Simultaneous Polymerization Acceleration and Mechanical Enhancement for Printing a Biomimetic PEDOT Adhesive by Coordinative and Orthogonal Ruthenium Photochemistry.

Conductive hydrogels are promising material candidates in fields ranging from flexible sensors and electronic skin applications to personalized medical monitoring. However, developing intrinsically conductive polymer hydrogels (ICPHs) with high mechanical properties and excellent printability is still challenging. Here, we introduce a simultaneous polymerization acceleration and mechanical enhancement (SPAME) strategy to construct PEDOT-based ICPHs via the rational design of coordinative and orthogonal ruthenium photochemistry (CORP). This orthogonal photochemistry triggers the oxidative polymerization of EDOT and the coupling of phenols within seconds under blue light irradiation. Benefiting from the bifunctional EDTA-Fe design, the photoreleased Fe(III) accelerated the EDOT polymerization and shortened the preparation time of ICPHs to a few seconds. At the same time, the addition of EDTA-Fe enhanced their mechanical properties, and both the critical strains and maximum stresses of the hydrogel doubled. Furthermore, the introduction of phenol residues in PAA-Ph significantly shortened the gelation time from several minutes to about 7 s. Thus, this fast and controllable CORP chemistry is compatible with standard printing techniques for engineering hydrogels for complex multifunctional structures for multifunctional bioelectronics and devices.

Customizable Low-Friction Tough Hydrogels for Potential Cartilage Tissue Engineering by a Rapid Orthogonal Photoreactive 3D-Printing Design.

Hydrogels have demonstrated wide applications in tissue engineering, but it is still challenging to develop strong, customizable, low-friction artificial scaffolds. Here, we report a rapid orthogonal photoreactive 3D-printing (ROP3P) strategy to achieve the design of high-performance hydrogels in tens of minutes. The orthogonal ruthenium chemistry enables the formation of multinetworks in hydrogels via phenol-coupling reaction and traditional radical polymerization. Further Ca2+-cross-linking treatment greatly improves their mechanical properties (6.4 MPa at a critical strain of 300%) and toughness (10.85 MJ m-3). The tribological investigation reveals that the high elastic moduli of the as-prepared hydrogels improve their lubrication (∼0.02) and wear-resistance performances. These hydrogels are biocompatible and nontoxic and promote bone marrow mesenchymal stem cell adhesion and propagation. The introduction of 1-hydroxy-3-(acryloylamino)-1,1-propanediylbisphosphonic acid units can greatly enhance their antibacterial property to kill typical Escherichia coli and Staphylococcus aureus. Moreover, the rapid ROP3P can achieve hydrogel preparation in several seconds and is readily compatible with making artificial meniscus scaffolds. The printed meniscus-like materials are mechanically stable and can maintain their shape under long-term gliding tests. It is anticipated that these high-performance customizable low-friction tough hydrogels and the highly efficient ROP3P strategy could promote further development and practical applications of hydrogels in biomimetic tissue engineering, materials chemistry, bioelectronics, and so on.

Trifunctional Microgel-Mediated Preparation and Toughening of Printable High-Performance Chitosan Hydrogels for Underwater Communications.

Natural and biocompatible chitosan has demonstrated wide applications. However, rapidly fabricating high-performance chitosan hydrogels in one-step controllable processes is still a challenge for some advanced applications. Here, we report a trifunctional microgel-mediated photochemical (TMMP) strategy to achieve the fabrication of printable tough chitosan-based hydrogels (PTCHs) in seconds. Such microgels help the slow release of persulfate anions and their uniform dispersion in an aqueous solution of cationic chitosan. The released persulfates are available for preparing multiple networks of phenolic coupling of modified chitosan and radical polymerization of Pluronic F127 via orthogonal tris(bipyridine)ruthenium(II)-based photochemistry, respectively. Trifunctional microgels have reversible Ca2+-crosslinked networks that further improve the hydrogels' mechanical properties and toughness. The maximum stress and toughness increase by >20 folds compared to the chitosan and F127 hydrogels with single network structures. Moreover, these microgels enable the precursor to have a good shearing-thinning property and benefit the controllable preparation of PTCHs in a short time, as low as ∼4 s under visible light irradiation. It, therefore, is compatible with standard printing techniques to make complex structures. Strain sensors based on structured PTCHs have stable mechanical and responsive properties in the water, which are applied for real-time underwater communications (<0.4 s). It is anticipated that this one-step TMMP strategy opens new horizons for designing advanced chitosan hydrogels.

Protein Crystallization-Mediated Self-Strengthening of High-Performance Printable Conducting Organohydrogels.

Conductive polymers have many advanced applications, but there is still an important target in developing a general and straightforward strategy for printable, mechanically stable, and durable organohydrogels with typical conducting polymers of, for example, polypyrrole, polyaniline, or poly(3,4-ethylenedioxythiophene). Here we report a protein crystallization-mediated self-strengthening strategy to fabricate printable conducting organohydrogels with the combination of rational photochemistry design. Such organohydrogels are one-step prepared via rapidly and orthogonally controllable photopolymerizations of pyrroles and gelatin protein in tens of seconds. As-prepared conducting organohydrogels are patterned and printed to complicated structures via shadow-mask lithography and 3D extrusion technology. The mild photocatalytic system gives the transition metal carbide/nitride (MXene) component high stability during the oxidative preparation process and storage. Controlling water evaporation promotes gelatin crystallization in the as-prepared organohydrogels that significantly self-strengthens their mechanical property and stability in a broad temperature range and durability against continuous friction treatment without introducing guest functional materials. Also, these organohydrogels have commercially electromagnetic shielding, thermal conducting properties, and temperature- and light-responsibility. To further demonstrate the merits of this simple strategy and as-prepared organohydrogels, prism arrays, as proofs-of-concept, are printed and applied to make wearable triboelectric nanogenerators. This self-strengthening process and 3D-printability can greatly improve their voltage, charge, and current output performances compared to the undried and flat samples.

Photoredox-Mediated Designing and Regulating Metal-Coordinate Hydrogels for Programmable Soft 3D-Printed Actuators.

Metal-organic coordination is widely applied for designing responsive polymers and soft devices. But it is still a challenge to prepare redox-responsive actuators with complicated structures, limiting their advanced applications in material and engineering fields. Here, we report a photoredox-mediated designing and regulating strategy to fabricate metal-coordinate hydrogels with the catalysis of Ru(II)/Co(III) under visible-light irradiation in seconds. Meanwhile, multiple polymer networks are formed and penetrated by each other, enabling as-prepared hydrogels excellent mechanical properties and toughness. This rapid, one-step, and controllable process is highly compatible with standard photography and printing techniques to make hierarchical 2D/3D structures. Importantly, the oxidization decomposition of Co(III) benefits the formation of cobalt cation-based redox-responsive networks, which have the potential for designing shape-memory materials and actuators by the regulation of Co3+/2+ states via tuning redox environmental conditions. As a proof-of-concept, a programmable air-driven actuator is successfully demonstrated to control cargo capturing/releasing by designing complicated, asymmetric structures and optimizing their performance with the combination of a typical extrusion 3D printing approach. In this Letter, we report a simple and general metal-organic coordination strategy for designing high-performance actuators, which shows promising applications in smart soft devices and electronics.

Bifunctional Phenol-Enabled Sequential Polymerization Strategy for Printable Tough Hydrogels.

Hydrogels are promising material candidates in engineering soft robotics, mechanical sensors, biomimetic regenerative medicine, etc. However, developing multinetwork hydrogels with high mechanical properties and excellent printability are still challenging. Here, a bifunctional phenol-enabled sequential polymerization (BPSP) strategy is reported to fabricate high-performance multinetwork hydrogels under the orthogonal catalysis of efficient ruthenium photochemistry. Benefiting from this bifunctional design, phenols can sequentially polymerize with typical monomers and themselves to fabricate various phenol-containing polymers (Ph-Ps) and Ph-Ps-based multinetwork tough hydrogels, respectively. The as-prepared hydrogels have maximum stress of 0.75 MPa and toughness of 2.2 MJ m- 3 under the critical strain of 800%. These property parameters are a maximum of 16 times higher than those of the phenol-postmodified and phenol-free hydrogels. Moreover, the rapid coupling polymerization of phenols can shorten the gelation times of hydrogels to as low as ≈4 s, which enables its printable property for customizable applications. As a proof of concept, a 3D scaffold-like structure is optimized as highly sensitive mechanical sensors for detecting various human motions.

Visible-Light-Mediated Nano-biomineralization of Customizable Tough Hydrogels for Biomimetic Tissue Engineering.

Biomineralized tough hydrogels (BTHs) have advanced applications in the fields of soft bioelectronics and biomimetic tissue engineering. But the development of rapid and general photomineralization strategies for one-step fabrication of customizable BTHs is still a challenging task. Here we report a straightforward, low-cost visible-light-mediated nano-biomineralization (VLMNB) strategy via a rational design of a phosphate source and efficient ruthenium photochemistry. Multinetwork tough hydrogels are simultaneously constructed under the same condition. Therefore, BTHs are rapidly prepared in a short time as low as ∼60 s under visible light irradiation. The in situ formation of calcium phosphate particles can improve BTHs' mechanical and biological properties and reduce the friction coefficient with bones. Furthermore, fast biomineralization and solidification processes in these BTHs benefit their injectable and highly flexible customizable design, showing applications of promoting customizable skin repair and bone regeneration.

Orthogonal photochemistry-assisted printing of 3D tough and stretchable conductive hydrogels.

3D-printing tough conductive hydrogels (TCHs) with complex structures is still a challenging task in related fields due to their inherent contrasting multinetworks, uncontrollable and slow polymerization of conductive components. Here we report an orthogonal photochemistry-assisted printing (OPAP) strategy to make 3D TCHs in one-pot via the combination of rational visible-light-chemistry design and reliable extrusion printing technique. This orthogonal chemistry is rapid, controllable, and simultaneously achieve the photopolymerization of EDOT and phenol-coupling reaction, leading to the construction of tough hydrogels in a short time (tgel ~30 s). As-prepared TCHs are tough, conductive, stretchable, and anti-freezing. This template-free 3D printing can process TCHs to arbitrary structures during the fabrication process. To further demonstrate the merits of this simple OPAP strategy and TCHs, 3D-printed TCHs hydrogel arrays and helical lines, as proofs-of-concept, are made to assemble high-performance pressure sensors and a temperature-responsive actuator. It is anticipated that this one-pot rapid, controllable OPAP strategy opens new horizons to tough hydrogels.

Visible-light-assisted multimechanism design for one-step engineering tough hydrogels in seconds.

Tough hydrogels that are capable of efficient mechanical energy dissipation and withstanding large strains have potential applications in diverse areas. However, most reported fabrication strategies are performed in multiple steps with long-time UV irradiation or heating at high temperatures, limiting their biological and industrial applications. Hydrogels formed with a single pair of mechanisms are unstable in harsh conditions. Here we report a one-step, biocompatible, straightforward and general strategy to prepare tough soft hydrogels in a few tens of seconds under mild conditions. With a multimechanism design, the network structures remarkably improve the mechanical properties of hydrogels and maintain their high toughness in various environments. The broad compatibility of the proposed method with a spectrum of printing technologies makes it suitable for potential applications requiring high-resolution patterns/structures. This strategy opens horizons to inspire the design and application of high-performance hydrogels in fields of material chemistry, tissue engineering, and flexible electronics.

A new soft-matter material with old chemistry: Passerini multicomponent polymerization-induced assembly of AIE-active double-helical polymers with rapid visible-light degradability.

Mimicking the superstructures and functions of natural chiral materials is beneficial to understand specific biological activities in living organisms and broaden applications in the fields of chemistry and materials sciences. However, it is still a great challenge to construct water-soluble, double-helical polymers with multiple responsiveness. Herein, we report for the first time a straightforward, general strategy to address this issue by taking advantage of Passerini multicomponent polymerization-induced assembly (PMPIA). The polymerization-induced generation of supramolecular interactions in chiral α-acyloxy amides drives the assembly of polymers and improves their stability in various solvents. This double-helical polymer is sensitive to metal ions, temperature, pH, and solvents, making both the superstructure and the AIE effect reversibly adjustable. Meanwhile, the hydrogen-bonding-assisted cyclization of photolabile α-acyloxy amides accelerates the degradation of helical polymers under visible-light irradiation. It is anticipated that this novel PMPIA strategy opens new horizons to inspire the design of advanced chiral/helical polymers with multiple functions.

Rapidly Visible-Light-Mediated Photogelations for One-Step Engineering Multifunctional Tough Hydrogel Tubes.

Hydrogel tubes as one kind of perfusable tubular materials, show promising applications in a wide spectrum of fields. However, there is still a great challenge to design a rapid, biocompatible, and straightforward strategy for one-step engineering tough hydrogel tubes, which have excellent mechanical properties, unique resilience, and multiple functions. Herein, we explore visible-light-mediated orthogonal photochemistry to achieve the fabrication of tough hydrogel tubes with double networks via a coaxial-nozzle spinning technique under short blue-light irradiation (∼20 s). The as-prepared tubes are tough (2.3 MJ m-3) and have mechanical strength (∼300 kPa) with a critical strain of 16, good fatigue resistance, and resilience (>95% within 3 min). These perfusable tubular hydrogels not only can be knitted and assembled to complicated 2D/3D structures, but also are designed to fabricate functional tubes in one step with the applications in fields of smart materials, soft electronics, and sensors.

Direct 3D Printing of Hybrid Nanofiber-Based Nanocomposites for Highly Conductive and Shape Memory Applications.

Three-dimensional (3D) printing with conductive polymer nanocomposites provides an attractive strategy for the "on-demand" fabrication of electrical devices. This paper demonstrates a family of highly conductive multimaterial composites that can be directly printed into ready-to-use multifunctional electrical devices using a flexible solvent-cast 3D printing technique. The new material design leverages the high aspect ratio and low contact resistance of the hybrid silver-coated carbon nanofibers (Ag@CNFs) with the excellent 3D printability of the thermoplastic polymer. The achieved nanocomposites are capable of printing in open air under ambient conditions, meanwhile presenting a low percolation threshold (i.e., <6 vol %) and high electrical conductivity (i.e., >2.1 × 105 S/m) without any post-treatments. We further find that this hybrid Ag@CNF-based nanocomposite shows a quick and low-voltage-triggered electrical-responsive shape memory behavior, making it a great candidate for printing electroactive devices. Multiple different as-printed Ag@CNF-based highly conductive nanocomposite structures used as high-performance electrical devices (e.g., ambient-printable conductive components, microstructured fiber sensors, flexible and lightweight scaffolds for electromagnetic interference shielding, and low-voltage-triggered smart grippers) are successfully demonstrated herein. This simple additive manufacturing approach combined with the synergic effects of the multimaterial nanocomposite paves new ways for further development of advanced and smart electrical devices in areas of soft robotics, sensors, wearable electronics, etc.

Direct-Write Fabrication of 4D Active Shape-Changing Structures Based on a Shape Memory Polymer and Its Nanocomposite.

Four-dimensional (4D) active shape-changing structures based on shape memory polymers (SMPs) and shape memory nanocomposites (SMNCs) are able to be controlled in both space and time and have attracted increasing attention worldwide. However, conventional processing approaches have restricted the design space of such smart structures. Herein, 4D active shape-changing architectures in custom-defined geometries exhibiting thermally and remotely actuated behaviors are achieved by direct-write printing of ultraviolet (UV) cross-linking poly(lactic acid)-based inks. The results reveal that, by the introduction of a UV cross-linking agent, the printed objects present excellent shape memory behavior, which enables three-dimensional (3D)-one-dimensional (1D)-3D, 3D-two-dimensional (2D)-3D, and 3D-3D-3D configuration transformations. More importantly, the addition of iron oxide successfully integrates 4D shape-changing objects with fast remotely actuated and magnetically guidable properties. This research realizes the printing of both SMPs and SMNCs, which present an effective strategy to design 4D active shape-changing architectures with multifunctional properties. This paves the way for the further development of 4D printing, soft robotics, flexible electronics, minimally invasive medicine, etc.

Shape-memory polymer nanocomposites with a 3D conductive network for bidirectional actuation and locomotion application.

Electrical stimulation of shape-memory polymers (SMPs) has many advantages over thermal methods; creating an efficient conductive path through the bulk polymers is essential for developing high performance electroactive systems. Here, we show that a three-dimensional (3D) porous carbon nanotube sponge can serve as a built-in integral conductive network to provide internal, homogeneous, in situ Joule heating for shape-memory polymers, thus significantly improving the mechanical and thermal behavior of SMPs. As a result, the 3D nanocomposites show a fast response and produce large exerting forces (with a maximum flexural stress of 14.6 MPa) during shape recovery. We further studied the construction of a double-layer composite structure for bidirectional actuation, in which the shape change is dominated by the temperature-dependent exerting force from the top and bottom layer, alternately. An inchworm-type robot is demonstrated whose locomotion is realized by such bidirectional shape memory. Our large stroke shape-memory nanocomposites have promising applications in many areas including artificial muscles and bionic robots.

Fast Triggering of Shape Memory Polymers using an Embedded Carbon Nanotube Sponge Network.

In this work, a 3-D porous carbon nanotube sponge (CNTS) was embedded within a shape memory polymer (SMPs) matrix. We demonstrate complete infiltration and filling of the SMPs into the CNTS by capillary force without any damage to the CNTS structure. With only ~0.2 wt% carbon nanotube loading, the glass transition temperature is increased by ~20 °C, indicating strong interaction between CNTS and the SMPs matrix. Further, we find that the uniform distribution of the carbon nanotubes in the nanocomposite results in high electrical conductivity, and thus highly effective electricity triggering capability. The carbon nanotube sponge shape memory polymer (CNTS/SMPs) nanocomposite could be triggered within ~10 seconds by the application of ~10 volts. Results from finite element simulations showed good agreement with the experimental results, and indicated that for our system the interface thermal energy loss does not have a significant effect on the heating rate of the polymer matrix.