Complex three-dimensional (3D) structures in biology (e.g., cytoskeletal webs, neural circuits, and vasculature networks) form naturally to provide essential functions in even the most basic forms of life. Compelling opportunities exist for analogous 3D architectures in human-made devices, but design options are constrained by existing capabilities in materials growth and assembly. We report routes to previously inaccessible classes of 3D constructs in advanced materials, including device-grade silicon. The schemes involve geometric transformation of 2D micro/nanostructures into extended 3D layouts by compressive buckling. Demonstrations include experimental and theoretical studies of more than 40 representative geometries, from single and multiple helices, toroids, and conical spirals to structures that resemble spherical baskets, cuboid cages, starbursts, flowers, scaffolds, fences, and frameworks, each with single- and/or multiple-level configurations.

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of responsive materials as machines is in robotics. The vision, leadership, and research of Bar-Cohen is seminal in both invigorating and focusing current-day research activities to develop responsive materials [2] and implement [3] them as lightweight, dexterous, and gentle (e.g., soft) robotic elements. In this spirit, this review exhaustively details the materials, the nature of their stimuli-response, and discusses considerations for their implementation in robotic systems and subsystems.Robotics is a well-established but growing field of research. Sustained progress in both performance and functionality continue to be realized in commercial robotic systems largely based on conventional materials and their integration with mechanisms. A recent example is the Atlas robot from Boston Dynamics [4] (Figure 1a). The incorporation of stimuli-responsive materials in robotics has largely focused on component-level demonstrations to extend the performance of a subsystem (such as a hand or gripper).Stimuli-responsive materials, spanning nearly all classes of materials and size scales, are currently subject to widespread examination in corporate, government, and academic research laboratories (Figure 1b-d). [5][6][7] In some cases, these materials have already found widespread commercial implementation in end use and are comparatively mature. The materials and fundamentals of their responses are summarized in Figure 2. Shape memory alloys (SMAs) and ceramic piezoelectric materials are distinctive in that they are hard, stimuli-responsive materials. Deformation of these materials can produce large energy densities due to their inherent stiffness. Electroactive polymers (EAPs) remain a topic of considerable interest, particularly dielectric elastomer actuators (DEAs). Engineered systems are rapidly emerging and enabling performance gains in robotics, largely based on pneumatic or fluidic (such as HASEL [8] actuators) transport processes that localize deformation to generate force or produce motion. Soft materials, such as shape memory polymers (SMPs), hydrogels, and liquid crystalline polymer networks (LCNs) and elastomers (LCEs) may offer distinctive functional performance to robotic systems in allowing local control of deformation without the need for complex interfacing with mechanisms. As will be evident, each of these materials has inherent advantages and performance tradeoffs that must be considered in functional implementations. However, responsive material systems have a common obstacle to widespread use: the performance and Machines are systems that harness input power to extend or advance function. Fundamentally, machines are based on the integration of materials with mechanisms to accomplish tasks-such as generating motion or lifting an object. An emerging research paradigm is the design, synthesis, and integration of responsive materials within or as machines. Herein, a particular focus is the integration of responsive materials to enable robotic (machine) functions such as gripping, lifting, or motility (walk...

Liquid crystalline elastomers (LCE) are stimuli‐responsive materials with a distinguished mechanical response. LCE have been subject to numerous recent functional examinations in robotics, health sciences, and optics. The liquid crystallinity of the elastomeric polymer networks of LCE are largely derived from liquid crystalline monomer precursors. Recent reports have utilized commercially available liquid crystalline diacrylate monomers in chain extension reactions to prepare LCE. These reactions have been largely based on monomeric precursors originally to enhance the and thermal stability of optical films. Here, it is demonstrated that preparing LCE via a liquid crystalline diacrylate with reduced mesogen–mesogen interaction enhances and sharpens the thermotropic actuation of these materials. Robust composition‐response correlations are demonstrated in LCE prepared by three common synthetic methods. The enhanced thermotropic response of LCE prepared from this precursor increases the thermomechanical efficiency by sixfold. Accordingly, this work addresses important limitations in utilizing the thermal response of LCE in robotics, health care, and consumer goods.

Liquid crystal elastomers (LCE) are an emerging class of material actuators. LCE undergo macroscopic dimensional changes when subjected to a stimulus. The large stimuli-response of LCE is associated with thermotropic disruption of order. Historically, comparatively high temperatures are required to disrupt orientation in LCE to achieve meaningful work output. Here, we introduce an approach to prepare LCE via thiol-Michael/thiol-ene reactions that actuate at or below ambient temperature. Alignment was imparted to the LCE by mechanical alignment and 3D printing. The LCE materials detailed here achieve strains of 40 % with a maximum deformation rate of 6.5 % °CÀ 1 . The functional utility of the tunability of the thermotropic response of these materials is illustrated in reconfiguration triggered via body heat and sequential actuation of a multi-material element.

Materials chemistries for hydrogel scaffolds that are capable of programming temporal (4D) attributes of cellular decision‐making in supported 3D microcultures are described. The scaffolds are fabricated using direct‐ink writing (DIW)—a 3D‐printing technique using extrusion to pattern scaffolds at biologically relevant diameters (≤ 100 µm). Herein, DIW is exploited to variously incorporate a rheological nanoclay, Laponite XLG (LAP), into 2‐hydroxyethyl methacrylate (HEMA)‐based hydrogels—printing the LAP–HEMA (LH) composites as functional modifiers within otherwise unmodified 2D and 3D HEMA microstructures. The nanoclay‐modified domains, when tested as thin films, require no activating (e.g., protein) treatments to promote robust growth compliances that direct the spatial attachment of fibroblast (3T3) and preosteoblast (E1) cells, fostering for the latter a capacity to direct long‐term osteodifferentiation. Cell‐to‐gel interfacial morphologies and cellular motility are analyzed with spatial light interference microscopy (SLIM). Through combination of HEMA and LH gels, high‐resolution DIW of a nanocomposite ink (UniH) that translates organizationally dynamic attributes seen with 2D gels into dentition‐mimetic 3D scaffolds is demonstrated. These analyses confirm that the underlying materials chemistry and geometry of hydrogel nanocomposites are capable of directing cellular attachment and temporal development within 3D microcultures—a useful material system for the 4D patterning of hydrogel scaffolds.

Direct-ink writing (DIW), a rapidly growing and advancing form of additive manufacturing, provides capacities for on-demand tailoring of materials to meet specific requirements for final designs. The penultimate challenge faced with the increasing demand of customization is to extend beyond modification of shape to create 4D structures, dynamic 3D structures that can respond to stimuli in the local environment. Patterning material gradients is foundational for assembly of 4D structures, however, there remains a general need for useful materials chemistries to generate gray scale gradients via DIW. Here, presented is a simple materials assembly paradigm using DIW to pattern ionotropic gradients in hydrogels. Using structures that architecturally mimic seajelly organisms, the capabilities of spatial patterning are highlighted as exemplified by selectively programming the valency of the ion-binding agents. Spatial gradients, when combined with geometry, allow for programming the flexibility and movement of iron oxide nanoparticleloaded ionotropic hydrogels to generate 4D-printed structures that actuate in the presence of local magnetic fields. This work highlights approaches to 4D design complexity that exploits 3D-printed gray-scale/gradient mechanics.

Understanding and controlling the interactions occurring between cells and engineered materials are central challenges towards progress in the development of biomedical devices. In this work, we describe materials for direct ink writing (DIW), an extrusion-based type of 3D printing, that embed a custom synthetic protein (RGD-PDL) within the microfilaments of 3D-hydrogel scaffolds to modify these interactions and differentially direct tissue-level organization of complex cell populations in vitro. The RGD-PDL is synthesized by modifying poly-D-lysine (PDL) to varying extents with peptides containing the integrin-binding motif Arg-Gly-Asp (RGD). Compositional gradients of the RGD-PDL presented by both patterned and thin-film poly-(2-hydroxyethyl) methacrylate (pHEMA) substrates allow the patterning of cell-growth compliance in a grayscale form. The surface chemistry-dependent guidance of cell growth on the RGD-PDL-modified pHEMA materials is demonstrated using a model NIH-3T3 fibroblast cell line. The formation of a more complex cellular system — organotypic primary murine dorsal root ganglion (DRG) – in culture is also achieved on these scaffolds, where distinctive forms of cell growth and migration guidance are seen depending on their RGD-PDL content and topography. This experimental platform for the study of physicochemical factors on the formation and the reorganization of organotypic cultures offers useful capabilities for studies in tissue engineering, regenerative medicine, and diagnostics.