The formation of well-defined and functional three-dimensional (3D) structures by buckling of thin sheets subjected to spatially nonuniform stresses is common in biological morphogenesis and has become a subject of great interest in synthetic systems, as such programmable shape-morphing materials hold promise in areas including drug delivery, biomedical devices, soft robotics, and biomimetic systems. Given their ability to undergo large changes in swelling in response to a wide variety of stimuli, hydrogels have naturally emerged as a key type of material in this field. Of particular interest are hybrid systems containing rigid inclusions that can define both the anisotropy and spatial nonuniformity of swelling as well as nanoparticulate additives that can enhance the responsiveness and functionality of the material. In this Account, we discuss recent progress in approaches to achieve well-defined shape morphing in hydrogel hybrids. First, we provide an overview of materials and methods that facilitate fabrication of such systems and outline the geometry and mechanics behind shape morphing of thin sheets. We then discuss how patterning of stiff inclusions within soft responsive hydrogels can be used to program both bending and swelling, thereby providing access to a wide array of complex 3D forms. The use of discretely patterned stiff regions to provide an effective composite response offers distinct advantages in terms of scalability and ease of fabrication compared with approaches based on smooth gradients within a single layer of responsive material. We discuss a number of recent advances wherein control of the mechanical properties and geometric characteristics of patterned stiff elements enables the formation of 3D shapes, including origami-inspired structures, concatenated helical frameworks, and surfaces with nonzero Gaussian curvature. Next, we outline how the inclusion of functional elements such as nanoparticles can enable unique pathways to programmable and even reprogrammable shape-morphing materials. We focus to a large extent on photothermally reprogrammable systems that include one of a variety of additives that serve to efficiently absorb light and convert it into heat, thereby driving the response of a temperature-sensitive hydrogel. Such systems are advantageous in that patterns of light can be defined with very high spatial and temporal resolution in addition to offering the potential for wavelength-selective addressability of multiple different inclusions. We highlight recent advances in the preparation of light-responsive hybrid systems capable of undergoing reprogrammable bending and buckling into well-defined 3D shapes. In addition, we describe several examples where shape tuning of hybrid systems enables control over the motion of responsive hydrogel-based materials. Finally, we offer our perspective on open challenges and future areas of interest for the field.

Patterning deformation within the plane of thin elastic sheets represents a powerful tool for the definition of complex and stimuli-responsive 3D buckled shapes. Previous experimental methods, however, have focused on sheets that access a limited number of shapes pre-programmed into the sheet, restricting the degree of dynamic control. Here, we demonstrate on-demand reconfigurable buckling of poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM) hydrogel network films containing gold nanoparticles (AuNPs) by patterned photothermal deswelling. Predictable, easily controllable, and reversible transformations from a single flat gel sheet to numerous different three-dimensional forms are shown. Importantly, the response time is limited by poroelastic mass transport, rather than photochemical switching kinetics, enabling reconfiguration of shape on timescales of several seconds, with further increases in speed possible by reducing film thickness.

The incorporation of gold nanoparticles within thermally responsive poly(N‐isopropyl acrylamide) hydrogels provides a simple means to define photothermally addressable materials. Relying on such composite gels, it is established here that micropatterned bilayer photoactuators demonstrate rapid and highly reversible bending and unbending behavior in response to illumination with visible light. In addition to actuation by free space light, as in most previous research on such responsive nanocomposite hydrogels, light from a 532 nm laser is also waveguided through a plastic optical fiber directly into the photoactuator, providing remotely controllable actuators that do not require line‐of‐sight access.

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We have demonstrated the two-stage preparation of block polymers with various architectures containing mechanistically incompatible monomers. Three new monounsaturated chain transfer agents (CTAs) were synthesized containing two, four, or eight hydroxyl groups and used for the preparation of telechelic poly(cis-cyclooctene) (PCOE) by ring-opening metathesis polymerization (ROMP). We observed excellent end-group fidelity along with well-controlled molecular weights based on the initial monomer to CTA ratio. Each PCOE was subsequently used as a macroinitiator for the polymerization of D,L-lactide to produce compositionally controlled B x AB x block polymers with linear (x = 1), H-shaped (x = 2), and arachne(spider)arm (x = 4) architectures. Block polymers were prepared containing PLA weight fractions (w L ) ranging from 0.25-0.85. This report significantly expands on the method of combining mechanistically incompatible monomers via tandem polymerizations by introducing branched architectures that can facilitate specific property tailoring.