Ultrafast underwater self-healing piezo-ionic elastomer via dynamic hydrophobic-hydrolytic domains.

The development of advanced materials capable of autonomous self-healing and mechanical stimulus sensing in aquatic environments holds great promise for applications in underwater soft electronics, underwater robotics, and water-resistant human-machine interfaces. However, achieving superior autonomous self-healing properties and effective sensing simultaneously in an aquatic environment is rarely feasible. Here, we present an ultrafast underwater molecularly engineered self-healing piezo-ionic elastomer inspired by the cephalopod's suckers, which possess self-healing properties and mechanosensitive ion channels. Through strategic engineering of hydrophobic C-F groups, hydrolytic boronate ester bonds, and ions, the material achieves outstanding self-healing efficiencies, with speeds of 94.5% (9.1 µm/min) in air and 89.6% (13.3 µm/min) underwater, coupled with remarkable pressure sensitivity (18.1 kPa-1) for sensing performance. Furthermore, integration of this mechanosensitive device into an underwater submarine for signal transmission and light emitting diode modulation demonstrates its potential for underwater robotics and smarter human-machine interactions.

Ion trap and release dynamics enables nonintrusive tactile augmentation in monolithic sensory neuron.

An iontronic-based artificial tactile nerve is a promising technology for emulating the tactile recognition and learning of human skin with low power consumption. However, its weak tactile memory and complex integration structure remain challenging. We present an ion trap and release dynamics (iTRD)-driven, neuro-inspired monolithic artificial tactile neuron (NeuroMAT) that can achieve tactile perception and memory consolidation in a single device. Through the tactile-driven release of ions initially trapped within iTRD-iongel, NeuroMAT only generates nonintrusive synaptic memory signals when mechanical stress is applied under voltage stimulation. The induced tactile memory is augmented by auxiliary voltage pulses independent of tactile sensing signals. We integrate NeuroMAT with an anthropomorphic robotic hand system to imitate memory-based human motion; the robust tactile memory of NeuroMAT enables the hand to consistently perform reliable gripping motion.

Ions-Silica Percolated Ionic Dielectric Elastomer Actuator for Soft Robots.

Soft robotics systems are currently under development using ionic electroactive polymers (i-EAP) as soft actuators for the human-machine interface. However, this endeavor has been impeded by the dilemma of reconciling the competing demands of force and strain in i-EAP actuators. Here, the authors present a novel design called "ions-silica percolated ionic dielectric elastomer (i-SPIDER)", which exhibits ionic liquid-confined silica microstructures that effectively resolve the chronic issue of conventional i-EAP actuators. The i-SPIDER actuator demonstrates remarkable electromechanical conversion capacity at low voltage, thanks to improved ion accumulation facilitated by interpreting electrode polarization at the electrolyte-electrode interface. This approach concurrently enhances both strain (by approximately 1.52%) and force (by roughly 1.06 mN) even at low Young's modulus (merely 5.9 MPa). Additionally, by demonstrating arachnid-inspired soft robots endowed with user-desired tasks through control of various form factors, the development of soft robots using the i-SPIDER that can concomitantly enhance strain and force holds promise as a compelling avenue for ushering in the next generation of miniaturized, low-powered soft robotics.

Exciton-Scissoring Perfluoroarenes Trigger Photomultiplication in Full Color Organic Image Sensors.

An unprecedented but useful functionality of perfluoroarenes to enable exciton scissoring in photomultiplication-type organic photodiodes (PM-OPDs) is reported. Perfluoroarenes that are covalently connected to polymer donors via a photochemical reaction enable the demonstration of high external quantum efficiency and B-/G-/R-selective PM-OPDs without the use of conventional acceptor molecules. The operation mechanism of the suggested perfluoroarene-driven PM-OPDs, how covalently bonded polymer donor:perfluoroarene PM-OPDs can perform as effectively as polymer donor:fullerene blend-based PM-OPDs, is investigated. By employing a series of arenes and conducting steady-state/time-resolved photoluminescence and transient absorption spectroscopy analyses, it is found that interfacial band bending between the perfluoroaryl group and polymer donor is responsible for exciton scissoring and subsequent electron trapping, which induces photomultiplication. Owing to the acceptor-free and covalently interconnected photoactive layer in the suggested PM-OPDs, superior operational and thermal stabilities are observed. Finally, finely patterned B-/G-/R-selective PM-OPD arrays that enable the construction of highly sensitive passive matrix-type organic image sensors are demonstrated.

Implantable Multi-Cross-Linked Membrane-Ionogel Assembly for Reversible Non-Faradaic Neurostimulation.

Neural interfaces play a major role in modulating neural signals for therapeutic purposes. To meet the demand of conformable neural interfaces for developing bioelectronic medicine, recent studies have focused on the performance of electrical neurostimulators employing soft conductors such as conducting polymers and electronic or ionic conductive hydrogels. However, faradaic charge injection at the interface of the electrode and nerve tissue causes irreversible gas evolution, oxidation of electrodes, and reduction of biological ions, thus causing undesired tissue damage and electrode degradation. Here we report a conformable neural interface engineering based on multicross-linked membrane-ionogel assembly (termed McMiA), which enables nonfaradaic neurostimulation without irreversible charge transfer reaction. The McMiA consists of a genipin-cross-linked biopolymeric ionogel coupled with a dopamine-cross-linked graphene oxide membrane to prevent ion exchange between biological and synthetic McMiA ions and to function as a bioadhesive forming covalent bonds with the target tissues. In addition, the demonstration of bioelectronic medicine via the McMiA-based neurostimulation of sciatic nerves shows the enhanced clinical utility in treating the overactive bladder syndrome. As the McMiA-based neural interface is soft, robust for bioadhesion, and stable in a physiological environment, it can offer significant advancement in biocompatibility and long-term operability for neural interface engineering.

Silicone engineered anisotropic lithography for ultrahigh-density OLEDs.

Ultrahigh-resolution patterning with high-throughput and high-fidelity is highly in demand for expanding the potential of organic light-emitting diodes (OLEDs) from mobile and TV displays into near-to-eye microdisplays. However, current patterning techniques so far suffer from low resolution, consecutive pattern for RGB pixelation, low pattern fidelity, and throughput issue. Here, we present a silicone engineered anisotropic lithography of the organic light-emitting semiconductor (OLES) that in-situ forms a non-volatile etch-blocking layer during reactive ion etching. This unique feature not only slows the etch rate but also enhances the anisotropy of etch direction, leading to gain delicate control in forming ultrahigh-density multicolor OLES patterns (up to 4500 pixels per inch) through photolithography. This patterning strategy inspired by silicon etching chemistry is expected to provide new insights into ultrahigh-density OLED microdisplays.

Ultrafast, autonomous self-healable iontronic skin exhibiting piezo-ionic dynamics.

The self-healing properties and ionic sensing capabilities of the human skin offer inspiring groundwork for the designs of stretchable iontronic skins. However, from electronic to ionic mechanosensitive skins, simultaneously achieving autonomously superior self-healing properties, superior elasticity, and effective control of ion dynamics in a homogeneous system is rarely feasible. Here, we report a Cl-functionalized iontronic pressure sensitive material (CLiPS), designed via the introduction of Cl-functionalized groups into a polyurethane matrix, which realizes an ultrafast, autonomous self-healing speed (4.3 µm/min), high self-healing efficiency (91% within 60 min), and mechanosensitive piezo-ionic dynamics. This strategy promotes both an excellent elastic recovery (100%) and effective control of ion dynamics because the Cl groups trap the ions in the system via ion-dipole interactions, resulting in excellent pressure sensitivity (7.36 kPa-1) for tactile sensors. The skin-like sensor responds to pressure variations, demonstrating its potential for touch modulation in future wearable electronics and human-machine interfaces.

Mitigating Lithium Dissolution and Polysulfide Shuttle Effect Phenomena Using a Polymer Composite Layer Coating on the Anode in Lithium-Sulfur Batteries.

To mitigate lithium dissolution and polysulfide shuttle effect phenomena in high-energy lithium sulfur batteries (LISBs), a conductive, flexible, and easily modified polymer composite layer was applied on the anode. The polymer composite layer included polyaniline and functionalized graphite. The electrochemical behavior of LISBs was studied by galvanostatic charge/discharge tests from 1.7 to 2.8 V up to 90 cycles and via COMSOL Multiphysics simulation software. No apparent overcharge occurred during the charge state, which suggests that the shuttle effect of polysulfides was effectively prevented. The COMSOL Multiphysics simulation provided a venue for optimal prediction of the ideal concentration and properties of the polymer composite layer to be used in the LISBs. The testing and simulation results determined that the polymer composite layer diminished the amount of lithium polysulfide species and decreased the amount of dissolved lithium ions in the LISBs. In addition, the charge/discharge rate of up to 2.0 C with a cycle life of 90 cycles was achieved. The knowledge acquired in this study was important not only for the design of efficient new electrode materials, but also for understanding the effect of the polymer composite layer on the electrochemical cycle stability.

Scalable Superior Chemical Sensing Performance of Stretchable Ionotronic Skin via a π-Hole Receptor Effect.

Skin-attachable gas sensors provide a next-generation wearable platform for real-time protection of human health by monitoring environmental and physiological chemicals. However, the creation of skin-like wearable gas sensors, possessing high sensitivity, selectivity, stability, and scalability (4S) simultaneously, has been a big challenge. Here, an ionotronic gas-sensing sticker (IGS) is demonstrated, implemented with free-standing polymer electrolyte (ionic thermoplastic polyurethane, i-TPU) as a sensing channel and inkjet-printed stretchable carbon nanotube electrodes, which enables the IGS to exhibit high sensitivity, selectivity, stability (against mechanical stress, humidity, and temperature), and scalable fabrication, simultaneously. The IGS demonstrates reliable sensing capability against nitrogen dioxide molecules under not only harsh mechanical stress (cyclic bending with the radius of curvature of 1 mm and cyclic straining at 50%), but also environmental conditions (thermal aging from -45 to 125 °C for 1000 cycles and humidity aging for 24 h at 85% relative humidity). Further, through systematic experiments and theoretical calculations, a π-hole receptor mechanism is proposed, which can effectively elucidate the origin of the high sensitivity (up to parts per billion level) and selectivity of the ionotronic sensing system. Consequently, this work provides a guideline for the design of ionotronic materials for the achievement of high-performance and skin-attachable gas-sensor platforms.

Analysis of Consumer Exposure Cases for Alcohol-Based Disinfectant and Hand Sanitizer Use against Coronavirus Disease 2019 (COVID-19).

The development and distribution of vaccines and treatments as well as the use of disinfectants and hand sanitizers to cope with coronavirus disease 2019 (COVID-19) infection has increased rapidly. As the use of disinfectants and hand sanitizers increased, the number of unintended exposures to these substances also increased. A total of 8016 cases of toxic exposure to disinfectants and hand sanitizers were reported to the American Association of Poison Control Centers (AAPCC) from 1 January 2017 to 30 May 2021. The cases have been characterized by substance, sex, patient age, exposure reason and site, treatments received, and outcomes. The number of exposures correlates closely to the rise of COVID-19 cases, rising significantly in March 2020. About half of the total cases involved children less than 10 years old and 97% of those exposures per year were unintentional. In addition, the most common exposure site was the patient's own residence. Over-exposure to disinfectants and hand sanitizers can cause symptoms such as burning and irritation of the eyes, nose, and throat, coughing, chest tightness, headache, choking, and, in severe cases, death.

Interpenetrating Polymer Semiconductor Nanonetwork Channel for Ultrasensitive, Selective, and Fast Recovered Chemodetection.

Organic semiconductor (OSC)-based gas detection has attracted considerable attention due to the facile manufacturing process and effective contact with target chemicals at room temperature. However, OSCs intrinsically suffer from inferior sensing and recovery capability due to lack of functional sites and deep gas penetration into the film. Here, we describe an interpenetrating polymer semiconductor nanonetwork (IPSN) channel possessing unreacted silanol (Si-OH) groups on its surface to overcome bottlenecks that come from OSC-based chemodetection. On the top of the IPSN, moreover, we introduced electron-donating amine (NH2) groups as a chemical receptor because they strongly interact with the electron-withdrawing nature of NO2 gas. The NH2-IPSN-based field-effect transistor exhibited high-performance chemodetection such as ultrasensitivity (990% ppm-1 at 5 ppm) and excellent NO2 selectivity against other toxic gases. Impressively, the gas recovery was significantly improved because the NH2 chemical receptors anchored on the surface of the IPSN suppress deep gas penetration into the film. This work demonstrates that our NO2 chemodetection is expected to provide inspiration and guideline for realization of practical gas sensors in various industries and daily life.

Universal three-dimensional crosslinker for all-photopatterned electronics.

All-solution processing of large-area organic electronics requires multiple steps of patterning and stacking of various device components. Here, we report the fabrication of highly integrated arrays of polymer thin-film transistors and logic gates entirely through a series of solution processes. The fabrication is done using a three-dimensional crosslinker in tetrahedral geometry containing four photocrosslinkable azide moieties, referred to as 4Bx. 4Bx can be mixed with a variety of solution-processable electronic materials (polymer semiconductors, polymer insulators, and metal nanoparticles) and generate crosslinked network under exposure to UV. Fully crosslinked network film can be formed even at an unprecedentedly small loading, which enables preserving the inherent electrical and structural characteristics of host material. Because the crosslinked electronic component layers are strongly resistant to chemical solvents, micropatterning the layers at high resolution as well as stacking the layers on top of each other by series of solution processing steps is possible.

Next-Generation Asymmetric Membranes Using Thin-Film Liftoff.

For the past 30 years, thin-film membrane composites have been the state-of-the-art technology for reverse osmosis, nanofiltration, ultrafiltration, and gas separation. However, traditional membrane casting techniques, such as phase inversion and interfacial polymerization, limit the types of material that are used for the membrane separation layer. Here, we describe a novel thin-film liftoff (T-FLO) technique that enables the fabrication of thin-film composite membranes with new materials for desalination, organic solvent nanofiltration, and gas separation. The active layer is cast separately from the porous support layer, allowing for the tuning of the thickness and chemistry of the active layer. A fiber-reinforced, epoxy-based resin is then cured on top of the active layer to form a covalently bound support layer. Upon submersion in water, the cured membrane lifts off from the substrate to produce a robust, freestanding, asymmetric membrane composite. We demonstrate the fabrication of three novel T-FLO membranes for chlorine-tolerant reverse osmosis, organic solvent nanofiltration, and gas separation. The isolable nature of support and active-layer formation paves the way for the discovery of the transport and selectivity properties of new polymeric materials. This work introduces the foundation for T-FLO membranes and enables exciting new materials to be implemented as the active layers of thin-film membranes, including high-performance polymers, two-dimensional materials, and metal-organic frameworks.

Universal Route to Impart Orthogonality to Polymer Semiconductors for Sub-Micrometer Tandem Electronics.

A universal method that enables utilization of conventional photolithography for processing a variety of polymer semiconductors is developed. The method relies on imparting chemical and physical orthogonality to a polymer film via formation of a semi-interpenetrating diphasic polymer network with a bridged polysilsesquioxane structure, which is termed an orthogonal polymer semiconductor gel. The synthesized gel films remain tolerant to various chemical and physical etching processes involved in photolithography, thereby facilitating fabrication of high-resolution patterns of polymer semiconductors. This method is utilized for fabricating tandem electronics, including pn-complementary inverter logic devices and pixelated polymer light-emitting diodes, which require deposition of multiple polymer semiconductors through solution processes. This novel and universal method is expected to significantly influence the development of advanced polymer electronics requiring sub-micrometer tandem structures.

Kerogen Swelling and Confinement: Its implication on Fluid Thermodynamic Properties in Shales.

Type I kerogen was isolated from Green River Shale and characterized using SEM, TGA, DSC, and nitrogen adsorption. The swelling behavior of this kerogen with decane was analyzed using traditional test-tube swelling experiment and Dynamic Light Scattering. The TGA and DSC were used to analyze the thermodynamic behavior of decane that was sorbed in the kerogen and show that kerogen suppresses the boiling point of decane due to the effect of confinement. However, the suppression is larger when oil (a multicomponent mixture) was used, possibly due to the combined effect of differential uptake of components by kerogen (kerogen prefers and sorbs polars and aromatics more than saturates, leading to splitting of oil into a sorbed and a free phase) and confinement in nano pores. Test-tube swelling, TGA, and DSC experiments were also performed on pyridine(polar-aromatic)-swelled kerogen. The combined and individual contributions from the two effects (the effect of confinement and differential uptake of hydrocarbon components) on properties of liquid in contact with kerogen, are studied in this work. Molecular Dynamics (MD) simulations revealed the variation in the swelling of type II kerogen in the presence of same amount of different liquids (differential swelling of kerogen).

Uniform distribution of TiO2 nanocrystals on reduced graphene oxide sheets by the chelating ligands.

Reduced graphene oxide-TiO(2) hybrids were successfully prepared by the hydrothermal approach using triethanolamine and acetylacetone as the chelating agents. Without any additive, large aggregated TiO(2) clusters were randomly distributed dominantly at the edge and less on the basil plane of coagulated reduced graphene oxide (RGO) layers. The presence of chelating ligands remarkably facilitated the selective growth and regular spread of TiO(2) nanocrystals onto individually exfoliated RGO sheet. Such sandwich-like structure with stronger coupling and chemical interaction resulted in the surface area increase, the rearrangement of energy level, the enhanced concentration of oxygen vacancies, leading to much higher adsorbability and photocatalytic degradation of Rhodamine B under both UV and visible irradiations. These RGO-TiO(2) hybrid systems are potentially beneficial for widely practical applications in air/water purification, electronic devices, batteries, solar cells or supercapacitors.