A backbone lever-arm effect enhances polymer mechanochemistry.

Journal Article

Mechanical forces along a polymer backbone can be used to bring about remarkable reactivity in embedded mechanically active functional groups, but little attention has been paid to how a given polymer backbone delivers that force to the reactant. Here, single-molecule force spectroscopy was used to directly quantify and compare the forces associated with the ring opening of gem-dibromo and gem-dichlorocyclopropanes affixed along the backbone of cis-polynorbornene and cis-polybutadiene. The critical force for isomerization drops by about one-third in the polynorbornene scaffold relative to polybutadiene. The root of the effect lies in more efficient chemomechanical coupling through the polynorbornene backbone, which acts as a phenomenological lever with greater mechanical advantage than polybutadiene. The experimental results are supported computationally and provide the foundation for a new strategy by which to engineer mechanochemical reactivity.

Full Text

Duke Authors

Cited Authors

  • Klukovich, HM; Kouznetsova, TB; Kean, ZS; Lenhardt, JM; Craig, SL

Published Date

  • February 2013

Published In

Volume / Issue

  • 5 / 2

Start / End Page

  • 110 - 114

PubMed ID

  • 23344431

Electronic International Standard Serial Number (EISSN)

  • 1755-4349

Digital Object Identifier (DOI)

  • 10.1038/nchem.1540

Language

  • eng

Conference Location

  • England