Plant cell-like tip-growing polymer precipitate with structurally embedded multistimuli sensing ability.

Soft systems that respond to external stimuli, such as heat, magnetic field, and light, find applications in a range of fields including soft robotics, energy harvesting, and biomedicine. However, most of the existing systems exhibit nondirectional, nastic movement as they can neither grow nor sense the direction of stimuli. In this regard, artificial systems are outperformed by organisms capable of directional growth in response to the sense of stimuli or tropic growth. Inspired by tropic growth schemes of plant cells and fungal hyphae, here we report an artificial multistimuli-responsive tropic tip-growing system based on nonsolvent-induced phase separation of polymer solution, where polymer precipitates as its solvent dissolves into surrounding nonsolvent. We provide a theoretical framework to predict the size and velocity of growing precipitates and demonstrate its capability of sensing the directions of gravity, mechanical contact, and light and adjusting its growing direction in response. Exploiting the embedded physical intelligence of sensing and responding to external stimuli, our soft material system achieves multiple tasks including printing 3D structures in a confined space, bypassing mechanical obstacles, and shielded transport of liquids within water.

Development of Organic/Inorganic Hybrid Materials for Fully Degradable Reactive Oxygen Species-Releasing Stents for Antirestenosis.

Despite innovative advances in stent technology, restenosis remains a crucial issue for the clinical implantation of stents. Reactive oxygen species (ROS) are known to potentially accelerate re-endothelialization and lower the risk of restenosis by selectively controlling endothelial cells and smooth muscle cells. Recently, several studies have been conducted to develop biodegradable polymeric stents. As biodegradable polymers are not electrically conductive, double metallic layers are required to constitute a galvanic couple for ROS generation. Here, we report a new biodegradable hybrid material composed of a biodegradable polymer substrate and double anodic/cathodic metallic layers for enhancing re-endothelialization and suppressing restenosis. Pure Zn and Mg films (3 µm thick) were deposited onto poly-l-lactic acid (PLLA) substrates by DC magnetron sputtering, and a long-term immersion test using biodegradable hybrid materials was performed in phosphate-buffered solution (PBS) for 2 weeks. The concentrations of superoxide anions and hydrogen peroxide generated by the corrosion of biodegradable metallic films were monitored every 1 or 2 days. Both superoxide anions and hydrogen peroxide were seamlessly generated even after the complete consumption of the anodic Mg layer. It was confirmed that the superoxide anions and hydrogen peroxide were formed not only by the galvanic corrosion between the anode and cathode layers but also by the corrosion of a single Mg or Zn layer. The corrosion products of the Mg and Zn films in PBS were phosphate, oxide, or chloride of the biodegradable metals. Thus, it is concluded that ROS generation by the corrosion of PLLA-based hybrid materials can be sustained until the exhaustion of the cathode metal layer.

Jammed Microgel-Based Inks for 3D Printing of Complex Structures Transformable via pH/Temperature Variations.

Structure changes mediated by anisotropic volume changes of stimuli-responsive hydrogels are useful for many research fields, yet relatively simple structured objects are mostly used due to limitation in fabrication methods. To fabricate complex 3 dimensional (3D) structures that undergo structure changes in response to external stimuli, jammed microgel-based inks containing precursors of stimuli-responsive hydrogels are developed for extrusion-based 3D printing. Specifically, the jammed microgel-based inks are prepared by absorbing precursors of poly(acrylic acid) or poly(N-isopropylacrylamide) in poly(acrylamide) (PAAm) microgels, and jamming them. The inks exhibit shear-thinning and self-healing properties that allow extrusion of the inks through a nozzle and rapid stabilization after printing. Stimuli-mediated volume changes are observed for the extruded structures when they are post-crosslinked by UV light to form interpenetrating networks of PAAm microgels and stimuli-responsive hydrogels. Using this method, a dumbbell-shaped object that can transform to a biconvex shape, and a gripper that can grasp and lift an object in response to stimuli are 3D-printed. The jammed microgel-based 3D printing strategy is a versatile method useful for variety of applications as diverse types of monomers absorbable in the microgels can be used to fabricate complex 3D objects transformable by external stimuli.

Agile reversible shape-morphing of particle rafts.

Materials that transform shapes responding to external stimuli can bring unprecedented innovations to soft matter physics, soft robotics, wearable electronics, and architecture. As most conventional soft actuation technologies induce large deformations only in a preprogrammed manner at designated locations, the material systems capable of agile reversible deformations without prescribed patterns are strongly desired for versatile mechanical morphing systems. Here we report a morphable liquid interface coated with dielectric particles, or a particle raft, which can reversibly change its topography under an external electric field. The rafts change from flat floors to towers within seconds, and the morphed structures are even capable of horizontal translation. Our experiments and theory show that the raft deformation is driven by electrostatic attraction between particles and electrodes, while being modulated by electric discharge. A broad range of materials serving as electrodes, e.g., human fingers and transparent polymers, suggests this system's diverse applications, including the human-machine interface and the three-dimensional physical display.

Fabrication of a Highly Stretchable, Wrinkle-Free Electrode with Switchable Transparency Using a Free-Standing Silver Nanofiber Network and Shape Memory Polymer Substrate.

Transparent and stretchable electrodes (TSEs) are a key technology for the next generation of stretchable electronics and optoelectronics. Metallic nanofibers are widely used because of their good optoelectrical properties, but they demonstrate low stretchability. To enhance stretchability, fabricating in-plane buckled nanofibers with the aid of a prestrained substrate has become crucial in this research field. Here, a composite comprising shape memory polymer-TSE (SMP-TSE) using crosslinked polycyclooctene as a substrate, which shows wrinkle-free deformation and switchable optical transparency, is fabricated. Because of its considerable elongation without residual strain and the shape memory behavior of polycyclooctene, in-plane buckled nanofibers are formed effectively. For fabrication of SMP-TSE, continuous and thin metallic nanofiber that can maintain its structural integrity is required; therefore, electrospinning and an ultraviolet reduction process to create a free-standing, conductive, nanofiber network are used. Because of its in-plane buckled nanofibers, the electrode maintained its resistance during 3000 cycles of a bending test and 900 cycles of a tensile test. Furthermore, SMP-TSE is able to electrically control its temperature, optical transparency, elastic modulus, and shape memory behavior. Finally, the use of SMP-TSE in a smart display that can control its optical and mechanical properties is demonstrated.

Highly stretchable and tough hydrogels.

Hydrogels are used as scaffolds for tissue engineering, vehicles for drug delivery, actuators for optics and fluidics, and model extracellular matrices for biological studies. The scope of hydrogel applications, however, is often severely limited by their mechanical behaviour. Most hydrogels do not exhibit high stretchability; for example, an alginate hydrogel ruptures when stretched to about 1.2 times its original length. Some synthetic elastic hydrogels have achieved stretches in the range 10-20, but these values are markedly reduced in samples containing notches. Most hydrogels are brittle, with fracture energies of about 10 J m(-2) (ref. 8), as compared with ∼1,000 J m(-2) for cartilage and ∼10,000 J m(-2) for natural rubbers. Intense efforts are devoted to synthesizing hydrogels with improved mechanical properties; certain synthetic gels have reached fracture energies of 100-1,000 J m(-2) (refs 11, 14, 17). Here we report the synthesis of hydrogels from polymers forming ionically and covalently crosslinked networks. Although such gels contain ∼90% water, they can be stretched beyond 20 times their initial length, and have fracture energies of ∼9,000 J m(-2). Even for samples containing notches, a stretch of 17 is demonstrated. We attribute the gels' toughness to the synergy of two mechanisms: crack bridging by the network of covalent crosslinks, and hysteresis by unzipping the network of ionic crosslinks. Furthermore, the network of covalent crosslinks preserves the memory of the initial state, so that much of the large deformation is removed on unloading. The unzipped ionic crosslinks cause internal damage, which heals by re-zipping. These gels may serve as model systems to explore mechanisms of deformation and energy dissipation, and expand the scope of hydrogel applications.

Bilayered laponite/alginate-poly(acrylamide) composite hydrogel for osteochondral injuries enhances macrophage polarization: An in vivo study.

Addressing osteochondral defects, the objective of current study was to synthesize bilayered hydrogel, where the cartilage layer was formed by alginate (Alg)-polyacrylamide (PAAm) with and without the addition of TGF-ß3 and bone layer by laponite XLS/Alg-PAAm and characterize by in vitro and in vivo experiments. Exceeding the mechanical strength of Alg-PAAm (32.95 ± 1.23 kPa) and XLS based (317.5 ± 21.72 kPa) hydrogels, XLS/Alg-PAAm hydrogel (469.7 ± 6.1 kPa) activated macrophages towards M2 phenotype and stimulated the expression of anti-inflammatory factors. The addition of TGF-ß3 accelerated transition of macrophage polarization, especially between day 4 and 7. The expression levels of M1-related genes such as CD80, iNOS and TNF-α decreased gradually after day 4, reaching lowest values at day 13, whereas the expression levels of M2-related genes, CD206, Arg1 and STAT6 significantly increased promoting M2 macrophage polarization, which might be associated with accelerated bone repair. Moreover, bilayer structure exhibited a better cell viability as well as repairment thorough the XLS contents. In vivo histological examinations verified the significant surface regularity and hyaline like tissue formation employment, along with synchronized degradation profile of the hydrogel with tissue healing at the end of 12 weeks. A mechanically durable, biocompatible and immunocompatible hydrogel was formulated to be utilized in bone-cartilage engineering applications.

An alginate-poly(acrylamide) hydrogel with TGF-ß3 loaded nanoparticles for cartilage repair: Biodegradability, biocompatibility and protein adsorption.

Current implantable materials are limited in terms of function as native tissue, and there is still no effective clinical treatment to restore articular impairments. Hereby, a functionalized polyacrylamide (PAAm)-alginate (Alg) Double Network (DN) hydrogel acting as an articular-like tissue is developed. These hydrogels sustain their mechanical stability under different temperature (+4 °C, 25 °C, 40 °C) and humidity conditions (60% and 75%) over 3 months. As for the functionalization, transforming growth factor beta-3 (TGF-ß3) encapsulated (NPTGF-ß3) and empty poly(lactide-co-glycolide) (PLGA) nanoparticles (PLGA NPs) are synthesized by using microfluidic platform, wherein the mean particle sizes are determined as 81.44 ± 9.2 nm and 126 ± 4.52 nm with very low polydispersity indexes (PDI) of 0.194 and 0.137, respectively. Functionalization process of PAAm-Alg hydrogels with ester-end PLGA NPs is confirmed by FTIR analysis, and higher viscoelasticity is obtained for functionalized hydrogels. Moreover, cartilage regeneration capability of these hydrogels is evaluated with in vitro and in vivo experiments. Compared with the PAAm-Alg hydrogels, functionalized formulations exhibit a better cell viability. Histological staining, and score distribution confirmed that proposed hydrogels significantly enhance regeneration of cartilage in rats due to stable hydrogel matrix and controlled release of TGF-ß3. These findings demonstrated that PAAm-Alg hydrogels showed potential for cartilage repair and clinical application.

Nanofiber Channel Organic Electrochemical Transistors for Low-Power Neuromorphic Computing and Wide-Bandwidth Sensing Platforms.

Organic neuromorphic computing/sensing platforms are a promising concept for local monitoring and processing of biological signals in real time. Neuromorphic devices and sensors with low conductance for low power consumption and high conductance for low-impedance sensing are desired. However, it has been a struggle to find materials and fabrication methods that satisfy both of these properties simultaneously in a single substrate. Here, nanofiber channels with a self-formed ion-blocking layer are fabricated to create organic electrochemical transistors (OECTs) that can be tailored to achieve low-power neuromorphic computing and fast-response sensing by transferring different amounts of electrospun nanofibers to each device. With their nanofiber architecture, the OECTs exhibit a low switching energy of 113 fJ and operate within a wide bandwidth (cut-off frequency of 13.5 kHz), opening a new paradigm for energy-efficient neuromorphic computing/sensing platforms in a biological environment without the leakage of personal information.

Sewable soft shields for the γ-ray radiation.

Soft shields are required to protect the human body during a radioactive accident. However, the modulus of most soft shields, such as HDPE and epoxy, is high, thereby making it difficult to process them in wearable forms like gloves and clothes. We synthesized a soft shield based on a hydrogel that is very compliant, stretchable, and biocompatible. The shields were fabricated by integrating γ-ray-shield particles into hydrogels with an interpenetrating network. The soft shields containing 3.33 M of PbO2 exhibited a high attenuation coefficient (0.284 cm-1) and were stretched to 400% without a rupture. Furthermore, the fabricated soft shield can be sewn without a fabric support due to its high energy-dispersion ability. A wearable arm shield for the γ-ray radiation was demonstrated using a direct sewing of the soft-shield materials.

Zirconia-Polyurethane Aneurysm Clip.

OBJECTIVE: Susceptibility artifacts from metal clips in magnetic resonance (MR) imaging present an obstacle to evaluating the status of clipped aneurysms, parent arteries, and adjacent brain parenchyma. We aimed to develop MR-compatible aneurysm clips. METHODS: Considering the mechanical and biologic properties, as well as MR compatibility of candidate materials, a prototype clip with a zirconia body and a polyurethane head spring (zirconia clip [ZC], straight, 9-mm long) was developed. The closing forces, opening width of blades, and in vitro and in vivo artifact volumes in 3 tesla MR imaging were compared among the prototype and commercial metal clips such as a Yasargil clip (YC, curved type, 8.3-mm long) and a Sugita clip (SC, straight type, 10-mm long). An in vivo animal study was performed with a canine venous pouch aneurysm model. RESULTS: The closing forces (N) at 1 mm and 8 mm from the blade tip were 2.09 and 3.77 in YC, 1.85 and 3.04 in SC, and 2.05 and 4.60 in ZC. The maximum opening widths (mm) was 6.8, 9.0, and 3.0 in YC, SC, and ZC, respectively. The in vitro artifact volumes of YC, SC, and ZC in time-of-flight MR imaging were 26.9, 29.7, and 1.9 times larger than the respective real volumes. The in vivo artifact volumes of YC, SC, and ZC were respectively 21.4, 29.4, and 2.6 times larger than real ones. CONCLUSIONS: ZC showed the smallest susceptibility artifacts and satisfactory closing forces. However, the narrow opening width of the blades was a weak point.

Highly Stretchable and Notch-Insensitive Hydrogel Based on Polyacrylamide and Milk Protein.

Protein-based hydrogels have received attention for biomedical applications and tissue engineering because they are biocompatible and abundant. However, the poor mechanical properties of these hydrogels remain a hurdle for practical use. We have developed a highly stretchable and notch-insensitive hydrogel by integrating casein micelles into polyacrylamide (PAAm) networks. In the casein-PAAm hybrid gels, casein micelles and polyacrylamide chains synergistically enhance the mechanical properties. Casein-PAAm hybrid gels are highly stretchable, stretching to more than 35 times their initial length under uniaxial tension. The hybrid gels are notch-insensitive and tough with a fracture energy of approximately 3000 J/m2. A new mechanism of energy dissipation that includes friction between casein micelles and plastic deformation of casein micelles was suggested.

Ionic skin.

Electronic skins (i.e., stretchable sheets of distributed sensors) report signals using electrons, whereas natural skins report signals using ions. Here, ionic conductors are used to create a new type of sensory sheet, called "ionic skin". Ionic skins are highly stretchable, transparent, and biocompatible. They readily measure strains from 1% to 500%, and pressures as low as 1 kPa.

Performance and biocompatibility of extremely tough alginate/polyacrylamide hydrogels.

Although hydrogels now see widespread use in a host of applications, low fracture toughness and brittleness have limited their more broad use. As a recently described interpenetrating network (IPN) of alginate and polyacrylamide demonstrated a fracture toughness of ≈ 9000 J/m(2), we sought to explore the biocompatibility and maintenance of mechanical properties of these hydrogels in cell culture and in vivo conditions. These hydrogels can sustain a compressive strain of over 90% with minimal loss of Young's Modulus as well as minimal swelling for up to 50 days of soaking in culture conditions. Mouse mesenchymal stem cells exposed to the IPN gel-conditioned media maintain high viability, and although cells exposed to conditioned media demonstrate slight reductions in proliferation and metabolic activity (WST assay), these effects are abrogated in a dose-dependent manner. Implantation of these IPN hydrogels into subcutaneous tissue of rats for 8 weeks led to mild fibrotic encapsulation and minimal inflammatory response. These results suggest the further exploration of extremely tough alginate/PAAM IPN hydrogels as biomaterials.

Strengthening alginate/polyacrylamide hydrogels using various multivalent cations.

We successfully synthesized a family of alginate/polyacrylamide hydrogels using various multivalent cations. These hydrogels exhibit exceptional mechanical properties. In particular, we discovered that the hydrogels cross-linked by trivalent cations are much stronger than those cross-linked by divalent cations. We demonstrate stretchability and toughness of the hydrogels by inflating a hydrogel sheet into a large balloon, and the elasticity by using a hydrogel block as a vibration isolator in a forced vibration test. The excellent mechanical properties of these hydrogels may open up applications for hydrogels.