Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.

Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.

Molecular composition, grafting density and film area affect the swelling-induced Au-S bond breakage.

In previous studies, we reported the first observation of the Au-S bond breakage induced mechanically by the swelling of the surface-tethered weak polyelectrolyte brushes in phosphate buffered saline (PBS), a phenomenon with broad applications in the fields of biosensors and functional surfaces. In this study, three factors, namely the molecular composition, grafting density and film area of the weak polyelectrolyte, carboxylated poly(oligo(ethylene glycol) methacrylate-random-2-hydroxyethyl methacrylate) (poly(OEGMA-r-HEMA)), were studied systematically on how they affected the swelling-induced Au-S bond breakage (ABB). The results showed that, first, the swelling-induced ABB is applicable to a range of molecular compositions and grafting densities; but the critical thickness (Tcritical,dry) varied with both of the two factors. An analysis on the swelling ratio further revealed that the difference in the Tcritical,dry arose from the difference in the swelling ability. A film needed to swell to ∼250 nm to induce ABB regardless of its composition or structure, thus a higher swelling ratio would lead to a lower Tcritical,dry value. Then, the impact of the film area was studied in micrometer- and sub-micrometer-scale brush patterns, which showed that only partial, rather than complete ABB was induced in these microscopic films, resulting in buckling instead of film detaching. These results demonstrated that the ABB is suitable to be used in the design of biosensors, stimulus-responsive materials and mechanochemical devices. Although the >160 µm(2) required area for uniform ABB hinders the application of ABB in nanolithography, the irreversible buckling provides a facile method of generating rough surfaces.