Department of Chemistry, University of Washington , Seattle, Washington 98195, United States.
J Am Chem Soc. 2013 Jun 5;135(22):8189-92. doi: 10.1021/ja403757p. Epub 2013 May 23.
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.
我们描述了机械化学转导研究，该研究探测了与伸长聚合物主链正交的键的激活。机械共振器交联材料的压缩导致小分子通过共价键的断裂释放，这些共价键不是伸长聚合物链段的整体组成部分。据推测，这种反应性源于通过聚合物网络的交联单元分布的力和随后的键弯曲运动，这些运动与整体反应的几何变化一致。这种与传统聚合物机械化学的背离，其中激活主要通过力诱导的键伸长来实现，是朝着能够释放侧链功能而不固有地损害整体大分子结构的机械共振器迈出的第一步。
