Base-Catalyzed One-Pot Synthesis of Selenosulfides: A Base Basicity-Controlled Approach.

We developed a novel and efficient sequential one-pot synthesis of selenosulfides via a base-catalyzed methodology utilizing readily available starting compounds, under mild reaction conditions. This method eliminated the need for excess oxidants or additives and simplified the synthesis procedure. Furthermore, organic amine bases served as exceptional catalysts for synthesizing the target products. The performance of a catalytic system depends on the basicity of the bases. The selection of suitable bases, based on their pKaH values, is crucial for the selective synthesis of selenosulfides without the formation of byproducts. This method provides a direct route for the preparation of selenosulfides, which are important scaffolds in organic chemistry.

Enhanced Performance of Field-Effect Transistors Based on Black Phosphorus Channels Reduced by Galvanic Corrosion of Al Overlayers.

Two-dimensional (2D)-layered semiconducting materials with considerable band gaps are emerging as a new class of materials applicable to next-generation devices. Particularly, black phosphorus (BP) is considered to be very promising for next-generation 2D electrical and optical devices because of its high carrier mobility of 200-1000 cm2 V-1 s-1 and large on/off ratio of 104 to 105 in field-effect transistors (FETs). However, its environmental instability in air requires fabrication processes in a glovebox filled with nitrogen or argon gas followed by encapsulation, passivation, and chemical functionalization of BP. Here, we report a new method for reduction of BP-channel devices fabricated without the use of a glovebox by galvanic corrosion of an Al overlayer. The reduction of BP induced by an anodic oxidation of Al overlayer is demonstrated through surface characterization of BP using atomic force microscopy, Raman spectroscopy, and X-ray photoemission spectroscopy along with electrical measurement of a BP-channel FET. After the deposition of an Al overlayer, the FET device shows a significantly enhanced performance, including restoration of ambipolar transport, high carrier mobility of 220 cm2 V-1 s-1, low subthreshold swing of 0.73 V/decade, and low interface trap density of 7.8 × 1011 cm-2 eV-1. These improvements are attributed to both the reduction of the BP channel and the formation of an Al2O3 interfacial layer resulting in a high- k screening effect. Moreover, ambipolar behavior of our BP-channel FET device combined with charge-trap behavior can be utilized for implementing reconfigurable memory and neuromorphic computing applications. Our study offers a simple device fabrication process for BP-channel FETs with high performance using galvanic oxidation of Al overlayers.

Brownmillerite thin films as fast ion conductors for ultimate-performance resistance switching memory.

An oxide-based resistance memory is a leading candidate to replace Si-based flash memory as it meets the emerging specifications for future memory devices. The non-uniformity in the key switching parameters and low endurance in conventional resistance memory devices are preventing its practical application. Here, a novel strategy to overcome the aforementioned challenges has been unveiled by tuning the growth direction of epitaxial brownmillerite SrFeO2.5 thin films along the SrTiO3 [111] direction so that the oxygen vacancy channels can connect both the top and bottom electrodes rather directly. The controlled oxygen vacancy channels help reduce the randomness of the conducting filament (CF). The resulting device displayed high endurance over 106 cycles, and a short switching time of ∼10 ns. In addition, the device showed very high uniformity in the key switching parameters for device-to-device and within a device. This work demonstrates a feasible example for improving the nanoscale device performance by controlling the atomic structure of a functional oxide layer.

Flexible resistive random access memory devices by using NiO x /GaN microdisk arrays fabricated on graphene films.

We report flexible resistive random access memory (ReRAM) arrays fabricated by using NiO x /GaN microdisk arrays on graphene films. The ReRAM device was created from discrete GaN microdisk arrays grown on graphene films produced by chemical vapor deposition, followed by deposition of NiO x thin layers and Au metal contacts. The microdisk ReRAM arrays were transferred to flexible plastic substrates by a simple lift-off technique. The electrical and memory characteristics of the ReRAM devices were investigated under bending conditions. Resistive switching characteristics, including cumulative probability, endurance, and retention, were measured. After 1000 bending repetitions, no significant change in the device characteristics was observed. The flexible ReRAM devices, constructed by using only inorganic materials, operated reliably at temperatures as high as 180 °C.

Synaptic Plasticity Selectively Activated by Polarization-Dependent Energy-Efficient Ion Migration in an Ultrathin Ferroelectric Tunnel Junction.

Selectively activated inorganic synaptic devices, showing a high on/off ratio, ultrasmall dimensions, low power consumption, and short programming time, are required to emulate the functions of high-capacity and energy-efficient reconfigurable human neural systems combining information storage and processing ( Li et al. Sci. Rep. 2014 , 4 , 4096 ). Here, we demonstrate that such a synaptic device is realized using a Ag/PbZr0.52Ti0.48O3 (PZT)/La0.8Sr0.2MnO3 (LSMO) ferroelectric tunnel junction (FTJ) with ultrathin PZT (thickness of ∼4 nm). Ag ion migration through the very thin FTJ enables a large on/off ratio (107) and low energy consumption (potentiation energy consumption = ∼22 aJ and depression energy consumption = ∼2.5 pJ). In addition, the simple alignment of the downward polarization in PZT selectively activates the synaptic plasticity of the FTJ and the transition from short-term plasticity to long-term potentiation.

Accurate and Precise Determination of Mechanical Properties of Silicon Nitride Beam Nanoelectromechanical Devices.

Accurate and precise determination of mechanical properties of nanoscale materials is mandatory since device performances of nanoelectromechanical systems (NEMS) are closely related to the flexural properties of the materials. In this study, the intrinsic mechanical properties of highly stressed silicon nitride (SiN) beams of varying lengths are investigated using two different techniques: Dynamic flexural measurement using optical interferometry and quasi-static flexural measurement using atomic force microscopy. The resonance frequencies of the doubly clamped, highly stressed beams are found to be inversely proportional to their length, which is not usually observed from a beam but is expected from a string-like structure. The mass density of the SiN beams can be precisely determined from the dynamic flexural measurements by using the values for internal stress and Young's modulus determined from the quasi-static measurements. As a result, the mass resolution of the SiN beam resonators was predicted to be a few attograms, which was found to be in excellent agreement with the experimental results. This work suggests that accurate and precise determination of mechanical properties can be achieved through combined flexural measurement techniques, which is a crucial key for designing practical NEMS applications such as biomolecular sensors and gas detectors.

Direct Observation of Domain Motion Synchronized with Resistive Switching in Multiferroic Thin Films.

The room-temperature resistive switching characteristics of ferroelectric, ferroelastic, and multiferroic materials are promising for application in nonvolatile memory devices. These resistive switching characteristics can be accompanied by a change in the ferroic order parameters via applied external electric and magnetic excitations. However, the dynamic evolution of the order parameters between two electrodes, which is synchronized with resistive switching, has rarely been investigated. In this study, for the first time, we directly monitor the ferroelectric/ferroelastic domain switching dynamics between two electrodes in multiferroic BiFeO3 (BFO) planar devices, which cause resistive switching, using piezoresponse force microscopy. It is demonstrated that the geometrical relationship between the ferroelectric domain and electrode in BFO planar capacitors with only 71° domain walls significantly affects both the ferroelectric domain dynamics and the resistive switching. The direct observation of domain dynamics relevant to resistive switching in planar devices may pave the way to a controllable combination of ferroelectric characteristics and resistive switching in multiferroic materials.

Real-time device-scale imaging of conducting filament dynamics in resistive switching materials.

ReRAM is a compelling candidate for next-generation non-volatile memory owing to its various advantages. However, fluctuation of operation parameters are critical weakness occurring failures in 'reading' and 'writing' operations. To enhance the stability, it is important to understand the mechanism of the devices. Although numerous studies have been conducted using AFM or TEM, the understanding of the device operation is still limited due to the destructive nature and/or limited imaging range of the previous methods. Here, we propose a new hybrid device composed of ReRAM and LED enabling us to monitor the conducting filament (CF) configuration on the device scale during resistive switching. We directly observe the change in CF configuration across the whole device area through light emission from our hybrid device. In contrast to former studies, we found that minor CFs were formed earlier than major CF contributing to the resistive switching. Moreover, we investigated the substitution of a stressed major CF with a fresh minor CF when large fluctuation of operation voltage appeared after more than 50 times of resistive switching in atmospheric condition. Our results present an advancement in the understanding of ReRAM operation mechanism, and a step toward stabilizing the fluctuations in ReRAM switching parameters.

Enhancement of resistive switching under confined current path distribution enabled by insertion of atomically thin defective monolayer graphene.

Resistive random access memory (ReRAM) devices have been extensively investigated resulting in significant enhancement of switching properties. However fluctuations in switching parameters are still critical weak points which cause serious failures during 'reading' and 'writing' operations of ReRAM devices. It is believed that such fluctuations may be originated by random creation and rupture of conducting filaments inside ReRAM oxides. Here, we introduce defective monolayer graphene between an oxide film and an electrode to induce confined current path distribution inside the oxide film, and thus control the creation and rupture of conducting filaments. The ReRAM device with an atomically thin interlayer of defective monolayer graphene reveals much reduced fluctuations in switching parameters compared to a conventional one. Our results demonstrate that defective monolayer graphene paves the way to reliable ReRAM devices operating under confined current path distribution.

Ultra-thin resistive switching oxide layers self-assembled by field-induced oxygen migration (FIOM) technique.

High-performance ultra-thin oxide layers are required for various next-generation electronic and optical devices. In particular, ultra-thin resistive switching (RS) oxide layers are expected to become fundamental building blocks of three-dimensional high-density non-volatile memory devices. Until now, special deposition techniques have been introduced for realization of high-quality ultra-thin oxide layers. Here, we report that ultra-thin oxide layers with reliable RS behavior can be self-assembled by field-induced oxygen migration (FIOM) at the interface of an oxide-conductor/oxide-insulator or oxide-conductor/metal. The formation via FIOM of an ultra-thin oxide layer with a thickness of approximately 2-5 nm and 2.5% excess oxygen content is demonstrated using cross-sectional transmission electron microscopy and secondary ion mass spectroscopy depth profile. The observed RS behavior, such as the polarity dependent forming process, can be attributed to the formation of an ultra-thin oxide layer. In general, as oxygen ions are mobile in many oxide-conductors, FIOM can be used for the formation of ultra-thin oxide layers with desired properties at the interfaces or surfaces of oxide-conductors in high-performance oxide-based devices.

Anti-Arthritic and Analgesic Effect of NDI10218, a Standardized Extract of Terminalia chebula, on Arthritis and Pain Model.

The fruit of Terminalia chebula Retzius has been used as a panacea in India and Southeast Asia but its biological activities have not been fully elucidated. Here we report anti-arthritic and analgesic effect of NDI10218, a standardized ethanol extract of Terminalia chebula, on collagen-induced arthritis and acetic acid-induced writhing model, respectively. Arthritis was induced in DBA/1J mice by immunizing bovine type II collagen and mice were treated with NDI10218 daily for 5 weeks after the onset of the disease. NDI10218 reduced the arthritis index and blocked the synovial hyperplasia in a dose-dependent manner. The serum levels of pro-inflammatory cytokines TNF-α, IL-6, and IL-1ß were significantly reduced in mice treated with NDI10218. Production of the inflammatory IL-17, but not immunosuppressive IL-10, was also inhibited in splenocytes isolated from NDI10218-treated arthritis mice. Administration of NDI10218 markedly decreased the number of T cell subpopulations in the regional lymph nodes of the arthritis mice. Finally, NDI10218 reduced the number of abdominal contractions in acetic acid-induced writhing model, suggesting an analgesic effect of this extract. Taken together, these results suggest that NDI10218 can be a new therapeutic candidate for the treatment of rheuma-toid arthritis.

Screening and isolation of a natural dopamine D1 receptor antagonist using cell-based assays.

To develop a cell-based assay to screen for human dopamine D(1) receptor agonists or antagonists from medicinal plant extracts, a stable Chinese hamster ovary (CHO) cell line (CHO-D1R) expressing the human dopamine D(1) receptor was established using an expression vector containing a scaffold attachment region (SAR) element. CHO-D1R cells showed specific binding to [(3)H]-SCH23390 with high affinity (K(d)=1.47+/-0.17 nM) and dose-dependent responses for the dopamine-mediated stimulation of cAMP concentrations (EC(50)=20.6+/-1.44 nM). The screening of medicinal plant extracts using cell-based cAMP assays revealed that an extract of Gleditsia sinensis Lam., which is known to be rich in saponin, had strong antagonist activity for the D(1) receptor. From the activity-guided fractionation and chemical structural analysis of the G. sinensis extract, a compound called gleditsioside F was isolated and was identified to have antagonist activity for the D(1) receptor. Gleditsioside F showed very effective D(1) antagonist activity by inhibiting ligand binding to the D(1) receptor as well as by inhibiting dopamine-mediated increases in cAMP concentration.

Shengmai-san-mediated enhancement of regenerative responses of spinal cord axons after injury in rats.

Shengmai-san (SMS) is a traditional Chinese medicine used to treat diverse symptoms including cardiovascular and neurological disorders. Here we investigated the effects of SMS on regenerative responses of spinal cord axons in rats that were given contusion injury at the lower thoracic level. The injury cavity was confined to a restricted area by SMS treatment, and the signals of glial scar protein chondroitin sulphate proteoglycan (CSPG) and inflammatory cell marker protein CD11beta were heavily observed within the injury cavity in SMS-treated animals. Anterograde tracing of DiI-labeled corticospinal tract (CST) axons revealed increases in collateral arborization around and within the injury cavity and caudal elongation by SMS treatment. Furthermore, SMS treatment facilitated neurite elongation of dorsal root ganglion (DRG) sensory neurons that were co-cultured with non-neuronal cells prepared from injured spinal cord. Phospho-Erk1/2 was strongly induced in both spinal cord and motor cortical areas after spinal cord injury (SCI), and it was further unregulated in the motor cortex by SMS treatment. In contrast, upregulation of cell division cycle 2 (Cdc2) production by SMS treatment was limited to a local, SCI area. These data suggest that SMS may play an active role in regenerative responses and facilitate axonal regrowth after SCI.

Immune-suppressive activity of punicalagin via inhibition of NFAT activation.

Since T cell activation is central to the development of autoimmune diseases, we screened a natural product library comprising 1400 samples of medicinal herbal extracts, to identify compounds that suppress T cell activity. Punicalagin (PCG) isolated from the fruit of Punica granatum was identified as a potent immune suppressant, based on its inhibitory action on the activation of the nuclear factor of activated T cells (NFAT). PCG downregulated the mRNA and soluble protein expression of interleukin-2 from anti-CD3/anti-CD28-stimulated murine splenic CD4+ T cells and suppressed mixed leukocytes reaction (MLR) without exhibiting cytotoxicity to the cells. In vivo, the PCG treatment inhibited phorbol 12-myristate 13-acetate (PMA)-induced chronic ear edema in mice and decreased CD3+ T cell infiltration of the inflamed tissue. These results suggest that PCG could be a potential candidate for the therapeutics of various immune pathologies.

Suppression of the onset and progression of collagen-induced arthritis by chebulagic acid screened from a natural product library.

OBJECTIVE: Chebulagic acid (CHE) from the immature seeds of Terminalia chebula was identified from a natural product library as a potent suppressor of T cell activity. This study examined the effectiveness of CHE against the onset and progression of collagen-induced arthritis (CIA) in mice. METHODS: Arthritis was induced in DBA/1J mice by subcutaneous immunization with bovine type II collagen on days 0 and 21. CHE was administered intraperitoneally for 3 weeks, either as prophylaxis (10 or 20 mg/kg) before disease onset or as therapy (20 mg/kg) after disease onset. Clinical scores, serum antibody levels, and cytokines were measured, and flow cytometric analysis and real-time reverse transcription-polymerase chain reaction were performed to evaluate the knee joints of mice with CIA. RESULTS: In both the prophylactic and therapeutic CHE dosing models, all clinical scores, serum levels of total and anticollagen IgG, and levels of interleukin-10 (IL-10) and IL-6 were reduced, while serum levels of transforming growth factor beta (TGFbeta) were markedly elevated. The number of granulocytes was reduced, but the proportion of CD4+,CD25+ T cells was greater in the knee joints of CHE-treated CIA mice. Expression of Foxp3 and TGFbeta messenger RNA was also augmented significantly in the knee joints of CHE-treated CIA mice in the therapeutic dosing model. CONCLUSION: CHE significantly suppressed the onset and progression of CIA in mice. Immune suppression via the induction of TGFbeta and CD4+,CD25+ T cells may represent a new strategy in the development of therapies for managing rheumatoid arthritis and other inflammatory diseases.