Development of 394.6 GHz CW Gyrotron (Gyrotron FU CW II) for DNP/Proton-NMR at 600 MHz

Gyrotron FU CW II with an 8 T liquid He free superconducting magnet, the second gyrotron of the THz Gyrotron FU CW Series, has been constructed and the operation test was successfully carried out. It will be used for enhancing the sensitivity of 600 MHz proton-NMR by use of Dynamic Nuclear Polarization (DNP). The designed operation mode of the gyrotron is TE_2,6 at the second harmonic. The corresponding frequency is 394.6 GHz. The real operation frequency is 394.3 GHz at TE₀₆ mode, because of fabrication error of the diameter of the cavity. The operation is in complete CW at the output power of around 30 W or higher at the TE₀₆ cavity mode. There are many other operation modes at the fundamental and the second harmonic. Typical output power of the fundamental and the second harmonic are higher than 100 W and 20 W, respectively. The highest frequency observed up to the present is 443.5 GHz at the second harmonic operation of TE_6,5 mode. The measured results are compared with the theoretical consideration.     

Amination of N-aryl prolinol via ring expansion and contraction: application to the chiral ligand for the catalytic asymmetric reaction

Chiral diaminophosphines 4 were prepared from (S)-prolinol-derived aminophosphine oxide 5 by bromination with ring expansion followed by amination with ring contraction and reduction, using trichlorosilane. In the presence of 4 as a ligand, palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate (11) with a dialkyl malonate-BSA-LiOAc system was successfully carried out with good enantioselectivities (up to 98% ee).     

Determination of psilocybin in hallucinogenic mushrooms by reversed-phase liquid chromatography with fluorescence detection

The determination of psilocybin was carried out by reversed-phase liquid chromatography (HPLC) with fluorescence (FL) detection. Psilocybin was labeled with 5-dimethylaminonaphthalene-1-[N-(2-aminoethyl)]sulfonamide (DNS-ED) at 60 °C for 4 h in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) as the activation reagent. The resulting derivative was separated on a Mightysil RP-18 GP column (150 mm × 4.6 mm, i.d. 3 μm) with the mixture of 50 mM ammonium acetate (AcONH₄) and CH₃CN, and detected at 539 nm (excitation at 321 nm). The structure of the derivative was identified by HPLC-ESI-MS. A good linear relation of the calibration curve of psilocybin was observed under the proposed conditions for labeling, separation and detection. The quantification limit was 4.4 ng in 1 mg dried mushroom. The proposed procedure was successfully used for the determination of psilocybin in real samples. The contents of psilocybin in six magic mushrooms by the proposed HPLC-FL method were less than 20.0 ng in 1 mg dried samples.     

Biodegradation of bisphenol a by fungi

The biologic degradation of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A [BPA]; 1) was studied with 26 fungi. An initial BPA concentration of 40 ppm in an aqueous solution was degraded in the dark for 14 d. Among the 26 strains tested, 11 degraded BPA at 50% or more. Furthermore, four strains (F. sporotrichioides NFRI-1012, F. moniliforme 2-2, A. terreus MT-13, and E. nidulans MT-98) were more effective for degradation of BPA.     

Backward-wave four-wave mixing and coherent oscillation in CdF<Subscript>2</Subscript>:Ga,Y

Cadmium fluoride doped with Ga and Y is shown to be a suitable medium for backward-wave four-wave mixing with a grating decay time of a few seconds at room temperature. A 3-mm-thick sample ensures amplified phase-conjugate reflectivity and can therefore be used for building a coherent oscillator with a conventional mirror. PACS 42.65.Hw; 42.70.Mp; 42.70.Nq     

Electronic structure of a polydiacetylene nanowire fabricated on highly ordered pyrolytic graphite

A molecular wire candidate, the polydiacetylene chain, fabricated in a substantial support layer of monomers self-assembled on a highly ordered pyrolytic graphite surface, was studied using scanning tunneling microscopy and spectroscopy. The density of states of individual polymers and constituent monomers were observed on the same surface, and then compared with the calculated results. The spectrum delineating the density of states of the polydiacetylene wire clearly reveals the theoretically predicted pi-band and band edge singularities of the one-dimensional polymer.     

Sawtooth oscillation in current-carrying plasma in the large helical device

Sawtooth oscillations have been observed in current-carrying helical plasmas by using electron-cyclotron-emission diagnostics in the Large Helical Device. The plasma current, which is driven by neutral beam injection, reduces the beta threshold of the sawtooth oscillation. When the central q value is increased due to the plasma current, the core region crashes, and, when it is decreased, the edge region crashes annularly. Observed rapid mixture of the plasma in the limited region suggests that these sawtooth crashes are reconnection phenomena. Unlike previous experiments, no precursor oscillation has been observed.     

Phonon trigonal warping effect in graphite and carbon nanotubes

The one-dimensional structure of carbon nanotubes leads to quantum confinement of the wave vectors for the electronic states, thus making the double resonance Raman process selective, not only of the magnitude, but also of the direction of the phonon wave vectors. This additional selectivity allows us to reconstruct the phonon dispersion relations of 2D graphite, by probing individual single wall carbon nanotubes of different chiralities by resonance Raman spectroscopy, and using different laser excitation energies. In particular, we are able to measure the anisotropy, or the trigonal warping effect, in the phonon dispersion relations around the hexagonal corner of the Brillouin zone of graphite.     

Assessment of ESR-CT imaging by comparison with autoradiography for the distribution of a blood-brain-barrier permeable spin probe, MC-PROXYL, to rodent brain

Blood-brain-barrier (BBB)-permeable, 3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine-1-yloxy (MC-PROXYL) and BBB-impermeable carbamoyl-PROXYL were used to assess the ESR imaging technique by comparing with autoradiography. For this purpose, spin probes, 14C-labeled at their five-membered ring, [14C]MC-PROXYL and [14C]carbamoyl-PROXYL, were newly synthesized. These probes were i.p. or i.v. injected into rats and autoradiograms were recorded. The autoradiograms of rat head showed that [14C]MC-PROXYL distributed well in the brain compared to [14C]carbamoyl-PROXYL. In vivo ESR spectra and two-dimensional ESR images of isolated rat brain treated with MC- or carbamoyl-PROXYL also indicated the extensive distribution of MC-PROXYL but not carbamoyl-PROXYL in the rat brain. The three-dimensional ESR images of the head of rats and mice were consistent with the fact that MC-PROXYL but not carbamoyl-PROXYL is incorporated into the brain. The ESR-CT images were better for mice than rats. However, the quality of the ESR-CT images was still not satisfactory. Although the resolution and sensitivity of the ESR-CT images were worse than those of the autoradiographic images, the former technique has unique features and advantages; e.g., functional, noninvasive and three-dimensional detection.