Self-Healing Polymer Network with High Strength, Tunable Properties, and Biocompatibility

Nature has designed and optimized materials to possess a range of properties and functions. Here, we introduced a molecular design strategy to impart customizable functionality and varying mechanical properties into gels; mimicking nature's range of tunable materials. We demonstrate a gel that is not only tough but also exhibits self-healing, is easily controllable, and the final materials have a broad range of mechanical properties. To develop these materials, we first prepared a methacrylic acid (MAAc) and poly(ethylene glycol) methyl ether methacrylate (OEGMA) random copolymer: poly(MAAc-co-OEGMA). The network's deliberate inter- and intramolecular hydrogen bondings were modified through some of the acid sites being postfunctionalized with benzaldehyde (BA) and cross-linked with diamine-terminated poly(dimethylsiloxane) (PDMS) to form dynamic imine bonds. Due to the low glass transition temperature of the PDMS cross-linker, the chain mobility can be enhanced, enabling rapid self-healing (>98% within seconds), in addition to improving the stretchability (tensile strain) from a few % to almost 500%. The prepared polymers and gels were well characterized through various techniques including Fourier transform infrared spectroscopy (FTIR), 1H NMR, and size-exclusion chromatography (SEC) analysis. Mechanical testing and dynamic mechanical analysis (DMA) revealed interesting insights into the broad-range (Young's modulus: 100 kPa to >300 MPa) and tunable mechanical properties, including the tensile strength (from 12 to 0.1 MPa) and strain (up to 500%) as well as the storage (0.1 to 60 MPa) and loss (1 to 40 MPa) moduli of the dynamic self-healing gel. Interestingly, the tensile strength decreasing with increasing cross-link density. Lastly, the biocompatibility of the gels was investigated, with an initial study of both human bone and skin cells indicating increased biocompatibility with gels that had been cross-linked with PDMS.Funding from the Australian Research Council (DP180103918) and the ANU Futures Scheme is gratefully acknowledge

Strong, Self-Healable, and Recyclable Visible-Light-Responsive Hydrogel Actuators

The most pressing challenges for light-driven hydrogel actuators include reliance on UV light, slow response, poor mechanical properties, and limited functionalities. Now, a supramolecular design strategy is used to address these issues. Key is the use of a benzylimine-functionalized anthracene group, which red-shifts the absorption into the visible region and also stabilizes the supramolecular network through π-π interactions. Acid-ether hydrogen bonds are incorporated for energy dissipation under mechanical deformation and maintaining hydrophilicity of the network. This double-crosslinked supramolecular hydrogel developed via a simple synthesis exhibits a unique combination of high strength, rapid self-healing, and fast visible-light-driven shape morphing both in the wet and dry state. As all of the interactions are dynamic, the design enables the structures to be recycled and reprogrammed into different 3D objects.Funding is gratefully acknowledged from the Australian Research Council(DP180103918),and the ANU Futures Scheme. Z.J.would like to acknowledge funding of ANU Early Career Researchers(ECR)Travel Grant(R.46850.4656)

Tough, Self-Healing Hydrogels Capable of Ultrafast Shape Changing

Achieving multifunctional shape-changing hydrogels with synergistic and engineered material properties is highly desirable for their expanding applications, yet remains an ongoing challenge. The synergistic design of multiple dynamic chemistries enables new directions for the development of such materials. Herein, a molecular design strategy is proposed based on a hydrogel combining acid-ether hydrogen bonding and imine bonds. This approach utilizes simple and scalable chemistries to produce a doubly dynamic hydrogel network, which features high water uptake, high strength and toughness, excellent fatigue resistance, fast and efficient self-healing, and superfast, programmable shape changing. Furthermore, deformed shapes can be memorized due to the large thermal hysteresis. This new type of shape-changing hydrogel is expected to be a key component in future biomedical, tissue, and soft robotic device applications.Funding was gratefully acknowledged from the Australian Research Council (DP180103918), and the ANU Futures Scheme. The authors thank Associate Professor Zbigniew Stachurski for assistance with tensile testing

Extrusion 3D Printing of Polymeric Materials with Advanced Properties

3D printing is a rapidly growing technology that has an enormous potential to impact a wide range of industries such as engineering, art, education, medicine, and aerospace. The flexibility in design provided by this technique offers many opportunities for manufacturing sophisticated 3D devices. The most widely utilized method is an extrusion-based solid-freeform fabrication approach, which is an extremely attractive additive manufacturing technology in both academic and industrial research communities. This method is versatile, with the ability to print a range of dimensions, multimaterial, and multifunctional 3D structures. It is also a very affordable technique in prototyping. However, the lack of variety in printable polymers with advanced material properties becomes the main bottleneck in further development of this technology. Herein, a comprehensive review is provided, focusing on material design strategies to achieve or enhance the 3D printability of a range of polymers including thermoplastics, thermosets, hydrogels, and other polymers by extrusion techniques. Moreover, diverse advanced properties exhibited by such printed polymers, such as mechanical strength, conductance, self-healing, as well as other integrated properties are highlighted. Lastly, the stimuli responsiveness of the 3D printed polymeric materials including shape morphing, degradability, and color changing is also discussed

Functional block copolymer nanoparticles: toward the next generation of delivery vehicles

The self-assembly of functional block copolymers (BCPs) into dispersed nanoparticles is a powerful technique for the preparation of novel delivery vehicles with precise control of morphology and architecture. Well-defined BCPs containing an alkyne-functional, biodegradable polylactide (PLA) block were synthesized and conjugated with azide-functional coumarin dyes via copper catalyzed azide alkyne cycloaddition ‘click’ chemistry. Self-assembled nanoparticles with internal nanophase-separated morphologies could then be accessed by carefully controlling the composition of the BCPs and release of the covalently attached model payload was shown to occur under physiological conditions via the degradation of the PLA scaffold. These results demonstrate the potential of self-assembled nanoparticles as modular delivery vehicles with multiple functionalities, nanostructures, and compartmentalized internal morphology

Supramolecular guests in solvent driven block copolymer assembly: from internally structured nanoparticles to micelles

Supramolecular interactions between different hydrogen-bonding guests and poly(2-vinylpyridine)-block-poly(styrene) can be exploited to prepare remarkably diverse self-assembled nanostructures in dispersion from a single block copolymer (BCP). The characteristics of the BCP can be efficiently controlled by tailoring the properties of a guest which preferentially binds to the P2VP block. For example, the incorporation of a hydrophobic guest creates a hydrophobic BCP complex that forms phase separated nanoparticles upon self-assembly. Conversely, the incorporation of a hydrophilic guest results in an amphiphilic BCP complex that forms spherical micelles in water. The ability to tune the self-assembly behavior and access dramatically different nanostructures from a single BCP substrate demonstrates the exceptional versatility of the self-assembly of BCPs driven by supramolecular interactions. This approach represents a new methodology that will enable the further design of complex, responsive self-assembled nanostructures

3D and 4D printable dual cross-linked polymers with high strength and humidity-triggered reversible actuation

It is highly desirable but challenging to develop humidity-responsive polymers with simultaneously improved mechanical properties and 3D printability, while still displaying fast, reversible and complex shape transformations. Herein, a facile and scalable supramolecular strategy of fabricating a new class of humidity-responsive polymers is proposed to address this issue. The multiple hydrogen-bond cross-linked network is used to provide high humidity sensitivity and shear-dependent rheological behavior. Further introduction of metal coordination bonds can not only improve mechanical strength and creep resistance, but also promote reversible humidity-driven actuation and generate viscoelastic hydrogel inks. This humidity-responsive polymer with these unique combined attributes enables the potential to fabricate diverse functional materials from artificial muscles, smart electronic and catalytic devices. Moreover, diverse arbitrary architectures with spatial thickness contrast exhibiting sophisticated biomimetic 4D printing process were manufactured by direct ink writing (DIW). This material and method not only provides a general route to tune versatile functionalities and intelligent responsiveness of polymeric actuators at the molecular level, but also provides new opportunities for building exceptional 4D printed products.Funding is gratefully acknowledged from the Australian Research Council (DP180103918), and the ANU Futures Schem

Mesostructured Block Copolymer Nanoparticles: Versatile Templates for Hybrid Inorganic/Organic Nanostructures

We present a versatile strategy to prepare a range of nanostructured poly(styrene)-block-poly(2-vinyl pyridine) copolymer particles with tunable interior morphology and controlled size by a simple solvent exchange procedure. A key feature of this strategy is the use of functional block copolymers incorporating reactive pyridyl moieties which allow the absorption of metal salts and other inorganic precursors to be directed. Upon reduction of the metal salts, well-defined hybrid metal nanoparticle arrays could be prepared, whereas the use of oxide precursors followed by calcination permits the synthesis of silica and titania particles. In both cases, ordered morphologies templated by the original block copolymer domains were obtained

The benefits of macromolecular hydrogen sulfide prodrugs

Hydrogen sulfide has significant therapeutic potential that is continually being implicated in a variety of biochemical processes. This highlight article will present the benefits and opportunities in designing macromolecule based H2S donors. Emphasis will be on how design of polymer systems can help drive the development of H2S therapeutics. With a better range of donor systems this field will progress rapidly and new applications for H2S therapeutics will be discovered