Visualizing Ribbon-to-Ribbon Heterogeneity of Chemically Unzipped Wide Graphene Nanoribbons by Silver Nanowire-Based Tip-Enhanced Raman Scattering Microscopy.

Graphene nanoribbons (GNRs), a quasi-one-dimensional form of graphene, have gained tremendous attention due to their potential for next-generation nanoelectronic devices. The chemical unzipping of carbon nanotubes is one of the attractive fabrication methods to obtain single-layered GNRs (sGNRs) with simple and large-scale production.  The authors recently found that unzipping from double-walled carbon nanotubes (DWNTs), rather than single- or multi-walled, results in high-yield production of crystalline sGNRs. However, details of the resultant GNR structure, as well as the reaction mechanism, are not fully understood due to the necessity of nanoscale spectroscopy. In this regard, silver nanowire-based tip-enhanced Raman spectroscopy (TERS) is applied for single GNR analysis and investigated ribbon-to-ribbon heterogeneity in terms of defect density and edge structure generated through the unzipping process.  The authors found that sGNRs originated from the inner walls of DWNTs showed lower defect densities than those from the outer walls. Furthermore, TERS spectra of sGNRs exhibit a large variety in graphitic Raman parameters, indicating a large variation in edge structures. This work at the single GNR level reveals, for the first time, ribbon-to-ribbon heterogeneity that can never be observed by diffraction-limited techniques and provides deeper insights into unzipped GNR structure as well as the DWNT unzipping reaction mechanism.

Influence of junction resistance on spatiotemporal dynamics and reservoir computing performance arising from an SWNT/POM 3D network formed via a scaffold template technique.

For scientists in numerous fields, creating a physical device that can function like the human brain is an aspiration. It is believed that we may achieve brain-like spatiotemporal information processing by fabricating an in materio reservoir computing (RC) device because of a complex random network topology with nonlinear dynamics. One of the significant drawbacks of a two-dimensional physical reservoir system is the difficulty in controlling the network density. This work reports the use of a 3D porous template as a scaffold to fabricate a three-dimensional network of a single-walled carbon nanotube polyoxometalate nanocomposite. Although the three-dimensional system exhibits better nonlinear dynamics and spatiotemporal dynamics, and higher harmonics generation than a two-dimensional system, the results suggest a correlation between a higher number of resistive junctions and reservoir performance. We show that by increasing the spatial dimension of the device, the memory capacity improves, while the scale-free network exponent (γ) remains nearly unchanged. The three-dimensional device also displays improved performance in the well-known RC benchmark task of waveform generation. This study demonstrates the impact of an additional spatial dimension, network distribution and network density on in materio RC device performance and tries to shed some light on the reason behind such behavior.

In-materio reservoir working at low frequencies in a Ag2S-island network.

A Ag2S-island network is fabricated with surrounding electrodes to enable it to be used as a reservoir for unconventional computing. Local conductance change occurs due to the growth/shrinkage of Ag filaments from/into each Ag2S island in the reservoir. The growth/shrinkage of Ag filaments is caused by the drift of Ag+ cations in each Ag2S island, which results in a unique non-linear response as a reservoir, especially at lower frequencies. The response of the reservoir is shown to depend on the frequency and amplitude of the input signals. So as to evaluate its capability as a reservoir, logical operations were performed using the subject Ag2S-island network, with the results showing an accuracy of greater than 99%.

In-Materio Reservoir Computing in a Sulfonated Polyaniline Network.

A sulfonated polyaniline (SPAN) organic electrochemical network device (OEND) is fabricated using a simple drop-casting method on multiple Au electrodes for use in reservoir computing (RC). The SPAN network has humidity-dependent electrical properties. Under high humidity, the SPAN OEND exhibits mainly ionic conduction, including charging of an electric double layer and ionic diffusion. The nonlinearity and hysteresis of the current-voltage characteristics progressively increase with increasing humidity. The rich dynamic output behavior indicates wide variations for each electrode, which improves the RC performance because of the disordered network. For RC, waveform generation and short-term memory tasks are realized by a linear combination of outputs. The waveform task accuracy and memory capacity calculated from a short-term memory task reach 90% and 33.9, respectively. Improved spoken-digit classification is realized with 60% accuracy by only 12 outputs, demonstrating that the SPAN OEND can manage time series dynamic data operation in RC owing to a combination of rich dynamic and nonlinear electronic properties. The results suggest that SPAN-based electrochemical systems can be applied for material-based computing, by exploiting their intrinsic physicochemical behavior.

Sacrificial gold coating enhances transport of liquid metal in pressurized fountain pen lithography.

Liquid metals have attracted attention as functional components for moldable electronics, such as soft flexible connectors, wires or conductive ink. The relatively high surface tension (> 400 mN m-1) and the fact that liquid metals do not readily wet ceramic or oxide surfaces have led to devising unique techniques to spread the liquid and mold its shape. These techniques include surface modification, electrowetting and vacuum filling of channels. This work presents an injection technique based on pressurized fountain pen lithography with glass nanopipettes developed to directly pattern liquid metal on flat hard substrates. The liquid metals were eutectic alloys of Gallium, including Gallium-Indium (EGaIn), Gallium-Indium-Zinc and Gallium-Indium-Tin. The nanopipettes were coated internally with gold, acting as a sacrificial layer and facilitating the wetting of the pipette down to its pore, with an inner diameter of ~ 100-300 nm. By applying hydrodynamic pressure to the connected end of the pipette, the metal was extruded through the pore, forming long continuous (> 3 mm) and narrow (~ 1-15 µm) metal lines on silicon oxide and gold surfaces at room temperature and ambient conditions. With this robust platform, it is possible to pattern liquid metals on a variety of substrates and geometries down to the micron range.

Visualization of Charge Migration in Conductive Polymers via Time-Resolved Electrostatic Force Microscopy.

Charge dynamics play an important role in numerous natural phenomena and artificial devices, and tracking charge migration and recombination is crucial for understanding the mechanism and function of systems involving charge transfer. Tip-synchronized pump-probe electrostatic force microscopy simultaneously permits highly sensitive detection, microsecond time resolution, and nanoscale spatial resolution, where the spatial distribution in static measurement (usual EFM) reflects differences in the carrier density and the time evolution reveals the surface carrier mobility. By using this method, carrier injection and ejection in sulfonated polyaniline (SPAN) thin films were visualized. Comparison of tr-EFM results of SPAN thin films with different doping levels revealed the individual differences in carrier density and mobility.

Local-field-induced current noise in shape-limited self-doped polyaniline.

Electronic noise generators are an essential component of molecular neuromorphic devices. To realize molecular noise generators with a high degree of freedom for design and integration into molecular devices, the utilization of the local electric field for the modulation of electrical conduction via a shape-limited conductive polymer is one promising strategy. Herein, a molecular noise generator composed of thin self-doped polyaniline (SPAN) lines is reported. SPAN lines fabricated via fountain pen lithography on SiO2/Si substrates were found to generate current noise upon laser irradiation. This current noise exhibited white-noise-like power spectral density in the frequency range of 1-25 Hz and was independent of temperature. Multiple independent noise generation on the same substrate was also successfully demonstrated. The present results indicate that the noise generation mechanism involves the local modulation of hopping conduction via SPAN lines owing to the spatial proximity of the conduction path in the SPAN line to the surface photovoltage region of the SiO2/Si interface. This on-site random noise generation in shape-limited conductive polymers is expected to be beneficial for the realization of molecular neuromorphic devices.

Functional mapping and implications of substrate specificity of the yeast high-affinity leucine permease Bap2.

Leucine is a major amino acid in nutrients and proteins and is also an important precursor of higher alcohols during brewing. In Saccharomyces cerevisiae, leucine uptake is mediated by multiple amino acid permeases, including the high-affinity leucine permease Bap2. Although BAP2 transcription has been extensively analyzed, the mechanisms by which a substrate is recognized and moves through the permease remain unknown. Recently, we determined 15 amino acid residues required for Tat2-mediated tryptophan import. Here we introduced homologous mutations into Bap2 amino acid residues and showed that 7 residues played a role in leucine import. Residues I109/G110/T111 and E305 were located within the putative α-helix break in TMD1 and TMD6, respectively, according to the structurally homologous Escherichia coli arginine/agmatine antiporter AdiC. Upon leucine binding, these α-helix breaks were assumed to mediate a conformational transition in Bap2 from an outward-open to a substrate-binding occluded state. Residues Y336 (TMD7) and Y181 (TMD3) were located near I109 and E305, respectively. Bap2-mediated leucine import was inhibited by some amino acids according to the following order of severity: phenylalanine, leucine>isoleucine>methionine, tyrosine>valine>tryptophan; histidine and asparagine had no effect. Moreover, this order of severity clearly coincided with the logP values (octanol-water partition coefficients) of all amino acids except tryptophan. This result suggests that the substrate partition efficiency to the buried Bap2 binding pocket is the primary determinant of substrate specificity rather than structural amino acid side chain recognition.

Significance of cervical ripening in pre-induction treatment for premature rupture of membranes at term.

AIM: This study aimed to determine whether mechanical cervical dilatation with a laminaria tent in women with premature rupture of membranes (PROM) at term may influence the maternal/neonatal outcomes. METHODS: We reviewed the medical records and histopathologic results of the placenta in 782 women with PROM at term. Of the 486 women seen prior to 2010 (group 1), 85 had Bishop scores of 5 or less and underwent insertion of laminaria tents (group A). In the 296 women admitted after 2010 (group 2), 27 had Bishop scores of 5 or less and underwent labor management without insertion of laminaria tents (group B). The patient characteristics, delivery course and neonatal outcomes were compared between the groups. RESULTS: There were no significant differences in the maternal age, percentage of nulliparas, body mass index, gestational age at delivery or Bishop score between the groups. The Bishop score improved from 2.5 to 6.1 after laminaria tent insertion in group A. However, there were no significant intergroup differences in the frequency of use of labor-inducing agents or the time interval from PROM to delivery. The incidence of clinical/pathological chorioamnionitis was not higher in group A than in group B. No significant differences were found in the Apgar scores, umbilical artery pH or frequency of asphyxia neonatorum between the groups. Mechanical cervical dilatation by laminaria tent insertion neither increased the incidence of infection nor contributed to improvement of the perinatal prognosis. CONCLUSION: Mechanical cervical dilatation does not provide any benefit for women with PROM at term.