Surface Patterning of Hydrogels for Programmable and Complex Shape Deformations by Ion Inkjet Printing

Convenient patterning and precisely programmable shape deformations are crucial for the practical applications of shape deformable hydrogels. Here, a facile and versatile computer‐assisted ion inkjet printing technique is described that enables the direct printing of batched, very complicated patterns, especially those with well‐defined, programmable variation in cross‐linking densities, on one or both surfaces of a large‐sized hydrogel sample. A mechanically strong hydrogel containing poly(sodium acrylate) is first prepared, and then digital patterns are printed onto the hydrogel surfaces by using a commercial inkjet printer and an aqueous ferric solution. The complexation between the polyelectrolyte and ferric ions increases the cross‐linking density of the printed regions, and hence the gel sample can undergo shape deformation upon swelling/deswelling. The deformation rates and degrees of the hydrogels can be conveniently adjusted by changing the printing times or the different/gradient grayscale distribution of designed patterns. By printing appropriate patterns on one or both surfaces of the hydrogel sheets, many complex 3D shapes are obtained from shape deformations upon swelling/deswelling, such as cylindrical shell and forsythia flower (patterns on one surface), ding (patterns on both surfaces), blooming flower (different/gradient grayscale distributive patterns on one surface), and non‐Euclidean plates (different/gradient grayscale distributive patterns on both surfaces).     

A Multiresponsive Anisotropic Hydrogel with Macroscopic 3D Complex Deformations

As one of the most promising smart materials, stimuli‐responsive polymer hydrogels (SPHs) can reversibly change volume or shape in response to external stimuli. They thus have shown promising applications in many fields. While considerable progress of 2D deformation of SPHs has been achieved, the realization of 3D or even more complex deformation still remains a significant challenge. Here, a general strategy towards designing multiresponsive, macroscopically anisotropic SPHs (MA‐SPHs) with the ability of 3D complex deformations is reported. Through a local UV‐reduction of graphene oxide sheets (GOs) with a patterned fashion in the GO‐poly(N‐isopropylacrylamide) (GO‐PNIPAM) composite hydrogel sheet, MA‐SPHs can be achieved after the introduction of a second poly(methylacrylic acid) network in the unreduced part of GO‐PNIPAM hydrogel sheet. The resulting 3D MA‐SPHs can provide remote‐controllable light‐driven, as well as thermo‐, pH‐, and ionic strength‐triggered multiresponsive 3D complex deformations. Approaches in this study may provide new insights in designing and fabricating intelligent soft materials for bioinspired applications.     

Soft Robotics Programmed with Double Crosslinking DNA Hydrogels

DNA nanotechnology is developed for decades to construct dynamic responsive systems in optics, quantum electronics, and therapeutics. While DNA nanotechnology is a powerful tool in nanomaterials, it is rare to see successful applications of DNA molecules in the macroscopic regime of material sciences. Here, a novel strategy to magnify the nanometer scale DNA self‐assembly into a macroscopic mechanical responsiveness is demonstrated. By incorporating molecularly engineered DNA sequences into a polymeric network, a new type of responsive hydrogel (D‐gel), whose overall morphology is dynamically controlled by DNA hybridization‐induced double crosslinking is able to be created. As a step toward manufacturing, the D‐gel in combination with a bottom‐up 3D printing technology is employed to rapidly create modular macroscopic structures that feature programmable reconfiguration and directional movement, which can even mimic the complex gestures of human hands. Mechanical operations such as catch and release are demonstrated by a proof‐of‐concept hydrogel palm, which possessed great promise for future engineering applications. Compared with previously developed DNA hydrogels, the D‐gel features an ease of synthesis, faster response, and a high degree of programmable control. Moreover, it is possible to scale up the production of D‐gel containing responsive devices through direct 3D printing.     

Programmed Deformations of 3D‐Printed Tough Physical Hydrogels with High Response Speed and Large Output Force

Shape‐morphing hydrogels have emerging applications in biomedical devices, soft robotics, and so on. However, successful applications require a combination of excellent mechanical properties and fast responding speed, which are usually a trade‐off in hydrogel‐based devices. Here, a facile approach to fabricate 3D gel constructs by extrusion‐based printing of tough physical hydrogels, which show programmable deformations with high response speed and large output force, is described. Highly viscoelastic poly(acrylic acid‐co‐acrylamide) (P(AAc‐co‐AAm)) and poly(acrylic acid‐co‐N‐isopropyl acrylamide) (P(AAc‐co‐NIPAm)) solutions or their mixtures are printed into 3D constructs by using multiple nozzles, which are then transferred into FeCl₃ solution to gel the structures by forming robust carboxyl–Fe³⁺ coordination complexes. The printed gel fibers containing poly(N‐isopropyl acrylamide) segment exhibit considerable volume contraction in concentrated saline solution, whereas the P(AAc‐co‐AAm) ones do not contract. The mismatch in responsiveness of the gel fibers affords the integrated 3D gel constructs the shape‐morphing ability. Because of the small diameter of gel fibers, the printed gel structures deform and recover with a fast speed. A four‐armed gripper is designed to clamp plastic balls with considerable holding force, as large as 115 times the weight of the gripper. This strategy should be applicable to other tough hydrogels and broaden their applications.     

4D Printing of Hydrogels: A Review

3D printing permits the construction of objects by layer‐by‐layer deposition of material, resulting in precise control of the dimensions and properties of complex printed structures. Although 3D printing fabricates inanimate objects, the emerging technology of 4D printing allows for animated structures that change their shape, function, or properties over time when exposed to specific external stimuli after fabrication. Among the materials used in 4D printing, hydrogels have attracted growing interest due to the availability of various smart hydrogels. The reversible shape‐morphing in 4D printed hydrogel structures is driven by a stress mismatch arising from the different swelling degrees in the parts of the structure upon application of a stimulus. This review provides the state‐of‐the‐art of 4D printing of hydrogels from the materials perspective. First, the main 3D printing technologies employed are briefly depicted, and, for each one, the required physico‐chemical properties of the precursor material. Then, the hydrogels that have been printed are described, including stimuli‐responsive hydrogels, non‐responsive hydrogels that are sensitive to solvent absorption/desorption, and multimaterial structures that are totally hydrogel‐based. Finally, the current and future applications of this technology are presented, and the requisites and avenues of improvement in terms of material properties are discussed.     

Direct 3D Printing of High Strength Biohybrid Gradient Hydrogel Scaffolds for Efficient Repair of Osteochondral Defect

The emerging 3D printing technique allows for tailoring hydrogel‐based soft structure tissue scaffolds for individualized therapy of osteochondral defects. However, the weak mechanical strength and uncontrollable swelling intrinsic to conventional hydrogels restrain their use as bioinks. Here, a high‐strength thermoresponsive supramolecular copolymer hydrogel is synthesized by one‐step copolymerization of dual hydrogen bonding monomers, N‐acryloyl glycinamide, and N‐[tris(hydroxymethyl)methyl] acrylamide. The obtained copolymer hydrogels demonstrate excellent mechanical properties—robust tensile strength (up to 0.41 MPa), large stretchability (up to 860%), and high compressive strength (up to 8.4 MPa). The rapid thermoreversible gel ? sol transition behavior makes this copolymer hydrogel suitable for direct 3D printing. Successful preparation of 3D‐printed biohybrid gradient hydrogel scaffolds is demonstrated with controllable 3D architecture, owing to shear thinning property which allows continuous extrusion through a needle and also immediate gelation of fluid upon deposition on the cooled substrate. Furthermore, this biohybrid gradient hydrogel scaffold printed with transforming growth factor beta 1 and β‐tricalciumphosphate on distinct layers facilitates the attachment, spreading, and chondrogenic and osteogenic differentiation of human bone marrow stem cells (hBMSCs) in vitro. The in vivo experiments reveal that the 3D‐printed biohybrid gradient hydrogel scaffolds significantly accelerate simultaneous regeneration of cartilage and subchondral bone in a rat model.     

Sub‐3 V ZnO Electrolyte‐Gated Transistors and Circuits with Screen‐Printed and Photo‐Crosslinked Ion Gel Gate Dielectrics: New Routes to Improved Performance

A facile, high‐resolution patterning process is introduced for fabrication of electrolyte‐gated transistors (EGTs) and circuits using a photo‐crosslinkable ion gel and stencil‐based screen printing. The photo‐crosslinkable gel is based on a triblock copolymer incorporating UV‐sensitive terminal azide functionality and a common ionic liquid. Using this material in conjunction with conventional photolithography and stenciling techniques, well‐defined 0.5–1 μm thick ion gel films are patterned on semiconductor channels as narrow as 10 μm. The resulting n‐type ZnO EGTs display high electron mobility (>2 cm² Vs^?1) and on/off current ratios (>10⁵). Further, EGT‐based inverters exhibit static gains >23 at supply voltages below 3 V, and five‐stage EGT ring oscillator circuits display dynamic propagation delays of 50 μs per stage. In general, the screen printing and photo‐crosslinking strategy provides a clean room‐compatible method to fabricate EGT circuits with improved sensitivity (gain) and computational power (gain × oscillating frequency). Detailed device analysis indicates that significantly shorter delay times, of order 1 μs, can be obtained by improving the ion gel conductance.     

Combining 3D Printing with Electrospinning for Rapid Response and Enhanced Designability of Hydrogel Actuators

Porous structures have emerged as a breakthrough of shape‐morphing hydrogels to achieve a rapid response. However, these porous actuators generally suffer from a lack of complexity and diversity in obtained 3D shapes. Herein, a simple yet versatile strategy is developed to generate shape‐morphing hydrogels with both fast deformation and enhanced designability in 3D shapes by combining two promising technologies: electrospinning and 3D printing. Elaborate patterns are printed on mesostructured stimuli‐responsive electrospun membranes, modulating in‐plane and interlayer internal stresses induced by swelling/shrinkage mismatch, and thus guiding morphing behaviors of electrospun membranes to adapt to changes of the environment. With this strategy, a series of fast deformed hydrogel actuators are constructed with various distinctive responsive behaviors, including reversible/irreversible formations of 3D structures, folding of 3D tubes, and formations of 3D structures with multi low‐energy states. It is worth noting that although poly(N‐isopropyl acrylamide) is chosen as the model system in the present research, our strategy is applicable to other stimuli‐responsive hydrogels, which enriches designs of rapid deformed hydrogel actuators.     

Highly Efficient Self‐Healable and Dual Responsive Cellulose‐Based Hydrogels for Controlled Release and 3D Cell Culture

To face the increasing demand of self‐healing hydrogels with biocompatibility and high performances, a new class of cellulose‐based self‐healing hydrogels are constructed through dynamic covalent acylhydrazone linkages. The carboxyethyl cellulose‐graft‐dithiodipropionate dihydrazide and dibenzaldehyde‐terminated poly(ethylene glycol) are synthesized, and then the hydrogels are formed from their mixed solutions under 4‐amino‐DL‐phenylalanine (4a‐Phe) catalysis. The chemical structure, as well as microscopic morphologies, gelation times, mechanical and self‐healing performances of the hydrogels are investigated with ¹H NMR, Fourier transform infrared spectroscopy, atomic force microscopy, rheological and compression measurements. Their gelation times can be controlled by varying the total polymer concentration or 4a‐Phe content. The resulted hydrogels exhibit excellent self‐healing ability with a high healing efficiency (≈96%) and good mechanical properties. Moreover, the hydrogels display pH/redox dual responsive sol‐gel transition behaviors, and are applied successfully to the controlled release of doxorubicin. Importantly, benefitting from the excellent biocompatibility and the reversibly cross‐linked networks, the hydrogels can function as suitable 3D culture scaffolds for L929 cells, leading to the encapsulated cells maintaining a high viability and proliferative capacity. Therefore, the cellulose‐based self‐healing hydrogels show potential applications in drug delivery and 3D cell culture for tissue engineering.     

Highly Elastic,Transparent, and Conductive 3D‐Printed Ionic Composite Hydrogels

Despite extensive progress to engineer hydrogels for a broad range of technologies, practical applications have remained elusive due to their (until recently) poor mechanical properties and lack of fabrication approaches, which constrain active structures to simple geometries. This study demonstrates a family of ionic composite hydrogels with excellent mechanical properties that can be rapidly 3D‐printed at high resolution using commercial stereolithography technology. The new material design leverages the dynamic and reversible nature of ionic interactions present in the system with the reinforcement ability of nanoparticles. The composite hydrogels combine within a single platform tunable stiffness, toughness, extensibility, and resiliency behavior not reported previously in other engineered hydrogels. In addition to their excellent mechanical performance, the ionic composites exhibit fast gelling under near‐UV exposure, remarkable conductivity, and fast osmotically driven actuation. The design of such ionic composites, which combine a range of tunable properties and can be readily 3D‐printed into complex architectures, provides opportunities for a variety of practical applications such as artificial tissue, soft actuators, compliant conductors, and sensors for soft robotics.     

Stomata‐Inspired Membrane Produced Through Photopolymerization Patterning

The programmed movements of responsive functional hydrogels have received much attention because of their abundant functions and wide range of engineering applications. In this study, an innovative stomata‐inspired membrane (SIM) is fabricated by using a temperature‐responsive hydrogel through a simple, cost‐effective, and high‐throughput patterned photopolymerization. Polymerization‐induced diffusion on the macroscale surface results in formation of a double‐parted polymer membrane with fine pores after single illumination. After heating the SIM, the less deformable thick frame supports the whole structure and the highly deformable thin base regulates pore shape. Among various SIM types, the slit pores of monocot SIM, which are lined up in parallel, exhibit the largest radius deformation. The morphological configuration of the SIM can be easily controlled by changing the photomask for a given application. As the developed SIM features the sensing‐to‐activation functions of stimuli‐responsive hydrogels and can be easily fabricated, this membrane can be potentially used for numerous practical applications, such as filter membranes with adjustable pores, membrane‐based sensors, membrane‐based actuators, and multifunctional membranes.     

Highly Processable Ionogels with Mechanical Robustness

Currently, the increasing needs of conductive ionogels with intricate shapes and high processability by individual requirements of next-generation flexible electronics constitute significant challenges. Here, the design of highly processable ionogels is reported with mechanical robustness by self-assembly of a common triblock copolymer into a precursor in functional mixed ionic liquids (ILs) containing conductivity-enhancing and polymerizable strength-enhancing components. The subsequent in situ polymerization of the precursor forms physical-co-chemical cross-linked networks, in which the entanglement between physical and chemical cross-linked networks and microphase separation give rise to mechanical robustness of as-fabricated ionogel. The viscosity of the self-assembled precursor can be rationally tuned, which makes the fabrication process compatible with diverse technologies including inkjet printing, spray coating, and 3D printing. By virtue of highly processable capability of the designed ionogels, an auxetic-structured ionogel can be easily generated using 3D printing, which exhibits greatly improved sensitivity and thus is able to monitor tiny deformations. This study that relies on designing functional mixed ILs as the dispersion phase rather than focusing on synthesizing new-type polymers establishes a new route for versatile and programmable fabrication of high-performance ionogels for broader applications.     

Patterned Carbon Nitride–Based Hybrid Aerogel Membranes via 3D Printing for Broadband Solar Wastewater Remediation

Controlled scalable assembly of 2D building blocks into macroscopic 3D architectures is highly significant. However, the assembly of g‐C₃N₄ into tailored, 3D architectures is not yet reported. Here, a 3D printing methodology to enable the programmable construction of carbon nitride–based hybrid aerogel membranes with patterned macroscopic architectures is proposed. g‐C₃N₄ nanosheets (CNNS) are used as the building block, and sodium alginate (SA) increases the viscosity of the ink to obtain the desired rheological properties. Three printing routes, including printing directly in air and in the supporting reservoirs composed of CaCl₂/glycerol solution or Pluronic F127, are demonstrated for printing versatility. The printed Au nanobipyramid–CNNS–SA hybrid aerogels exhibit broadband visible‐light absorption and superior solar wastewater remediation performance with excellent cyclic stability and easy manipulation features. Remarkably, the activity of the 3D‐printed aerogel is about 2.5 times of that of the contrast sample, attributing to the enhanced liquid velocity and solution diffusion efficiency because of the 3D‐printed structure, which is demonstrated by experimental and theoretical simulations. This approach can be extended to the macroscopic assembly of other 2D materials for myriad applications.     

3D Printing of Multifunctional Hydrogels

3D printing technology has been widely explored for the rapid design and fabrication of hydrogels, as required by complicated soft structures and devices. Here, a new 3D printing method is presented based on the rheology modifier of Carbomer for direct ink writing of various functional hydrogels. Carbomer is shown to be highly efficient in providing ideal rheological behaviors for multifunctional hydrogel inks, including double network hydrogels, magnetic hydrogels, temperature‐sensitive hydrogels, and biogels, with a low dosage (at least 0.5% w/v) recorded. Besides the excellent printing performance, mechanical behaviors, and biocompatibility, the 3D printed multifunctional hydrogels enable various soft devices, including loadable webs, soft robots, 4D printed leaves, and hydrogel Petri dishes. Moreover, with its unprecedented capability, the Carbomer‐based 3D printing method opens new avenues for bioprinting manufacturing and integrated hydrogel devices.     

Programmable 3D Shape Changes in Liquid Crystal Polymer Networks of Uniaxial Orientation

3D programmable materials are highly interesting and have a great potential to enable smart robotic devices. Stimuli‐responsive liquid crystal polymer networks (LCNs) offer an attractive platform for the design and fabrication of 3D programmable materials. To date, extensive efforts have been devoted to the design of 3D programmable LCNs by spatially modulating the orientation of liquid crystals. However, the practical application of LCN actuators has been elusive, partly due to tedious orientation technology and monotonous geometry. To resolve this issue, programmable 3D shape changes achieved in LCNs with uniaxial orientation and homogenous composition using a mechanical programming process inspired by the “programming process” of shape‐memory polymers are reported. The mechanical programming process is suitable for LCNs with distinct geometries, for example, the film and fiber, suggesting a promising way for the design of 3D programmable LCN actuators with complex geometries, and deformation profiles (buckle, helix, horn).     

Programmable Electrofabrication of Porous Janus Films with Tunable Janus Balance for Anisotropic Cell Guidance and Tissue Regeneration

Janus films with controlled pore structures can be particularly important in diverse applications. There remains a challenge for simple, rapid, and scalable fabrication methods to control Janus balance (JB) including the thickness of the individual face as well as porosity and pore size. Here the electrofabrication of a porous Janus film with controlled Janus balance from aminopolysaccharide chitosan under the salt effect is reported. Sequential deposition of chitosan under programmable salt environment and electrochemical conditions enables construction of Janus films with precisely controlled Janus balance. Bioactive partially soluble calcium phosphate (CaP) salts can also generate porous structure in Janus film. It is specifically reported that a chitosan/hydroxyl apatite (HAp) composite Janus film can serve as an effective scaffold for guided bone regeneration. The dense layer functions to provide mechanical support and serves as a barrier for fibrous connective tissue penetration. The porous composite layer functions to provide the microenvironment for osteogenesis. In vivo studies using a rat calvarial defect model confirm the beneficial features of this Janus composite for guided bone regeneration. These results suggest the potential of electrofabrication as a simple and scalable platform technology to tune the self‐organization of soft matter for a range of emerging applications.     

Ambient‐Dried, 3D‐Printable and Electrically Conducting Cellulose Nanofiber Aerogels by Inclusion of Functional Polymers

This study presents a novel, green, and efficient way of preparing crosslinked aerogels from cellulose nanofibers (CNFs) and alginate using non‐covalent chemistry. This new process can ultimately facilitate the fast, continuous, and large‐scale production of porous, light‐weight materials as it does not require freeze‐drying, supercritical CO₂ drying, or any environmentally harmful crosslinking chemistries. The reported preparation procedure relies solely on the successive freezing, solvent‐exchange, and ambient drying of composite CNF‐alginate gels. The presented findings suggest that a highly‐porous structure can be preserved throughout the process by simply controlling the ionic strength of the gel. Aerogels with tunable densities (23–38 kg m^?3) and compressive moduli (97–275 kPa) can be prepared by using different CNF concentrations. These low‐density networks have a unique combination of formability (using molding or 3D‐printing) and wet‐stability (when ion exchanged to calcium ions). To demonstrate their use in advanced wet applications, the printed aerogels are functionalized with very high loadings of conducting poly(3,4‐ethylenedioxythiophene):tosylate (PEDOT:TOS) polymer by using a novel in situ polymerization approach. In‐depth material characterization reveals that these aerogels have the potential to be used in not only energy storage applications (specific capacitance of 78 F g^?1), but also as mechanical‐strain and humidity sensors.     

Covalent Poly(2‐Isopropenyl‐2‐Oxazoline) Hydrogels with Ultrahigh Mechanical Strength and Toughness through Secondary Terpyridine Metal‐Coordination Crosslinks

The present study reports the synthesis of poly(2‐isopropenyl‐2‐oxazoline) (PiPOx) dual‐crosslinked hydrogels by both covalent and physical (i.e., metal–ligand coordination) interactions. First, chemical crosslinking of a modified PiPOx polymer containing terpyridine (TPy) unit is achieved by reacting with azelaic acid (non‐anedioic acid). Transient crosslinks are subsequently introduced by complexation of the TPy units with different divalent transition metal ions. This strategy provides access to hydrogels with superior mechanical properties compared to the pure covalently crosslinked PiPOx hydrogels. The mechanical properties and water uptake of the hydrogels could be easily controlled by swelling in different aqueous metal ion solutions. PiPOx hydrogels swollen in Zn²⁺ solution are found to possess ultrahigh compression strength (9 MPa), remarkable toughness (99 MJ m^?3) and outstanding self‐recoverability (98% toughness recovery after swelling for 60 min without external stimuli), which are among the highest reported in literature to date. These remarkable properties are assigned to the thermodynamically stable, but kinetically labile Zn²⁺‐TPy complexes that produce a dynamic network with fewer imperfections and better adaptive properties under mechanical stress compared to those with other metal ions.     

Spatiotemporally Controlled Photoresponsive Hydrogels: Design and Predictive Modeling from Processing through Application

Photoresponsive hydrogels (PRHs) are soft materials whose mechanical and chemical properties can be tuned spatially and temporally with relative ease. Both photo‐crosslinkable and photodegradable hydrogels find utility in a range of biomedical applications that require tissue‐like properties or programmable responses. Progress in engineering with PRHs is facilitated by the development of theoretical tools that enable optimization of their photochemistry, polymer matrices, nanofillers, and architecture. This review brings together models and design principles that enable key applications of PRHs in tissue engineering, drug delivery, and soft robotics, and highlights ongoing challenges in both modeling and application.     

Double-Interlinked Colloidal Gels for Programable Fabrication of Supraparticle Architectures

Engineering colloidal gel inks with suitable features for fabricating robust supraparticle architectures through 3D printing may overcome the challenges of precisely controlling nanoparticles spatial distribution across multiple scales. Herein, oppositely charged proteinaceous-polymeric nanoparticles are combined to generate multi-component colloidal gel (COGEL) inks for fabricating supraparticle volumetric architectures. Leveraging on different nano-functional units, double-interlinked supraparticle assemblies are established via electrostatic interactions and on-demand covalent photocrosslinking. The COGEL inks are readily processable through in-air extrusion 3D printing, forming stable colloidal filaments. 3D printing yielded architecturally defined and robust supraparticle constructs that supported human stem cells attachment and cytoskeletal spreading. Owing to double interparticle interlinks the fabricated supraparticle constructs remained stable under physiological conditions and high/low shear stress, improving over the lower mechanical stability of single-interlinked platforms. Double-interlinked COGELs are processable via suspension 3D printing, unlocking the freeform volumetric writing of nanoparticle inks in protein-based hydrogels volume. The dual-interlinked COGEL technology opens new possibilities for generating user-defined supraparticle architectures with precise volumetric distribution of nanoparticles, both in-air and in-hydrogel platforms. The freedom to select modular multi-particle combinations, as well as the rapid 3D programming of COGEL inks, broadens the range of modular colloidal materials that can be fabricated for a variety of biomedical applications.