Bioinspired mechanical mineralization of organogels.

Mineralization is a long-lasting method commonly used by biological materials to selectively strengthen in response to site specific mechanical stress. Achieving a similar form of toughening in synthetic polymer composites remains challenging. In previous work, we developed methods to promote chemical reactions via the piezoelectrochemical effect with mechanical responses of inorganic, ZnO nanoparticles. Herein, we report a distinct example of a mechanically-mediated reaction in which the spherical ZnO nanoparticles react themselves leading to the formation of microrods composed of a Zn/S mineral inside an organogel. The microrods can be used to selectively create mineral deposits within the material resulting in the strengthening of the overall resulting composite.

Bio-inspired mechanically adaptive materials through vibration-induced crosslinking.

In nature, bone adapts to mechanical forces it experiences, strengthening itself to match the conditions placed upon it. Here we report a composite material that adapts to the mechanical environment it experiences-varying its modulus as a function of force, time and the frequency of mechanical agitation. Adaptation in the material is managed by mechanically responsive ZnO, which controls a crosslinking reaction between a thiol and an alkene within a polymer composite gel, resulting in a mechanically driven ×66 increase in modulus. As the amount of chemical energy is a function of the mechanical energy input, the material senses and adapts its modulus along the distribution of stress, resembling the bone remodelling behaviour that materials can adapt accordingly to the loading location. Such material design might find use in a wide range of applications, from adhesives to materials that interface with biological systems.

Mechanically Promoted Synthesis of Polymer Organogels via Disulfide Bond Cross-Linking.

Mechanically adaptive polymers could significantly improve the life-cycle of current materials. Piezo-polymerization is a novel approach that harnesses vibrational mechanical energy through piezoelectric nanoparticles to generate chemical promoters for linear polymerization and cross-linking reactions. However, the available piezo-polymerization systems rely on reactions forming irreversible covalent bonds. Dynamic covalent linkages could impart further adaptability to these polymeric systems. Here we show the first example of the piezoelectrochemical synthesis of disulfide bonds to form organogels from polymers with thiol side groups. We demonstrate that the reaction proceeds via piezo-oxidation of the thiol to disulfide in the presence of ZnO nanoparticles and iodide anions under mechanical agitation. We use mechanical energy in the form of ultrasound (40 kHz) and low frequency vibrations (2 kHz) to synthesize a variety of organogels from common synthetic polymers. Additionally, we show that the polymers in these gels can be chemically recycled with a reducing agent. Finally, we study the thermal and mechanical properties of the composites obtained after drying the gels. We believe this new system adds to the piezo-polymerization repertoire and serves as the basis to fabricate mechanically adaptive polymeric materials via dynamic covalent bonds.

100th Anniversary of Macromolecular Science Viewpoint: Piezoelectrically Mediated Mechanochemical Reactions for Adaptive Materials.

Synthetic polymeric materials with adaptive capabilities triggered by mechanical stimuli could significantly extend their life cycle and boost performance. To achieve this, robust mechanically responsive chemistries must be developed. Piezoelectrically mediated chemistry is an emergent area of interest for this purpose since environmental mechanical energy can be harvested and directly converted to chemical energy. This Viewpoint summarizes state-of-the-art knowledge about mechanochemical reactions mediated by the piezoelectrochemical effect, provides mechanistic insight on reactivity, and describes its application for conducting polymerization and cross-linking reactions. In addition, it highlights current challenges with regard to expanding the chemical repertoire and the transition of such methods to solid matrices.

Mechanically Initiated Bulk-Scale Free-Radical Polymerization.

Mechanical initiation of polymerization offers the chance to generate polymers in new environments using an energy source with unique capabilities. Recently, a renewed interest in mechanically controlled polymerization has yielded many techniques for controlled radical polymerization by ultrasound. However, other types of polymerizations induced by mechanical activation are rare, especially for generating high-molecular-weight polymers. Herein is an example of using piezoelectric ZnO nanoparticles to generate free-radical species that initiate chain-growth polymerization and polymer crosslinking. The fast generation of high amounts of reactive radicals enable the formation of polymer/gel by ultrasound activation. This chemistry can be used to harness mechanical energy for constructive purposes in polymeric materials and for controlled polymerizations for bulk-scale reactions.

Ultrasound Promoted Step-Growth Polymerization and Polymer Crosslinking Via Copper Catalyzed Azide-Alkyne "Click" Reaction.

Mechano-activated chemistry is a powerful tool for remodeling of synthetic polymeric materials, however, few reactions are currently available. Here we show that using piezochemical reduction of a CuII -based pre-catalyst, a step-growth polymerization occurs via the copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction to form a linear polytriazole. Furthermore, we show that a linear polymer can be crosslinked mechanochemically using the same chemistry to form a solid organogel. We envision that this chemistry can be used to harness mechanical energy for constructive purposes in polymeric materials.