Search

Self-sustained motions are widespread in biological systems by harvesting energy from surrounding environments, which inspire scientists to develop autonomous soft robots. However, most-existing soft robots require dynamic heterogeneous stimuli or complex fabrication with different components. Recently, control of topological geometry has been promising to afford soft robots with physical intelligence and thus life-like motions. Reported here are a series of closed twisted ribbon robots, which exhibit self-sustained flipping and rotation under constant light irradiation. Both Möbius strip and Seifert ribbon robots are devised for the first time by using an identical hydrogel, which responds to light irradiation on either side. Experiment and simulation results indicate that the self-regulated motions of the hydrogel robots are related to fast and reversible response of muscle-like gel, self-shadowing effect, and topology-facilitated refresh of light-exposed regions. The motion speeds and directions of the hydrogel robots can be tuned over a wide range. These closed twisted ribbon hydrogels are further applied to execute specific tasks in aqueous environments, such as collecting plastic balls, climbing a vertical rod, and transporting objects. This work presents new design principle for autonomous hydrogel robots by benefiting from material response and topology geometry, which may be inspirative for the robotics community., (© 2024 Wiley‐VCH GmbH.)

Most hydrogels become frozen at subzero temperatures, leading to degraded properties and limited applications. Cryoprotectants are massively employed to improve anti-freezing property of hydrogels; however, there are accompanied disadvantages, such as varied networks, reduced mechanical properties, and the risk of cryoprotectant leakage in aqueous conditions. Reported here is the glassy hydrogel having intrinsic anti-freezing capacity and excellent optical and mechanical properties at ultra-low temperatures. Supramolecular hydrogel of poly(acrylamide-co-methacrylic acid) with moderate water content (≈50 wt.%) and dense hydrogen-bond associations is in a glassy state at room temperature. Since hydrogen bonds become strengthened as the temperature decreases, this gel becomes stronger and stiffer, yet still ductile, with Young's modulus of 900 MPa, tensile strength of 30 MPa, and breaking strain of 35% at -45 °C. This gel retains high transparency even in liquid nitrogen. It also exhibits unique phosphorescence due to presence of carbonyl clusters, which is further enhanced at subzero temperatures. Further investigations elucidate that the intrinsic anti-freezing property is related to a fact that most water molecules are tightly bound and confined in the glassy matrix and become non-freezable. This correlation, as validated in several systems, provides a roadmap to develop intrinsic anti-freezing hydrogels for widespread applications at extreme conditions., (© 2023 Wiley-VCH GmbH.)

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., (© 2023 Wiley-VCH GmbH.)

Processing tough hydrogels into sophisticated architectures is crucial for their applications as structural elements. However, Digital Light Processing (DLP) printing of tough hydrogels is challenging because of the low-speed gelation and toughening process. Described here is a simple yet versatile system suitable for DLP printing to form tough hydrogel architectures. The aqueous precursor consists of commercial photoinitiator, acrylic acid, and zirconium ion (Zr 4+ ), readily forming tough metallo-supramolecular hydrogel under digital light because of in situ formation of carboxyl-Zr 4+ coordination complexes. The high-stiffness and antiswelling properties of as-printed gel enable high-efficiency printing to form high-fidelity constructs. Furthermore, swelling-induced morphing of the gel is also achieved by encoding structure gradients during the printing with grayscale digital light. Mechanical properties of the printed hydrogels are further improved after incubation in water due to the variation of local pH and rearrangement of coordination complex. The swelling-enhanced stiffness affords the printed hydrogel with shape fixation ability after manual deformations, and thereby provides an additional avenue to form more complex configurations. These printed hydrogels are used to devise an impact-absorption element or a high-sensitivity pressure sensor as proof-of-concept examples. This work should merit engineering of other tough gels and extend their scope of applications in diverse fields., (© 2022 Wiley-VCH GmbH.)

A stimuli-responsive invisible ink for time-dependent encryption of information is reported. Consisting of a pillar[5]arene-based supramolecular network grafted with spiropyran moieties, these materials display time-dependent photochromic behavior with tailorable fading rates. Ultraviolet (UV) light results in isomerization of the colorless spiropyran to the corresponding colored merocyanine, while visible light or heat causes the reverse isomerization with a rate that is dependent on the density of host-guest crosslinks. The kinetics of discoloration are a function of merocyanine aggregation, which becomes more pronounced as the host-guest crosslink density is increased, leading to a reduced conversion rate and slower time-dependent fading. The degree of crosslinking, and hence the fading rate, may be modulated via the addition of unbound pillar[5]arene host or nitrile guest as competitors. Time-dependent information encryption is enabled by combining selective placement of host and guest competitors and UV patterning. UV patterning provides an initially "false" image that does not reveal the desired information, and it is only after a given time that the encrypted data appears. This work provides a unique approach to enhance the security of information storage associated with offline portable data encryption., (© 2021 Wiley-VCH GmbH.)

Materials capable of shape-morphing and/or fluorescence imaging have practical significances in the fields of anti-counterfeiting, information display, and information protection. However, it's challenging to realize these functions in hydrogels due to the poor mechanical properties and lack of tunable fluorescence. A tough hydrogel with good shape-memory ability and phototunable fluorescence is reported here, which affords reprogrammable shape designing and information encoding for dual-encryption. This hydrogel is prepared by incorporating donor-acceptor chromophore units into a poly(1-vinylimidazole-co-methacrylic acid) network, in which the dense intra- and interchain hydrogen bonds lead to desirable features including high stiffness, high toughness, and temperature-mediated shape-memory property. Additionally, the hydrogel shows photomediated tunable fluorescence through a unimer-to-dimer transformation of the chromophores. By combining photolithography and origami/kirigami designs, hydrogel sheets encoded with fluorescent patterns can deform into specific 3D configurations. The geometrically encrypted fluorescent information in the architected hydrogels is readable only after sequential shape recovery and UV light irradiation. As demonstrated by proof-of-concept experiments, both the fluorescent pattern and the 3D configuration are reprogrammable, facilitating repeated information protection and display. The design of tough hydrogels with rewritable fluorescent patterns and reconfigurable shapes should guide the future development of smart materials with improved security and wider applications in aqueous environments., (© 2021 Wiley-VCH GmbH.)

Morphing hydrogels have versatile applications in soft robotics, flexible electronics, and biomedical devices. Controlling component distribution and internal stress within a hydrogel is crucial for shape-changing. However, existing gradient structures of hydrogels are usually non-reconstructable, once encoded by chemical reactions and covalent bonds. Fabricating hydrogels with distinct gradient structures is inevitable for every new configuration, resulting in poor reusability, adaptability, and sustainability that are disadvantageous for diverse applications. Herein, a hydrogel containing reversible photo-crosslinks that enable reprogramming of the gradient structures and 3D deformations into various configurations is reported. The hydrogel is prepared by micellar polymerization of hydrophobic coumarin monomer and hydrophilic acrylic acid. The presence of hexadecyltrimethylammonium chloride micelles increases the local concentration of coumarin units and also improves the mechanical properties of the hydrogel by forming robust polyelectrolyte/surfactant complexes that serve as the physical crosslinks. High-efficiency photodimerization and photocleavage reactions of coumarins are realized under 365 and 254 nm light irradiation, respectively, affording reversible tuning of the network structure of the hydrogel. Through photolithography, different gradient structures are sequentially patterned in one hydrogel that direct the deformations into distinct configurations. Such a strategy should be applicable for other photolabile hydrogels toward reprogrammable control of network structures and versatile functions., (© 2021 Wiley-VCH GmbH.)

Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) and its copolymer hydrogels are typical polyelectrolyte gels with extremely high swelling capacity that are widely used in industry. It's common to consider these hydrogels as weak materials that are difficult to toughen. Reported here is a facile strategy to transform swollen and weak poly(acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) [P(AAm-co-AMPS)] hydrogels to tough ones by forming strong sulfonate-Zr 4+ metal-coordination complexes. The resultant hydrogels with moderate water content possess high stiffness, strength, and fracture energy, which can be tuned over 3-4 orders of magnitude by controlling the composition and metal-to-ligand ratio. Owing to the dynamic nature of the coordination bonds, these hydrogels show rate- and temperature-dependent mechanical performances, as well as good self-recovery properties. This strategy is universal, as manifested by the drastically improved mechanical properties of hydrogels of various natural and synthetic sulfonate-containing polymers. The toughened hydrogels can be converted to the original swollen ones by breaking up the metal-coordination complexes in alkaline solutions. The reversible brittle-tough transition and concomitant dramatic volume change of polyelectrolyte hydrogels afford diverse applications, as demonstrated by the design of a tubular grasper with holding force a thousand times its own weight for objects with different geometries. It is envisioned that these hydrogels enable versatile applications in the biomedical and engineering fields., (© 2020 Wiley-VCH GmbH.)

Living organisms use musculatures with spatially distributed anisotropic structures to actuate deformations and locomotion with fascinating functions. Replicating such structural features in artificial materials is of great significance yet remains a big challenge. Here, a facile strategy is reported to fabricate hydrogels with elaborate ordered structures of nanosheets (NSs) oriented under a distributed electric field. Multiple electrodes are distributed with various arrangements in the precursor solution containing NSs and gold nanoparticles. A complex electric field induces sophisticated orientations of the NSs that are permanently inscribed by subsequent photo-polymerization. The resultant anisotropic nanocomposite poly(N-isopropylacrylamide) hydrogels exhibit rapid deformation upon heating or photoirradiation, owing to the fast switching of permittivity of the media and electric repulsion between the NSs. The complex alignments of NSs and anisotropic shape change of discrete regions result in programmed deformation of the hydrogels into various configurations. Furthermore, locomotion is realized by a spatiotemporal light stimulation that locally triggers time-variant shape change of the composite hydrogel with complex anisotropic structures. Such a strategy on the basis of the distributed electric-field-generated ordered structures should be applicable to gels, elastomers, and thermosets loaded with other anisotropic particles or liquid crystals, for the design of biomimetic/bioinspired materials with specific functionalities., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Stimuli-responsive shape-transforming hydrogels have shown great potential toward various engineering applications including soft robotics and microfluidics. Despite significant progress in designing hydrogels with ever more sophisticated shape-morphing behaviors, an ultimate goal yet to be fulfilled is programmable reversible shape transformation. It is reported here that transient structural anisotropy can be programmed into copolymer hydrogels of N-isopropylacrylamide and stearyl acrylate. Structural anisotropy arises from the deformed hydrophobic domains of the stearyl groups after thermomechanical programming, which serves as a template for the reversible globule-to-coil transition of the poly(N-isopropylacrylamide) chains. The structural anisotropy is transient and can be erased upon cooling. This allows repeated programming for reversible shape transformation, an unknown feature for the current hydrogels. The programmable reversible transformation is expected to greatly extend the technical scope for hydrogel-based devices., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Morphing materials have promising applications in soft robots, intelligent devices, and so forth. Among the various design strategies, kirigami structures are recognized as a powerful tool to obtain sophisticated 3D configurations and unprecedented properties from planar designs on common materials. Here, some kirigami designs are demonstrated for programmable, multistable 3D configurations from composite hydrogel sheets. Via photolithographic polymerization, perforated composite hydrogel sheets are fabricated, in which soft and active hydrogel strips are patterned in stiff and passive hydrogel frames. When immersed in water, the gel strips buckle out of plane due to swelling mismatch. In the kirigami structures, the geometric continuity is disrupted by the introduction of cutouts, and thus the degrees of deformation freedom increases remarkably. Multiple configurations are obtained in a single composite hydrogel by controlling the buckling direction of each strip. Multitier configurations are also obtained by using a hierarchically designed kirigami structure. A multicontact switch of an electric circuit is designed by harnessing the multitier gel configurations. Furthermore, a rotation mode is realized by introducing chirality in the kirigami design. The versatile design of the kirigami structure for programmable deformations should be applicable for other intelligent materials toward promising applications in biomedical devices and flexible electronics., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel ion-conducting supramolecular hydrogel with reversible photoconductive properties in which the azobenzene motif, α-cyclodextrin (α-CD), and ionic liquid are grafted onto the gel matrix is reported. Host-guest interactions with different association constants between α-CD and azobenzene or the anionic part of the ionic liquid can be readily tuned by photoinduced trans-cis isomerization of the azobenzene unit. When irradiated by 365 nm light, α-CD prefers to form a complex with the anionic part of the ionic liquid, resulting in decreased ionic mobility and thus high resistance of the hydrogel. However, under 420 nm light irradiation, a more stable complex is again formed between α-CD and trans-azobenzene, thereby releasing the bound anions to regenerate the low-resistive hydrogel. As such, remote control of the ionic conductivity of the hydrogel is realized by simple host-guest chemistry. With the incorporation of a logic gate, this hydrogel is able to reversibly switch an electric circuit on and off by light irradiation with certain wavelengths. The concept of photoswitchable ionic conductivity of a hydrogel mediated by competitive molecular recognition is potentially promising toward the fabrication of optoelectronic devices and applications in bioelectronic technology., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Multifluorescent supramolecular gels with complex structures are constructed from discrete fluorescent gels, which serve as the building blocks, through hydrogen bonding interactions at interfaces. The multifluorescent gel can realize rapid healing within only ≈100 s., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)