Adsorption-induced scission of carbon-carbon bonds

Covalent carbon-carbon bonds are hard to break. Their strength is evident in the hardness of diamonds(1,2) and tensile strength of polymeric fibres(3-6); on the single-molecule level, it manifests itself in the need for forces of several nanonewtons to extend and mechanically rupture one bond. Such forces have been generated using extensional flow(7-9), ultrasonic irradiation(10), receding meniscus(11) and by directly stretching a single molecule with nanoprobes(12-16). Here we show that simple adsorption of brush-like macromolecules with long side chains on a substrate can induce not only conformational deformations(17), but also spontaneous rupture of covalent bonds in the macromolecular backbone. We attribute this behaviour to the fact that the attractive interaction between the side chains and the substrate is maximized by the spreading of the side chains, which in turn induces tension along the polymer backbone. Provided the side-chain densities and substrate interaction are sufficiently high, the tension generated will be strong enough to rupture covalent carbon-carbon bonds. We expect similar adsorption-induced backbone scission to occur for all macromolecules with highly branched architectures, such as brushes and dendrimers. This behaviour needs to be considered when designing surface-targeted macromolecules of this type either to avoid undesired degradation, or to ensure rupture at predetermined macromolecular sites.