Force-induced activation of covalent bonds in mechanoresponsive polymeric materials.

Mechanochemical transduction enables an extraordinary range of physiological processes such as the sense of touch, hearing, balance, muscle contraction, and the growth and remodelling of tissue and bone. Although biology is replete with materials systems that actively and functionally respond to mechanical stimuli, the default mechanochemical reaction of bulk polymers to large external stress is the unselective scission of covalent bonds, resulting in damage or failure. An alternative to this degradation process is the rational molecular design of synthetic materials such that mechanical stress favourably alters material properties. A few mechanosensitive polymers with this property have been developed; but their active response is mediated through non-covalent processes, which may limit the extent to which properties can be modified and the long-term stability in structural materials. Previously, we have shown with dissolved polymer strands incorporating mechanically sensitive chemical groups-so-called mechanophores-that the directional nature of mechanical forces can selectively break and re-form covalent bonds. We now demonstrate that such force-induced covalent-bond activation can also be realized with mechanophore-linked elastomeric and glassy polymers, by using a mechanophore that changes colour as it undergoes a reversible electrocyclic ring-opening reaction under tensile stress and thus allows us to directly and locally visualize the mechanochemical reaction. We find that pronounced changes in colour and fluorescence emerge with the accumulation of plastic deformation, indicating that in these polymeric materials the transduction of mechanical force into the ring-opening reaction is an activated process. We anticipate that force activation of covalent bonds can serve as a general strategy for the development of new mechanophore building blocks that impart polymeric materials with desirable functionalities ranging from damage sensing to fully regenerative self-healing.

Highly efficient mechanochemical scission of silver-carbene coordination polymers.

The ultrasound-induced scission of silver carbene coordination complexes with polytetrahydrofuran-functionalized N-heterocyclic carbene ligands is reported. In solution, scission is very efficient, with complete conversion within 10 min when the polymers have a molecular weight of 6.7 kDa. The mechanochemical origin of the scission is supported by the molecular weight dependence of the scission rate and by the low reactivity of the silver complex with low molecular weight ligands. The mechanochemical process at room temperature is much faster than thermal scission at 60 degreesC, which has a conversion of 30% in 18 h.