Molecularly-ordered hydrogels with controllable, anisotropic stimulus response

Abstract

Hydrogels which morph between programmed shapes in response to aqueous stimuli are of significant interest for biosensors and artificial muscles, among other applications. However, programming hydrogel shape change at small size scales is a significant challenge. Here we use the inherent ordering capabilities of liquid crystals to create a mechanically anisotropic hydrogel; when coupled with responsive comonomers, the mechanical anisotropy in the network guides shape change in response to the desired aqueous condition. Our synthetic strategy hinges on the use of a methacrylic chromonic liquid crystal monomer which can be combined with a non-polymerizable chromonic of similar structure to vary the magnitude of shape change while retaining liquid crystalline order. This shape change is directional due to the mechanical anisotropy of the gel, which is up to 50% stiffer along the chromonic stack direction than perpendicular. Additionally, we show that the type of stimulus to which these anisotropic gels respond can be switched by incorporating responsive, hydrophilic comonomers without destroying the nematic phase or alignment. The utility of these properties is demonstrated in polymerized microstructures which exhibit Gaussian curvature in response to high pH due to emergent ordering in a micron-sized capillary.