent intramolecular attack of the metalated cyclopropane ring onto the epoxide.A series of seven bromoc
- Last, Larry A.,Fretz, E. Robert,Coates, Robert M.
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p. 3211 - 3219
(2007/10/02)
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