Programmable Morphing Hydrogels for Soft Actuators and Robots: From Structure Designs to Active Functions.

Nature provides abundant inspiration and elegant paradigms for the development of smart materials that can actuate, morph, and move on demand. One remarkable capacity of living organisms is to adapt their shapes or positions in response to stimuli. Programmed deformations or movements in plant organs are mainly driven by water absorption/dehydration of cells, while versatile motions of mollusks are based on contraction/extension of muscles. Understanding the general principles of these morphing and motion behaviors can give rise to disruptive technologies for soft robotics, flexible electronics, biomedical devices, etc. As one kind of intelligent material, hydrogels with high similarity to soft biotissues and diverse responses to external stimuli are an ideal candidate to construct soft actuators and robots.The objective of this Account is to give an overview of the fundamental principles for controllable deformations and motions of hydrogels, with a focus on the structure designs and responsive functions of the corresponding soft actuators and robots. This field has been rapidly developed in recent years with a growing understanding of working principles in natural organisms and a substantial revolution of manufacturing technologies to devise bioinspired hydrogel systems with desired structures. Diverse morphing hydrogels and soft actuators/robots have been developed on the basis of several pioneering works, ranging from bending and folding deformations of bilayer hydrogels to self-shaping of non-Euclidean hydrogel surfaces, and from thermoactuated bilayer gel "hands" to electrodriven polyelectrolyte gel "worms". These morphing hydrogels have demonstrated active functions and versatile applications in biomedical and engineering fields.In this Account, we discuss recent progress in morphing hydrogels and highlight the design principles and relevant applications. First, we introduce the fundamentals of basic deformation modes, together with generic structure features, actuation strategies, and morphing mechanisms. The advantages of in-plane gradient structures are highlighted for programmable deformations by harnessing the out-of-plane buckling with bistability nature to obtain sophisticated three-dimensional configurations. Next, we give an overview of soft actuators and robots based on morphing hydrogels and focus on the working principles of the active systems with different structure designs. We discuss the advancements of hydrogel-based soft robots capable of swift locomotion with different gaits and emphasize the significances of structure control and dynamic actuation. Then we summarize versatile applications of hydrogel-based actuators and robots in biomedicines, cargo delivery, soft electronics, information encryption, and so forth. Some hydrogel robots with a built-in feedback loop and self-sensing system exhibit collaborative functions and advanced intelligence that are informative for the design of next-generation hydrogel machines. Finally, concluding remarks are given to discuss future opportunities and remaining challenges in this field. For example, miniature hydrogel-based actuators/robots with therapeutic or diagnostic functions are highly desired for biomedical applications. The morphing mechanisms summarized in this Account should be applicable to other responsive materials. We hope that this Account will inspire more scientists to be involved in this emerging area and make contributions to reveal novel working principles, design multifunctional soft machines, and explore applications in diverse fields.

An Opto- and Thermal-Rewrite PCM/CNF-IR 780 Energy Storage Nanopaper with Mechanical Regulated Performance.

In spite of efforts to fabricate self-assembled energy storage nanopaper with potential applications in displays, greenhouses, and sensors, few studies have investigated their multiple stimuli-sensitivities. Here, an opto- and thermal-rewrite phase change material/cellulose nanofibril (PCM/CNF) energy storage nanopaper with mechanical regulated performance is facilely fabricated, through 5 min sonication of PCMs and CNFs in an aqueous system. The combination of PCM and CNF not only guarantees the recyclability of PCM without leakage, but also offers nanopaper adaptive properties by leveraging the mobility and optical variation accompanying solid-to-liquid transition of PCM. Besides, trace near-infrared (NIR) dye (IR 780) in it imparts a PCM-embedded nanopaper photothermal effect to modulate the local transparency via time- and position-controlled laser exposure, leading to a reusable opto-writing nanopaper. Furthermore, since the synergistic effect of stick-and-slip function attributes from PCMs and pore structures are produced by calcium ions, the PCM/CNF energy storage nanopaper exhibits excellent mechanically regulated performance from rigid to flexible, which greatly enriches their application in energy-efficient smart buildings and displays.

Highly Mineralized Biomimetic Polysaccharide Nanofiber Materials Using Enzymatic Mineralization.

Many biological high-performance composites, such as bone, antler, and crustacean cuticles, are composed of densely mineralized and ordered nanofiber materials. The mimicry of even simplistic bioinspired structures, i.e., of densely and homogeneously mineralized nanofibrillar materials with controllable mechanical performance, continues to be a grand challenge. Here, using alkaline phosphatase as an enzymatic catalyst, we demonstrate the dense, homogeneous, and spatially controlled mineralization of calcium phosphate nanostructures within networks of anionically charged cellulose nanofibrils (CNFs) and cationically charged chitin nanofibrils (ChNFs)-both emerging biobased nanoscale building blocks for sustainable high-performance materials design. Our study reveals that anionic CNFs lead to a more homogeneous nanoscale mineralization with very high mineral contents up to ca. 70 wt % with a transition from amorphous to crystalline deposits, while cationic ChNFs yield rod-like crystalline morphologies. The bone-inspired CNF bulk films exhibit a significantly increased stiffness, maintain good flexibility and translucency, and have a significant gain in wet state mechanical properties. The mechanical properties can be tuned both by the enzyme concentration and the mineralization time. Moreover, we also show a spatial control of the mineralization using kinetically controlled substrate uptake in a dialysis reactor, and by spatially selectively incorporating the enzyme into 2D printed filament patterns. The strategy highlights possibilities for spatial encoding of enzymes in tailored structures and patterns and programmed mineralization processes, promoting the potential application of mineralized CNF biomaterials with complex gradients for bone substitutes and tissue regeneration in general.

Vitrimer Chemistry Meets Cellulose Nanofibrils: Bioinspired Nanopapers with High Water Resistance and Strong Adhesion.

Nanopapers containing cellulose nanofibrils (CNFs) are an emerging and sustainable class of high performance materials. The diversification and improvement of the mechanical and functional property space critically depend on integration of CNFs with rationally designed, tailor-made polymers following bioinspired nanocomposite designs. Here we combine for the first time CNFs with colloidal dispersions of vitrimer nanoparticles (VP) into mechanically coherent nanopaper materials. Vitrimers are permanently cross-linked polymer networks that undergo temperature-induced bond shuffling through an associative mechanism and which allow welding and reshaping on the macroscale. The choice of low glass transition, hydrophobic vitrimers derived from fatty acids and polydimethylsiloxane (PDMS), and achieving dynamic reshuffling of cross-links through transesterification reactions enables excellent compatibility and covalent attachment onto the CNF surfaces. Moreover, the resulting films are ductile, stretchable and offer high water resistance. The success of imparting the vitrimeric polymeric behavior into the nanocomposite, as well as the curing mechanism of the vitrimer, is highlighted through thorough analysis of structural and mechanical properties. The dynamic exchange chemistry of the vitrimers enables efficient welding of two nanocomposite parts as characterized by good bonding strength during single lap shear tests. In the future, we expect that the dynamic character of vitrimers becomes a promising option for the design of mechanically adaptive bioinspired nanocomposites and for shaping and reshaping such materials.

Biodegradable Laser Arrays Self-Assembled from Plant Resources.

The transition toward future sustainable societies largely depends on disruptive innovations in biobased materials to substitute nonsustainable advanced functional materials. In the field of optics, advanced devices (e.g., lasers or metamaterial devices) are typically manufactured using top-down engineering and synthetic materials. This work breaks with such concepts and switchable lasers self-assembled from plant-based cellulose nanocrystals and fluorescent polymers at room temperature and from water are shown. Controlled structure formation allows laser-grade cholesteric photonic bandgap materials, in which the photonic bandgap is matched to the fluorescence emission to function as an efficient resonator for low threshold multimode lasing. The lasers can be switched on and off using humidity, and can be printed into pixelated arrays. Additionally, the materials exhibit stiffness above typical thermoplastic polymers and biodegradability in soil. The concept showcases that highly advanced functions can be encoded into biobased materials, and opens the design space for future sustainable optical devices of unprecedented function.