Iontronic analog of synaptic plasticity: Hydrogel-based ionic diode with chemical precipitation and dissolution.

In this study, an aqueous nonlinear synaptic element showing plasticity behavior is developed, which is based on the chemical processes in an ionic diode. The device is simple, fully ionic, and easily configurable, requiring only two terminals-for input and output-similar to biological synapses. The key processes realizing the plasticity features are chemical precipitation and dissolution, which occur at forward- or reverse-biased ionic diode junctions in appropriate reservoir electrolytes. Given that the precipitate acts as a physical barrier in the circuit, the above processes change the diode conductivity, which can be interpreted as adjusting "synaptic weight" of the system. By varying the operating conditions, we first demonstrate the four types of plasticity that can be found in biological system: long-term potentiation/depression and short-term potentiation/depression. The plasticity of the proposed iontronic device has characteristics similar to those of neural synapses. To demonstrate its potential use in comparatively complex information processing, we develop a precipitation-based iontronic synapse (PIS) capable of both potentiation and depression. Finally, we show that the postsynaptic signals from the multiple excitatory or inhibitory PISs can be integrated into the total "dendritic" current, which is a function of time and input history, as in actual hippocampal neural circuits.

Anti-Photoaging Effect of Hydrolysates from Pacific Whiting Skin via MAPK/AP-1, NF-κB, TGF-ß/Smad, and Nrf-2/HO-1 Signaling Pathway in UVB-Induced Human Dermal Fibroblasts.

Chronic exposure to ultraviolet (UV) light promotes the breakdown of collagen in the skin and disrupts the extracellular matrix (ECM) structure, leading to skin wrinkling. Pacific whiting (Merluccius productus) is a fish abundant on the Pacific coast. In the current study, we investigated the anti-wrinkle effect of hydrolysate from Pacific whiting skin gelatin (PWG) in UVB-irradiated human dermal fibroblasts and the molecular mechanisms involved. PWG effectively restored type 1 procollagen synthesis reduced by UVB-irradiation. Also, we found that PWG inhibited collagen degradation by inhibiting MMP1 expression. Furthermore, PWG decreased cytokines TNF-α, IL-6, and IL-1ß associated with inflammatory responses and increased antioxidant enzymes, HO-1, SOD, GPx, CAT, and GSH content, a defense system against oxidative stress. In terms of molecular mechanisms, PWG increased collagen synthesis through activating the transforming growth factor ß (TGF-ß)/Smad pathway and decreased collagen degradation through inhibiting the mitogen-activated protein kinases/activator protein 1 (MAPK/AP-1) pathway. It also suppressed the inflammatory response through suppressing the nuclear factor-κB (NF-κB) pathway and increased antioxidant enzyme activity through activating the nuclear factor erythroid 2/heme oxygenase 1 (Nrf-2/HO-1) pathway. These multi-target mechanisms suggest that PWG may serve as an effective anti-photoaging material.

Inverted Ion Current Rectification-Based Chemical Delivery Probes for Stimulation of Neurons.

Ion current rectification (ICR), diodelike behavior in surface-charged nanopores, shows promise in the design of delivery probes for manipulation of neural networks as it can solve diffusive leakages that might be critical in clinical and research applications. However, it has not been achieved because ICR has restrictions in nanosized dimension and low electrolyte concentration, and rectification direction is inappropriate for delivery. Herein, we present a polyelectrolyte gel-filled (PGF) micropipette harnessing inverted ICR as a delivery probe, which quantitatively transports glutamate to stimulate primary cultured neurons with high efficiency while minimizing leakages. Since the gel works as an ensemble of numerous surface-charged nanopores, the current is rectified in the micro-opening and physiological environment. By extending the charge-selective region using the gel, inverted ICR is generated, which drives outward deliveries of major charge carriers. This study will help in exploring new aspects of ICR and broaden its applications for advanced chemical delivery.

Hydrogel-Based Iontronics on a Polydimethylsiloxane Microchip.

In response to the extensive utilization of ionic circuits, including in iontronics and wearable devices, a new method for fabricating a hydrogel-based ionic circuit on a polydimethylsiloxane (PDMS) microchip is reported. Prolonged UV/ozone oxidation combined with proper surface functionalizations and a novel microchip bonding method using thiol-epoxy click reaction enable the robust attachment of the photopolymerized hydrogel to the microchannel surface for eventual operation in electrolytes as an ionic circuit. The stretchable ionic diode constructed on the PDMS microchip shows a superior rectification ratio even under tensile stress and long-term storage stability. Furthermore, the combination of the ionic circuit and unique material properties of PDMS allows us to maximize the versatility and diversify the functionalities of the iontronic device, as demonstrated in a pressure-driven ionic switch and chip-integrated ionic regulator. Its iontronic signal transmission mimicking the excitatory and inhibitory synapses also evinces the potential of the hydrogel-based iontronics on the PDMS microchip as developed toward an aqueous neuromimetic information processor while opening up new opportunities for various bioinspired applications.

In Situ Real-Time Monitoring of ITO Film under a Chemical Etching Process Using Fourier Transform Electrochemical Impedance Spectroscopy.

As a novel approach to the in situ real-time investigation of an ITO electrode during the wet etching process, step-excitation Fourier-transform electrochemical impedance spectroscopy (FT-EIS) was implemented. The equivalent circuit parameters (e.g., Rct, Cdl) continuously obtained by the FT-EIS measurements during the entire etching process showed an electrode activation at the initial period as well as the completion of etching. The FT-EIS results were further validated by cyclic voltammograms and impedance measurements of partially etched ITO films using ferri- and ferrocyanide solution in combination with FESEM imaging, EDS, XRD analyses, and COMSOL simulation. We also demonstrated that this technique can be further utilized to obtain intact interdigitated array (IDA) electrodes in a reproducible manner, which is generally considered to be quite tricky due to delicacy of the pattern. Given that the FT-EIS allows for instantaneous snapshots of the electrode at every moment, this work may hold promise for in situ real-time examination of structural, electrokinetic, or mass transfer-related information on electrochemical systems undergoing constantly changing, transient processes including etching, which would be impossible with conventional electroanalytical techniques.

Effects of Azole Fungicides on Secreted Metabolomes of Botrytis cinerea.

Botrytis cinerea, gray mold, is one of the most notorious phytopathgens, causing serious economic loss in the agricultural industry. The phytotoxic effects are mainly derived from secreted virulence proteins and terpenoid-type secondary metabolites. Azole fungicides are commonly used to manage the disease. However, their biochemical effects other than sterol biosynthesis were not documented, especially toxic secreted metabolites. In this study, six azole fungicides were treated with in vitro and in vivo conditions. Comprehensive profiles of primary and secondary metabolites in culture media were evaluated to assess the fungal metabolomes under pesticide-stressed conditions. The results indicated that extensive metabolic differentiation was induced by azole fungicides. Epoxiconazole clearly reduced the extracellular phytotoxin concentrations, while the level of indole-3-acetic acid was increased. In addition, significant differentiation of primary metabolism could be deduced from secreted metabolite profiles, including the tricarboxylic acid cycle and aromatic amino acid catabolism. Cellular lipid profiles, including fatty acids and sterol, have been altered drastically by azoles, which indicate extensive changes of cellular lipid metabolism. These system-wide metabolic alterations resulted in reduced plant damages, proven by the in vivo assay with tomato. Overall, azole fungicides induced significant changes of endo- and exometabolomes and could reduce the fungal infection. The experimental results will provide a more detailed understanding of physiological changes of phytopathogens under pesticide treatment and information for new pesticide development.

Ion-to-ion amplification through an open-junction ionic diode.

As biological signals are mainly based on ion transport, the differences in signal carriers have become a major issue for the intimate communication between electrical devices and biological areas. In this respect, an ionic device which can directly interpret ionic signals from biological systems needs to be designed. Particularly, it is also required to amplify the ionic signals for effective signal processing, since the amount of ions acquired from biological systems is very small. Here, we report the signal amplification in ionic systems as well as sensing through the modified design of polyelectrolyte hydrogel-based ionic diodes. By designing an open-junction structure, ionic signals from the external environment can be directly transmitted to an ionic diode. Moreover, the minute ionic signals injected into the devices can also be amplified to a large amount of ions. The signal transduction mechanism of the ion-to-ion amplification is suggested and clearly verified by revealing the generation of breakdown ionic currents during an ion injection. Subsequently, various methods for enhancing the amplification are suggested.

Long-Term Efficacy of Mirabegron Add-On Therapy to Antimuscarinic Agents in Patients With Spinal Cord Injury.

OBJECTIVE: To evaluate the long-term efficacy of mirabegron add-on therapy in patients with spinal cord injury (SCI) based on an urodynamic study. METHODS: This retrospective study involved a chart audit of individuals with SCI who underwent two consecutive urodynamic studies between April 1, 2015 and April 1, 2018. After adding 50 mg of mirabegron once a day to the pre-existing antimuscarinic therapy for a period of, at least 6 months, the following variables were analyzed: change in cystometric capacity, change in bladder compliance, change in maximal detrusor pressure, change in reflex volume, and presence of significant leakage during filling cystometry. RESULTS: A total of 31 participants with a mean age of 41±15 years were included in the analysis. A significant increase in cystometric capacity (mean, 362 to 424 mL; p=0.03), reflex volume (mean, 251 to 329 mL; p=0.02), and bladder compliance (median, 12 to 18 mL/cmH2O; p=0.04) was observed. The presence of leakage during filling cystometry was significantly reduced (29% to 10%; p=0.03). Likewise, a non-significant decrease in the change in maximal detrusor pressure was observed (mean, 31 to 27 cmH2O; p=0.39). CONCLUSION: Adding mirabegron to conventional antimuscarinics further improved urodynamic parameters in patients with chronic SCI, and sustained efficacy was observed in long-term use.

A miniaturized solid salt reverse electrodialysis battery: a durable and fully ionic power source.

A novel pump-free miniaturized reverse electrodialysis (RED) system was designed to provide lasting power transduced from salinity gradients, named solid salt RED (ssRED), and this quasi-battery uses a solid salt instead of electrolyte solution for streamlined usage. It is portable, flexible, comparable in size to a universal serial bus flash drive, and easily activated with a small amount of water. It maintains a constant ionic concentration gradient through precipitation reactions between a pair of different salts. This precipitation-assisted solid salt RED (PssRED) is an unprecedented ionic power source as it can generate steady electricity in the absence of a driving pump. The PssRED was successfully coupled with bipolar electrode (BPE) microchip sensors which require stable ionic electricity and a polyelectrolyte ionic diode to realize a fully ionic circuit. It is envisioned that the range of application could be expanded to supply electromotive force to various devices through an ionic charge flow.

Miniaturized Reverse Electrodialysis-Powered Biosensor Using Electrochemiluminescence on Bipolar Electrode.

We suggest an electrochemiluminescence (ECL)-sensing platform driven by ecofriendly, disposable, and miniaturized reverse electrodialysis (RED) patches as an electric power source. The flexible RED patches composed of ion-exchange membranes (IEMs) can produce voltage required for ECL sensing by simply choosing the appropriate number of IEMs and the ratio of salt concentrations. We integrate the RED patch with a bipolar electrode on the microfluidic chip to demonstrate the proof-of-concept, i.e., glucose detection in the range of 0.5-10 mM by observing ECL emissions with naked eyes. The miniaturized RED-powered biosensing system is widely applicable for electrochemical-sensing platforms. This is expected to be a solution for practical availability of battery-free electrochemical sensors for disease diagnosis in developing countries.

Dielectric Breakdown and Post-Breakdown Dissolution of Si/SiO2 Cathodes in Acidic Aqueous Electrochemical Environment.

Understanding the conducting mechanisms of dielectric materials under various conditions is of increasing importance. Here, we report the dielectric breakdown (DB) and post-breakdown mechanism of Si/SiO2, a widely used semiconductor and dielectric, in an acidic aqueous electrochemical environment. Cathodic breakdown was found to generate conduction spots on the Si/SiO2 surface. Using scanning electrochemical microscopy (SECM), the size and number of conduction spots are confirmed to increase from nanometer to micrometer scale during the application of negative voltage. The morphologies of these conduction spots reveal locally recessed inverted-pyramidal structures with exposed Si{111} sidewalls. The pits generation preceded by DB is considered to occur via cathodic dissolution of Si and exfoliation of SiO2 that are induced by local pH increases due to the hydrogen evolution reaction (HER) at the conduction spots. The HER at the conduction spots is more sluggish due to strongly hydrogen-terminated Si{111} surfaces.

3D interdigitated electrode array in the microchannel free of reference and counter electrodes.

We demonstrate the three-dimensional (3D) interdigitated array (IDA) chip that operates without reference and counter electrodes, which are necessary components to apply enough potential to trigger the intended redox process, but used unwieldy for chip-based electrochemical detection. Using the electrode configuration, we propose a unique electrochemical system that is capable of controlling applied potential to a pair of working electrodes despite absence of reference and counter electrodes by fixing the electron transfer mediator on the electrodes in a microchannel. The electrochemical potential of the 2-electrode (2E) system is defined by the potential of the electron transfer mediator, poly(methylene green) (PMG), immobilized with poly(dopamine) (PDA) on the ITO surface by electropolymerization. The 3D IDA chip in the 2E system successfully acts as an electrochemical immunosensing platform. Creatine Kinase-MB in human serum was measured down to ~ pg / mL level. Therefore, the 3D IDA in the 2E system constitutes a simple and scalable platform that needs only nL level of sample volume for sensitive electrochemical detection in miniaturized multiplex immunoassay field.

Ionic Circuits Powered by Reverse Electrodialysis for an Ultimate Iontronic System.

Despite numerous reports on iontronic devices, there has been no whole circuit working in aqueous media including even power source. Herein, we introduce complete ionic circuits powered by reverse electrodialysis (RED) for the first time without employing any electronic components. The RED-driven polyelectrolyte diode successfully shows rectification behavior which is verified by monitoring dynamic ion distribution through fluorescence in real-time. We can also turn on and off the voltage applied to the circuit, and apply an arbitrary voltage by precisely manipulating the pressure imposed to an elastic connection tube filled with electrolyte. Furthermore, this new concept containing ionic power source advances to a more sophisticated ionic OR logic gate. The proposed system paves the way to develop not only passive iontronic devices (e.g. current ionic diode), but active ones requiring a source of energy, particularly such as a neuron-like information processor powered by fully ionic systems, and thereby aqueous computers.

Prosody processing of korean language in stroke patients: a preliminary study.

OBJECTIVE: To investigate the hemispheric contributions to prosody recognitions and interference effects of semantic processing on prosody for stroke patients by using the Korean language. METHODS: Ten right hemisphere damaged patients (RHD), nine left hemisphere damaged patients (LHD), and eleven healthy controls (HC) participated. In pure prosody recognition task, four semantically neutral sentences were selected and presented in both sad and happy prosodies. In interference task, participants listened to emotionally intoned sentences in which the semantic contents were congruent or incongruent with prosody. Participants were asked to rate the valence of prosody while ignoring the semantic contents, and thus, reaction time and accuracy were estimated. RESULTS: In pure prosody recognition task, RHD showed low accuracy as compared to HC (p=0.013), and the tendency of group response showed that RHD performed worse than HC and LHD with regards to accuracy and reaction time. In interference task, analysis of accuracy revealed a significant main effect of groups (p=0.04), and the tendency implied that RHD is less accurate as compared to LHD and HC. The RHD took longer reaction times than HC in congruent and incongruent items (p<0.001). CONCLUSION: Right hemispheric laterality to prosody processing of Korean language in stroke patients was observed. Interference effects of semantic contents to prosody processing were not observed, which suggested unique characteristics of prosody for Korean language. These results could be referred as preliminary data for future researches on Korean languages.