Photo-steered rapid and multimodal locomotion of 3D-printed tough hydrogel robots.

Hydrogels are an ideal material to develop soft robots. However, it remains a grand challenge to develop miniaturized hydrogel robots with mechanical robustness, rapid actuation, and multi-gait motions. Reported here is a facile strategy to fabricate hydrogel-based soft robots by three-dimensional (3D) printing of responsive and nonresponsive tough gels for programmed morphing and locomotion upon stimulations. Highly viscoelastic poly(acrylic acid-co-acrylamide) and poly(acrylic acid-co-N-isopropyl acrylamide) aqueous solutions, as well as their mixtures, are printed with multiple nozzles into 3D constructs followed by incubation in a solution of zirconium ions to form robust carboxyl-Zr4+ coordination complexes, to produce tough metallo-supramolecular hydrogel fibers. Gold nanorods are incorporated into ink to afford printed gels with response to light. Owing to the mechanical excellence and small diameter of gel fibers, the printed hydrogel robots exhibit high robustness, fast response, and agile motions when remotely steered by dynamic light. The design of printed constructs and steering with spatiotemporal light allow for multimodal motions with programmable trajectories of the gel robots. The hydrogel robots can walk, turn, flip, and transport cargos upon light stimulations. Such printed hydrogels with good mechanical performances, fast response, and agile locomotion may open opportunities for soft robots in biomedical and engineering fields.

Bistable Joints Enable the Morphing of Hydrogel Sheets with Multistable Configurations.

Joints, as a flexing element to connect different parts, are widespread in natural systems. Various joints exist in the body and play crucial roles to execute gestures and gaits. These scenarios have inspired the design of mechanical joints with passive, hard materials, which usually need an external power supply to drive the transformations. The incorporation of soft and active joints provides a modular strategy to devise soft actuators and robots. However, transformations of responsive joints under external stimuli are usually in uni-mode with a pre-determined direction. Here, hydrogel joints capable of folding and twisting transformation in bi-mode are reported, which enable the composite hydrogel to form multiple configurations under constant conditions. These joints have an in-plane gradient structure and comprise stiff, passive gel as the frame and soft, active gel as the actuating unit. Under external stimuli, the response mismatch between different gels leads to out-of-plane folding or twisting deformation with the feature of bistability. These joints can be modularly integrated with other gels to afford complex deformations and multistable configurations. This approach favors selective control of hydrogel's architectures and versatile design of hydrogel devices, as demonstrated by proof-of-concept examples. It shall also merit the development of metamaterials, soft actuators, and robots, etc.

Magneto-Orientation of Magnetic Double Stacks for Patterned Anisotropic Hydrogels with Multiple Responses and Modulable Motions.

Reported here is a multi-response anisotropic poly(N-isopropylacrylamide) hydrogel developed by using a rotating magnetic field to align magnetic double stacks (MDSs) that are fixed by polymerization. The magneto-orientation of MDSs originates from the unique structure with γ-Fe2 O3 nanoparticles sandwiched by two silicate nanosheets. The resultant gels not only exhibit anisotropic optical and mechanical properties but also show anisotropic responses to temperature and light. Gels with complex ordered structures of MDSs are further devised by multi-step magnetic orientation and photolithographic polymerization. These gels show varied birefringence patterns with potentials as information materials, and can deform into specific configurations upon stimulations. Multi-gait motions are further realized in the patterned gel through dynamic deformation under spatiotemporal light and friction regulation by imposed magnetic force. The magneto-orientation assisted fabrication of hydrogels with anisotropic structures and additional functions should bring opportunities for gel materials in biomedical devices, soft actuators/robots, etc.

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.

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.

Electrical switching of high-performance bioinspired nanocellulose nanocomposites.

Nature fascinates with living organisms showing mechanically adaptive behavior. In contrast to gels or elastomers, it is profoundly challenging to switch mechanical properties in stiff bioinspired nanocomposites as they contain high fractions of immobile reinforcements. Here, we introduce facile electrical switching to the field of bioinspired nanocomposites, and show how the mechanical properties adapt to low direct current (DC). This is realized for renewable cellulose nanofibrils/polymer nanopapers with tailor-made interactions by deposition of thin single-walled carbon nanotube electrode layers for Joule heating. Application of DC at specific voltages translates into significant electrothermal softening via dynamization and breakage of the thermo-reversible supramolecular bonds. The altered mechanical properties are reversibly switchable in power on/power off cycles. Furthermore, we showcase electricity-adaptive patterns and reconfiguration of deformation patterns using electrode patterning techniques. The simple and generic approach opens avenues for bioinspired nanocomposites for facile application in adaptive damping and structural materials, and soft robotics.

Recyclable and Light-Adaptive Vitrimer-Based Nacre-Mimetic Nanocomposites.

Nacre's natural design consists of a perfect hierarchical assembly that resembles a brick-and-mortar structure with synergistic stiffness and toughness. The field of bioinspired materials often provides attractive architecture and engineering pathways which allow to explore outstanding property areas. However, the study of nacre-mimetic materials should not be limited to the design of its architecture but ought to include the understanding, operation, and improvement of internal interactions between their components. Here, we introduce a vitrimer prepolymer system that, once integrated into the nacre-mimetic nanocomposites, cures and cross-links with the presence of Lewis acid catalyst and further manifests associative dynamic exchange reactions. Bond exchanges are controllable by molecular composition and catalyst content and characterized by creep, shear-lag, and shape-locking tests. We exploit the vitrimer properties by laminating ca. 70 films into thick bulk materials, and characterize the flexural resistance and crack propagation. More importantly, we introduce recycling by grinding and hot-pressing. The recycling for highly reinforced nacre-mimetic nanocomposites is critically enabled by the vitrimer chemistry and improves the sustainability of bioinspired nanocomposites in cyclic economy. Finally, we integrate photothermal converters into the structures and use laser irradiation as external trigger to activate the vitrimer exchange reactions.

Room-Temperature Phosphorescence Enabled through Nacre-Mimetic Nanocomposite Design.

A generic, facile, and waterborne strategy is introduced to fabricate flexible, low-cost nanocomposite films with room-temperature phosphorescence (RTP) by incorporating waterborne RTP polymers into self-assembled bioinspired polymer/nanoclay nanocomposites. The excellent oxygen barrier of the lamellar nanoclay structure suppresses the quenching effect from ambient oxygen (kq ) and broadens the choice of polymer matrices towards lower glass transition temperature (Tg ), while providing better mechanical properties and processability. Moreover, the oxygen permeation and diffusion inside the films can be fine-tuned by varying the polymer/nanoclay ratio, enabling programmable retention times of the RTP signals, which is exploited for transient information storage and anti-counterfeiting materials. Additionally, anti-interception materials are showcased by tracing the interception-induced oxygen history that interferes with the preset self-erasing time. Merging bioinspired nanocomposite design with RTP materials contributes to overcoming the inherent limitations of molecular design of organic RTP compounds, and allows programmable temporal features to be added into RTP materials by controlled mesostructures. This will assist in paving the way for practical applications of RTP materials as novel anti-counterfeiting materials.

Glass Transition Temperature Regulates Mechanical Performance in Nacre-Mimetic Nanocomposites.

Although research in bioinspired nanocomposites is delivering mechanically superior nanocomposite materials, there remain gaps in understanding some fundamental design principles. This article discusses how the mechanical properties of nacre-mimetic polymer/nanoclay nanocomposites with nanoconfined polymer layers are controlled by the thermo-mechanical polymer properties, that is, glass transition temperature, Tg, using a series of poly(ethylene glycol methyl ether methacrylate-co-N,N-dimethylacrylamide) copolymers with tunable Tg from 130 to -55 °C. It is elucidated that both the type of copolymer and the nanoconfined polymer layer thickness control energy dissipation and inelastic deformation at high fractions of reinforcements in such bioinspired nanocomposites.

Self-Assembled Bioinspired Nanocomposites.

Bioinspired materials engineering impacts the design of advanced functional materials across many domains of sciences from wetting behavior to optical and mechanical materials. In all cases, the advances in understanding how biology uses hierarchical design to create failure and defect-tolerant materials with emergent properties lays the groundwork for engaging into these topics. Biological mechanical materials are particularly inspiring for their unique combinations of stiffness, strength, and toughness together with lightweightness, as assembled and grown in water from a limited set of building blocks at room temperature. Wood, nacre, crustacean cuticles, and spider silk serve as some examples, where the correct arrangement of constituents and balanced molecular energy dissipation mechanisms allows overcoming the shortcomings of the individual components and leads to synergistic materials performance beyond additive behavior. They constitute a paradigm for future structural materials engineering-in the formation process, the use of sustainable building blocks and energy-efficient pathways, as well as in the property profiles-that will in the long term allow for new classes of high-performance and lightweight structural materials needed to promote energy efficiency in mobile technologies.This Account summarizes our efforts of the past decade with respect to designing self-assembling bioinspired materials aiming for both mechanical high-performance structures and new types of multifunctional property profiles. The Account is set out to first give a definition of bioinspired nanocomposite materials and self-assembly therein, followed by an in-depth discussion on the understanding of mechanical performance and rational design to increase the mechanical performance. We place a particular emphasis on materials formed at high fractions of reinforcements and with tailor-made functional polymers using self-assembly to create highly ordered structures and elucidate in detail how the soft polymer phase needs to be designed in terms of thermomechanical properties and sacrificial supramolecular bonds. We focus on nanoscale reinforcements such as nanoclay and nanocellulose that lead to high contents of internal interfaces and intercalated polymer layers that experience nanoconfinement. Both aspects add fundamental challenges for macromolecular design of soft phases using precision polymer synthesis. We build upon those design criteria and further develop the concepts of adaptive bioinspired nanocomposites, whose properties are switchable from the outside using molecularly defined triggers with light. In a last section, we discuss how new types of functional properties, in particular flexible and transparent gas barrier materials or fire barrier materials, can be reached on the basis of the bioinspired nanocomposite design strategies. Additionally, we show new types of self-assembled photonic materials that can even be evolved into self-assembling lasers, hence moving the concept of mechanical nanocomposite design to other functionalities.The comparative discussion of different bioinspired nanocomposite architectures with nematic, fibrillar, and cholesteric structures, as based on different reinforcing nanoparticles, aims for a unified understanding of the design principles and shall aid researchers in the field in the more elaborate design of future bioinspired nanocomposite materials based on molecular control principles. We conclude by addressing challenges, in particular also the need for a transfer from fundamental molecular materials science into scalable engineering materials of technological and societal relevance.

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.

Hierarchical cross-linking for synergetic toughening in crustacean-mimetic nanocomposites.

The twisted plywood structure as found in crustacean shells possesses excellent mechanical properties with high stiffness and toughness. Synthetic mimics can be produced by evaporation-induced self-assembly of cellulose nanocrystals (CNCs) with polymer components into bulk films with a cholesteric liquid crystal structure. However, these are often excessively brittle and it has remained challenging to make materials combining high stiffness and toughness. Here, we describe self-assembling cholesteric CNC/polymer nanocomposites with a crustacean-mimetic structure and tunable photonic band gap, in which we engineer combinations of thermo-activated covalent and supramolecular hydrogen-bonded crosslinks to tailor the energy dissipation properties by precise molecular design. Toughening occurs upon increasing the polymer fractions in the nanocomposites, and, critically, combinations of both molecular bonding mechanisms lead to a considerable synergetic increase of stiffness and toughness - beyond the common rule of mixtures. Our concept following careful molecular design allows one to enter previously unreached areas of mechanical property charts for cholesteric CNC-based nanocomposites. The study shows that the subtle engineering of molecular energy dissipation units using sophisticated chemical approaches enables efficient enhancing of the properties of bioinspired CNC/polymer nanocomposites, and opens the design space for future molecular enhancement using tailor-made interactions.

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.

Waterborne Methacrylate-Based Vitrimers.

We demonstrate waterborne, unimolecularly dissolved vitrimer prepolymer systems that can be transferred into a vitrimer material using catalytic transesterification. The one-component prepolymer system can be processed via film casting and subsequent heat-induced cross-linking. A variation of the density of side chain hydroxy groups over ester and amide groups in the methacrylate/methacrylamide backbone, as well as of the Lewis acid catalyst loading, allow control of the extent of cross-linking and exchange rates. The increase of the amount of both catalyst and hydroxy groups leads to an acceleration of the relaxation times and a decrease of the activation energy of the transesterification reactions. The system features elastomeric properties, and the tensile properties are maintained after two recycling steps. Thus far, vitrimers have been limited largely to hydrophobic polymers; this system is a step forward toward waterborne, one-component materials, and we demonstrate its use in waterborne bioinspired nanocomposites.

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.

Facile and On-Demand Cross-Linking of Nacre-Mimetic Nanocomposites Using Tailor-Made Polymers with Latent Reactivity.

The development of on-demand cross-linking strategies is a key aspect in promoting mechanical properties of high-performance bioinspired nanocomposites. Here, we embed styrene sulfonyl azide groups with latent chemical reactivity into water-soluble copolymers and assemble those with high-aspect-ratio synthetic nanoclays to generate well-defined layered polymer/nanoclay nacre-mimetics. A considerable stiffening and strengthening occurs upon activation of the covalent cross-linking using simple heating. Varying the amount of cross-linkable units allows molecular control of mechanical properties from ductile to stiff and strong. Moreover, the covalent cross-linking enhances the moisture stability of water-borne nacre-mimetics. The strategy is facile and versatile allowing for a transfer into applications.

Highly Anisotropic Thermal Conductivity of Layer-by-Layer Assembled Nanofibrillated Cellulose/Graphene Nanosheets Hybrid Films for Thermal Management.

An anisotropic thermally conductive film with tailorable microstructures and macroproperties is fabricated using a layer-by-layer (LbL) assembly of graphene oxide (GO) and nanofibrillated cellulose (NFC) on a flexible NFC substrate driven by hydrogen bonding interactions, followed by chemical reduction process. The resulting NFC/reduced graphene oxide (RGO) hybrid film reveals an orderly hierarchical structure in which the RGO nanosheets exhibit a high degree of orientation along the in-plane direction. The assembly cycles dramatically increase the in-plane thermal conductivity (λX) of the hybrid film to 12.6 W·m-1·K-1, while the cross-plane thermal conductivity (λZ) shows a lower value of 0.042 W·m-1·K-1 in the hybrid film with 40 assembly cycles. The thermal conductivity anisotropy reaches up to λX/λZ = 279, which is substantially larger than that of similar polymeric nanocomposites, indicating that the LbL assembly on a flexible NFC substrate is an efficient technique for the preparation of polymeric nanocomposites with improved heat conducting property. Moreover, the layered hybrid film composed of 1D NFC and 2D RGO exhibits synergetic mechnical properties with outstanding flexibility and a high tensile strength (107 MPa). The combination of anisotropic thermal conductivity and superior mechanical performance may facilitate the applications in thermal management.

Development of self-assembling peptide nanovesicle with bilayers for enhanced EGFR-targeted drug and gene delivery.

Development of rational vectors for efficient drug and gene delivery is crucial for cancer treatment. In this study, epidermal growth factor receptor (EGFR)-binding peptide amphiphile (PA) were used as the primary bilayer skeleton material to construct ultra-stable self-assembling peptide nanovesicle (SPV). The resulted EGFR-targeted SPV (ESPV) could efficiently encapsulate therapeutic cargos (drugs or small interfering RNAs [siRNAs]) or labelled fluorescent cargo (quantum dots [QDs]) and exhibited excellent affinity for EGFR-positive cancer cells. Moreover, ESPV could deliver more drug or plasmid DNA to tumour sites and promote gene expression (a three-fold ratio of ESPVs vs cationic liposomes). Notably, the individual delivery or co-delivery of doxorubicin (DOX) and the acetylcholinesterase (AChE) gene via the ESPVs resulted in excellent drug/gene delivery both in vitro and in vivo and exerted a significant growth-suppressing effect on a liver cancer xenograft. This nanoscale, targeted cargo-packaging technology may provide a new strategy for the design of highly targeted cancer therapy vectors.