Marangoni Effect-Driven Motion of Miniature Robots and Generation of Electricity on Water.

The well-known Marangoni effect perfectly supports the dynamic mechanism of organic solvent-swollen gels on water. On this basis, we report a series of energy conversion processes of concentrated droplets of polyvinylidene fluoride/dimethyl formamide (PVDF/DMF) that can transfer chemical-free energy to kinetic energy to rapidly rotate itself on water. This droplet (22.2 mg) is capable to offer kinetic energy of 0.099 µJ to propel an artificial paper rocket of 31.8 mg to move over 560 cm on water at an initial velocity of 7.9 cm s-1. As the droplet increases to 35.0 mg, a paper goldfish of 10.6 mg can be driven to swim longer at a higher initial velocity of 20 cm s-1. The kinetic energy of the droplet can be further converted to electrical energy through an electromagnetic generator, in which as a 0.5 MΩ resistor is loaded, the peak output reaches 6.5 mV that corresponds to the power density of 0.293 µW kg-1. We believe that this report would open up a promising avenue to exploit energies for applications in miniature robotics.

Supramolecular Polymer Co-Assembled Multifunctional Chiral Hybrid Hydrogels with Adhesive, Self-Healing and Antibacterial Properties.

Amino acid-derived self-assembled nanofibers comprising supramolecular chiral hydrogels with unique physiochemical characteristics are highly demanded biomaterials for various biological applications. However, their narrow functionality often limits practical use, necessitating the development of biomaterials with multiple features within a single system. Herein, chiral co-assembled hybrid hydrogel systems termed LPH-EGCG and DPH-EGCG were constructed by co-assembling L/DPFEG gelators with epigallocatechin gallate (EGCG) followed by cross-linking with polyvinyl alcohol (PVA) and hyaluronic acid (HA). The developed hybrid hydrogels exhibit superior mechanical strength, self-healing capabilities, and adhesive properties, owing to synergistic non-covalent interactions. Integrating hydrophilic polymers enhances the system's capacity to demonstrate favorable swelling characteristics. Furthermore, the introduction of EGCG facilitated the hybrid gels to display notable antibacterial properties against both Gram-positive and Gram-negative bacterial strains, alongside showcasing strong antioxidant capabilities. In vitro investigation demonstrated enhanced cell adhesion and migration with the LPH-EGCG system in comparison to DPH-EGCG, thus emphasizing the promising prospects of these hybrid hydrogels in advanced tissue engineering applications.

Electrochemical Bonding of Hydrogels at Rigid Surfaces.

Flexible hydrogels can be chemically/physically bonded on soft surfaces. However, there is a lack of a facile method to build strong interfacial adhesion between hydrogel and various rigid surfaces. Herein, an electrochemical bonding protocol, which improves the interfacial adhesion energy of hydrogel from initial 8 to 3480 J m-2 , ≈435 times enhancement at rigid glass surface, superior to the most of traditional methods, is proposed. A series of electrochemical bonding models to analyze the bonding mechanism, is demonstrated. The results indicate that the electrode reactions generate Fe3+ ions at the anode and OH- ions at the cathode, which migrate and react to form nanoparticles of Fe(OH)3 . These nanoparticles form hump-like physical structures at the interface and work as mechanical-bonding sites, enabling the strong interfacial adhesion. Upon applying acidic solution to decompose the nanoparticles, the strong adhesion can be weakened to easily remove hydrogel from the bonded surface. The electrochemically-bonded hydrogel can maintain its adhesion in water, which enables the electrochemical bonding of hydrogels for repairing various damaged surfaces such as plastic water tubes/bags, indicating promising potential for adhesive engineering applications.

Swelling-Induced Information Camouflage and Optical Decryption on a Transparent Recoverable Hydrogel Surface.

Information camouflage and decryption on hydrogels rely on chemical stimuli such as pH, ultraviolet light, and chemical reactions, in which the cyclability is limited. This work develops a simpler yet effective physical method that can achieve the information camouflage on hydrogels by water swelling and decrypt it under white light. The information camouflage and decryption can proceed with unlimited cycles. To successfully reach the information camouflage, the hydrogel is synthesized with the water swelling ratio in weight as high as 250, which is enabled by the strong electrostatic repulsion of cationic moieties inside the network. At such a high water-swollen state, the hydrogel is still robust and elastic, which provides a mechanical basis to maintain the stability of the camouflaged information. We write information on the hydrogel surface by laser cutting. Upon immersing the hydrogel in water, the high swelling results in huge expansion of the hydrogel, thus inducing the information camouflage. With exposure to white light, the information can be decrypted and becomes visible again. Our protocol utilizes a simple physical process to enable the camouflage and decryption of complex information, which might open an alternative pathway for the development of hydrogel materials in the application of informatics.

Quantitative Insights into the Effects of Post-Cross-Linking on Physical Performance Improvement and Surface-Cracking Healing of a Hydrogel.

We report a post-cross-linking protocol that can improve the mechanical properties, freezing resistance, and fracture energies of a covalent cross-linking hydrogel and can also enable its surface-cracking healing. We design a covalent cross-linking reaction based on 3-(methacryloylamino) propyl-trimethylammonium chloride (MPTC) and sodium acrylate (SA) to give rise to a PMPTC@PSA model hydrogel. After post-cross-linking treatment, the mechanical stress is improved by 9.0-fold, accompanied by a 3.5-fold improvement in elongation; the freezing resistance is increased by 2.5-fold, which is reflected by the stretchability improvement at -35 °C. In addition, the fracture energy increased from 266 to 4686 J/m2, an ∼17-fold improvement. Importantly, a surface-cracking hydrogel can be healed through the post-cross-linking treatment that enables the healing efficiency to approach 100% in terms of mechanical modulus and >81% in terms of maximum mechanical stress. This protocol is expected to provide a new option for physical performance improvement and crack healing of hydrogels in soft actuator, sensing device, and robotic applications.

Photocrosslinking Patterning of Single-Layered Polymer Actuators for Controllable Motility and Automatic Devices.

Shape-programmed deformation of soft polymer films is essential for applications in robotics, self-adaptive devices, and sensors. In comparison to bilayer polymer actuators, the challenge remains to manipulate single-layered soft actuators for rapid, reversible, and shape-programmed deformations in response to external stimuli owing to their homogeneous composite structures. Herein, this work reports a soft polymer film actuator that has a single-layered structure, yet demonstrates the shape-programmed motility. The actuator is composed of polyvinylidene fluoride film as a matrix and patterned by photocrosslinking of acrylamide and N', N'-methylenebisacrylamide, which generates soft-hard alternating segments in the structure. As it is exposed to acetone vapors, the soft-hard structures lead to an unequal response that results in the shape-programmed deformation. The actuator is elastic (strain: 160%) and tough (stress: 40 MPa) and can maintain its rapid, reversible, and shape-programmed motions for a few hours, even longer. The soft-hard structure enables the film actuator (3.5 mg) to give a contracting stress of 4 MPa that is used in an automatic device able to lift a cargo of 5.09 g, ∼1453 times heavier than the film itself. The power output reaches 474 J kg-1, ∼100 times higher than the reported soft actuators. This simple application indicates a potential for the soft actuator used in acetone vapor sensing devices.

Pre-patterning and post-oxidation-crosslinking of Fe(0) particles for a humidity-sensing actuator.

We propose a pre-patterning and post-oxidation-crosslinking protocol to prepare a humidity-sensing actuator. Fe(0) particles (FeP) are introduced into a sodium alginate (SA) film under a magnetic field (15 mT) to achieve directional pre-patterning, followed by treatment in hydrochloric acid that oxidates FeP into Fe2+, and triggers the crosslinking between Fe2+ and SA, which provides the actuator with differential mechanical tensors and induces controlled response to humidity.

Multiresponsive Kinematics and Robotics of Surface-Patterned Polymer Film.

Soft robots, sensors, and energy harvesters require materials that are capable of converting external stimuli to visible deformations, especially when shape-programmable deformations are desired. Herein, we develop a polymer film that can reversibly respond to humidity, heating, and acetone vapors with the generation of shape-programmable large deformations. Poly(vinylidene fluoride) film, capable of providing acetone responsiveness, is designed with microchannel patterns created on its one side by using templates, and the microchannels-patterned side is then treated with hygroscopic 3-aminopropyltriethoxysilane (APTES) to give humidity/heating-responsive elements. The APTES-modified microchannels lead to anisotropic flexural modulus and hygroscopicity in the film, resulting in the shape-programmed kinematics depending on the orientations of surface microchannels. As the microchannels align at oblique/right angles with respect to the long axis of the film strips, the coiling/curling motions can be generated in response to the stimuli, and the better motion performances are found in humidity- and heating-driven systems. This material utilized in self-adaptive soft robots exhibits prominent toughness, powerful strength, and long endurance for converting humidity and heat to mechanical works including transportation of lightweight objects, automatic sensing cap, and mimicking crawling in nature. We thus believe that this material with shape-programmable multisensing capability might be suitable for soft machines and robotics.

Humidity- and Sunlight-Driven Motion of a Chemically Bonded Polymer Bilayer with Programmable Surface Patterns.

We report a bilayer of sodium alginate/polyvinylidene fluoride (SA/PVDF) that is chemically bonded through a series of interfacial coupling reactions. The SA layer is hydrophilic in structure and is capable of strong interaction with water molecules, thus presenting high sensitivity to humidity, whereas the PVDF layer is hydrophobic, inert to humidity. This structural feature results in the bilayer having asymmetric humidity-responsive performances that can thus make its shape change with directionality, which cannot be achieved in an SA single layer. The responsive process to humidity can be adjusted by exposure of the bilayer to sunlight by means of a photothermal effect that accelerates dehydration of the bilayer to cause more rapid shape deformations. When the sunlight is removed, the bilayer adsorbs humidity again and returns to its original shape, indicating good reversibility. To exactly regulate the shape deformations of the bilayer with external stimuli, we employ Ca2+-treated filter paper to customize crosslinking reactions in the SA layer as desired patterns which are capable of causing different mechanical tensors and swellabilities in the bilayer so as to regulate and control the actuations for self-folding, curling, twisting, and coiling in response to sunlight and humidity.On the other hand, the chemically bonded bilayer has stronger interfacial toughness and is capable of reaching 300 J m-2, which is around 12 times the interfacial toughness of the physically combined bilayer; as a result, the chemically bonded bilayer is capable of sustaining continuous shape deformations without interfacial failure. The directionally mechanical actuations can be utilized in designing an indicator to roughly indicate the range of intensity of sunlight by coupling the chemically bonded bilayer into a typical electric circuit, in which the range of intensity of sunlight can be easily estimated by visual observation of the light-emitting diodes.