Scanning probe analysis of twisted graphene grown on a graphene/silicon carbide template.

Overlayer growth of graphene on an epitaxial graphene/silicon carbide (SiC) as a solid template by ethanol chemical vapor deposition is performed over a wide growth temperature range from 900 °C to 1450 °C. Structural analysis using atomic force and scanning tunneling microscopies reveal that graphene islands grown at 1300 °C form hexagonal twisted bilayer graphene as a single crystal. When the growth temperature exceeds 1400 °C, the grown graphene islands show a circular shape. Moreover, moiré patterns with different periods are observed in a single graphene island. This means that the graphene islands grown at high temperature are composed of several graphene domains with different twist angles. From these results, we conclude that graphene overlayer growth on the epitaxial graphene/SiC solid at 1300 °C effectively synthesizes the twisted few-layer graphene with a high crystallinity.

Prominent luminescence of silicon-vacancy defects created in bulk silicon carbide p-n junction diodes.

We investigate fluorescent defect centers in 4H silicon carbide p-n junction diodes fabricated via aluminum-ion implantation into an n-type bulk substrate without the use of an epitaxial growth process. At room temperature, electron-irradiated p-n junction diodes exhibit electroluminescence originating from silicon-vacancy defects. For a diode exposed to an electron dose of [Formula: see text] at [Formula: see text], the electroluminescence intensity of these defects is most prominent within a wavelength range of 400-[Formula: see text]. The commonly observed [Formula: see text] emission was sufficiently suppressed in the electroluminescence spectra of all the fabricated diodes, while it was detected in the photoluminescence measurements. The photoluminescence spectra also displayed emission lines from silicon-vacancy defects.

Self-Folded Three-Dimensional Graphene with a Tunable Shape and Conductivity.

Three-dimensional (3D) graphene architectures are of great interest as applications in flexible electronics and biointerfaces. In this study, we demonstrate the facile formation of predetermined 3D polymeric microstructures simply by transferring monolayer graphene. The graphene adheres to the surface of polymeric films via noncovalent π-π stacking bonding and induces a sloped internal strain, leading to the self-rolling of 3D microscale architectures. Micropatterns and varied thicknesses of the 2D films prior to the self-rolling allows for control over the resulting 3D geometries. The strain then present on the hexagonal unit cell of the graphene produces a nonlinear electrical conductivity across the device. The driving force behind the self-folding process arises from the reconfiguration of the molecules within the crystalline materials. We believe that this effective and versatile way of realizing a 3D graphene structure is potentially applicable to alternative 2D layered materials as well as other flexible polymeric templates.

Direct growth of graphene on SiC(0001) by KrF-excimer-laser irradiation.

In this report, we propose a direct patterning method of graphene on the SiC(0001) surface by KrF-excimer-laser irradiation. In this method, Si atoms are locally sublimated from the SiC surface in the laser-irradiated area, and direct graphene growth is induced by the rearrangement of surplus carbon on the SiC surface. Using Raman microscopy, we demonstrated the formation of graphene by laser irradiation and observed the growth process by transmission electron microscopy and conductive atomic force microscopy. When SiC was irradiated by 5000 shots of the laser beam with a fluence of 1.2 J/cm2, two layers of graphene were synthesized on the SiC(0001) surface. The number of graphene layers increased from 2 to 5-7 with an increase in the number of laser shots. Based on the results of conductive-atomic force microscopy measurements, we conclude that graphene formation was initiated from the step area, after which the graphene grew towards the terrace area by further Si evaporation and C recombination with increasing laser irradiation.

Energy Dissipation in Graphene Mechanical Resonators with and without Free Edges.

Graphene-based nanoelectromechanical systems (NEMS) have high future potential to realize sensitive mass and force sensors owing to graphene's low mass density and exceptional mechanical properties. One of the important remaining issues in this field is how to achieve mechanical resonators with a high quality factor (Q). Energy dissipation in resonators decreases Q, and suppressing it is the key to realizing sensitive sensors. In this article, we review our recent work on energy dissipation in doubly-clamped and circular drumhead graphene resonators. We examined the temperature (T) dependence of the inverse of a quality factor ( Q - 1 ) to reveal what the dominant dissipation mechanism is. Our doubly-clamped trilayer resonators show a characteristic Q - 1 -T curve similar to that observed in monolayer resonators: Q - 1 ∝ T 2 above ∼100 K and ∝ T 0.3 below ∼100 K. By comparing our results with previous experimental and theoretical results, we determine that the T 2 and T 0.3 dependences can be attributed to tensile strain induced by clamping metals and vibrations at the free edges in doubly-clamped resonators, respectively. The Q - 1 -T curve in our circular drumhead resonators indicates that removing free edges and clamping metal suppresses energy dissipation in the resonators, resulting in a linear T dependence of Q - 1 in a wide temperature range.

Graphene-modified interdigitated array electrode: fabrication, characterization, and electrochemical immunoassay application.

We have developed a new procedure for fabricating interdigitated array gold electrodes (Au-IDA) modified with reduced graphene oxide (rGO). In this procedure, we coated the gold surface of the micrometer order electrodes with graphene oxide (GO) prior to the reduction and the lift-off processes to avoid short-circuiting the pair of electrodes by conductive rGO flakes after the reduction. We then studied the basic electrochemical activity of the prepared electrodes, rGO/Au-IDA, mainly on p-aminophenol (pAP), because pAP is a good probe for an electrochemical immunoassay. The voltammograms showed that denser rGO provides better electrode reactivity for pAP. We confirmed that redox cycling between the anode and cathode at the rGO/Au-IDA was established, which yields more sensitive detection than with a single electrode. As one application of the electrochemical immunoassay using the rGO/Au-IDA, we demonstrated the quantitative detection of cortisol, a stress marker, at levels found in human saliva.

Synthesis and biological activity of novel alpha-substituted beta-phenylpropionic acids having pyridin-2-ylphenyl moiety as antihyperglycemic agents.

We previously reported the identification of novel oximes having 5-benzyl-2,4-thiazolidinedione with antihyperglycemic activity. We now report the synthesis and biological activity of a novel series of oximes and amides having alpha-substituted-beta-phenylpropionic acids. In this series, we obtained potent PPAR alpha/gamma dual agonist (S)-9d, with which activation of PPAR alpha and PPAR gamma was considerably more potent than that of the reference compounds GW9578 22 and rosiglitazone 3, respectively. This means (S)-9d is of the strongest class of PPAR alpha/gamma dual agonists. In the course of this study, we also obtained 8h, which indicated potent plasma glucose lowering effect in spite of weak PPAR alpha/gamma agonistic activity.

Efficient synthesis of antihyperglycemic (S)-alpha-aryloxy-beta-phenylpropionic acid using a bifunctional asymmetric catalyst.

Antihyperglycemic (S)-alpha-aryloxy-beta-phenylpropionic acid was prepared using catalytic asymmetric cyanosilylation as a key reaction to construct alpha-oxycarboxylic acid moiety.

Heterodimerization of dye-modified cyclodextrins with native cyclodextrins.

The heterodimerization behavior of dye-modified beta-cyclodextrins (1-6) with native cyclodextrins (CDs) was investigated by means of absorption and induced circular dichroism spectroscopy in an aqueous solution. Three types of azo dye-modified beta-CDs (1-3) show different association behaviors, depending on the positional difference and the electronic character of substituent connected to the CD unit in the dye moiety. p-Methyl red-modified beta-CD (1), which has a 4-(dimethylamino)azobenzene moiety connected to the CD unit at the 4' position by an amido linkage, forms an intramolecular self-complex, inserting the dye moiety in its beta-CD cavity. It also associates with the native alpha-CD by inserting the moiety of 1 into the alpha-CD cavity. The association constants for such heterodimerization are 198 M(-1) at pH 1.00 and 305 M(-1) at pH 6.59, which are larger than the association constant of 1 for beta-CD (43 M(-1) at pH 1.00). Methyl red-modified 2, which has the same dye moiety as that for 1 although its substituent position is different from that of 1, does not associate even with alpha-CD due to the stable self-intramolecular complex, in which the dye moiety is deeply included in its own cavity of beta-CD. Alizarin yellow-modified CD (3), which has an azo dye moiety different from that of 1 and 2, caused a slight spectral variation upon addition of alpha-CD, suggesting that the interaction between 3 and alpha-CD is weak. On the other hand, phenolphthalein-modified beta-CD (4), which forms an intermolecular association complex in its higher concentrations, binds with beta-CD with an association constant of 787 M(-1) at pH 10.80, where 4 exists as the dianion monomer in the absence of beta-CD. p-Nitorophenol-modified beta-CDs (5 and 6), each having p-nitorophenol moieties with a different connecting part with an amido and amidophenyl group, respectively, associated with alpha-CD with association constants of 66 and 16 M(-1) for 5 and 6, respectively. The phenyl unit in the connecting part of 6 may prevent the smooth binding with alpha-CD. All these results suggest that the dye-modified CDs, in which the dye part is not tightly included in its CD cavity, associate with the native CD to form heterodimer composed of two different CD units by inserting the dye moiety into the native CD unit. The resulting heterodimers have a cavity that can bind another appending moiety of host molecules. On this basis, more ordered molecular arrays or the supramolecular hereropolymers can be constructed.