Potential formation and high density plasma production on the tandem mirror GAMMA 10

GAMMA 10 experiments have advanced in high density experiments after the last EPS Workshop where we reported high density plasma production by using an ion cyclotron range of frequency heating at a high harmonic frequency and neutral beam injection in the central cell. Recently a high density plasma was obtained with much improved reproducibility than before and without degradation of diamagnetic signal. The high density plasma was attained by adjusting the spacing of the conducting plates installed in the anchor transition regions. Dependencies of particle confinement time, ion energy confinement time and plasma confining potential on plasma density were obtained for the first time in the high density region. Presented at 5th Workshop “Role of Electric Fields in Plasma Confinement and Exhaust”, Montreus, Switzerland, June 23–24, 2002.     

Magnetic interactions in a series of paramagnetic Ln(III) complexes with a chelated imino nitroxide radical

The magnetic interactions in a new series of isostructural imino nitroxide radical lanthanide(III) complexes, [Ln(hfac)₃(IM2py)] (Ln = Gd–Yb: IM2py = 2-(2′-pyridyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-1-oxy; hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), are examined by considering the intrinsic paramagnetic contribution of the Ln(III) ion from the corresponding [Ln(hfac)₃(pybzim)] with a diamagnetic pybzim(2-(2-pyridyl)benzimidazole) ligand; the Ln(III)–IM2py interaction being antiferromagnetic for the 4f⁷ to 4f¹³ Ln(III) complexes and negligibly small for the other complexes. This series is the first example reverse to the previous cases for the series of Ln–Cu or Ln–aminoxyl(NIT) radical (4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-3-oxide-1-oxy) complexes, other than only a few examples of semiquinone Ln complexes. This reverse nature of the magnetic interaction, as compared with the NIT complexes, validates the empirical approach by O. Kahn et al. [Inorg. Chem. 38 (1999) 3692; J. Am. Chem. Soc. 122 (2000) 3413] in the spin-coupled systems for a series of Ln(III) complexes.     

Photocatalytic decomposition of an alkylammonium cation in a Langmuir-Blodgett film of a titania nanosheet

The formation of inorganic-organic hybrid films of a titania nanosheet and an amphiphilic alkylammonium cation has been investigated, and the photocatalytic decomposition of the alkylammonium cation in the film has been pursued. When a solution of the amphiphilic alkylammonium salt (octadecylammonium chloride: ODAH+ Cl-) was spread on an interface between the air and a titania nanosheet suspension, the negatively charged nanosheets were adsorbed onto the floating monolayer of ODAH+ to form a hybrid monolayer. The hybridization was confirmed by pi-A isotherm measurements, atomic force microscopy, and X-ray photoelectron spectroscopy. Multilayered films were fabricated in a layer-by-layer way by transferring the hybrid monolayers onto glass plates. Areas per ODAH+ cation in the films were estimated from the infrared (IR) spectra of the films, but these areas were smaller than those estimated from the pi-A isotherm curves. The orientation of the alkyl chain of ODAH+ in the hybrid film was determined by means of polarized IR spectroscopy. The alkyl chains were tilted 41 +/- 1 degrees and 47 +/- 1 degrees from the surface normal for the films prepared from the 8 and 20 ppm (ppm = mg dm(-3)) suspensions, respectively. Together with X-ray diffraction data of the films, the structure of the hybrid film was discussed. When the films were illuminated with a UV light, the absorption intensities due to the alkyl chain of ODAH+ decreased exponentially, indicating the photocatalytic decomposition of ODAH+ by the titania nanosheets in the films. Deviation from the exponential trend in the decomposition rate was observed in the initial period for the hybrid films prepared from the suspensions at low concentrations. Interestingly, the layered structure of the hybrid film was disturbed significantly after the ODAH+ cations were decomposed.     

Development of pyrrole-imidazole polyamide for specific regulation of human aurora kinase-A and -B gene expression

Pyrrole-imidazole polyamide (PIP) is a nuclease-resistant novel compound that inhibits gene expression through binding to the minor groove of DNA. Human aurora kinase-A (AURKA) and -B (AURKB) are important regulators in mitosis during the cell cycle. In this study, two specific PIPs (PIP-A and PIP-B) targeting AURKA and AURKB promoter regions were designed and synthesized, and their biological effects were investigated by several in vitro assays. PIP-A and PIP-B significantly inhibited the promoter activities, mRNA expression, and protein levels of AURKA and AURKB, respectively, in a concentration-dependent manner. Moreover, 1:1 combination treatment with both PIPs demonstrated prominent antiproliferative synergy (CI value [ED(50)] = 0.256) to HeLa cells as a result of inducing apoptosis-mediated severe catastrophe of cell-cycle progression. The novel synthesized PIP-A and PIP-B are potent and specific gene-silencing agents for AURKA and AURKB.     

Ligand-free Sonogashira coupling reactions with heterogeneous Pd/C as the catalyst

A variety of aryl iodides were coupled with aromatic and aliphatic terminal alkynes to give the corresponding 1,2-disubstituted aromatic alkynes in good yields by using only 0.4 mol % of the heterogeneous 10 % Pd/C as the catalyst without a ligand, copper salt, or amine in an aqueous medium.     

Low-energy states of a semiflexible polymer chain with attraction and the whip-toroid transitions

We establish a general model for the whip-toroid transitions of a semiflexible homopolymer chain using the path integral method and the O3 nonlinear sigma model on a line segment with the local inextensibility constraint. We exactly solve the energy levels of classical solutions and show that some of its classical configurations exhibit toroidal forms, and the system has phase transitions from a whip to toroidal states with a conformation parameter c = (W2l)(L2pi)2. We also discuss the stability of the toroid states and propose the low-energy effective Green's function. Finally, with the finite size effect on the toroid states, predicted toroidal properties are successfully compared to experimental results of DNA condensation.     

New layered rare-earth hydroxides with anion-exchange properties

We report the synthesis of a new series of layered hydroxides based on rare-earth elements with a composition of RE(OH)2.5Cl(0.5).0.8 H2O (RE: Eu, Tb, etc.) through the homogeneous precipitation of RECl3.x H2O with hexamethylenetetramine (HMT). Rietveld analysis combined with direct methods revealed an orthorhombic layered structure comprising a positively charged layer of [RE(OH)2.5-(H2O)0.8]0.5+ and interlayer Cl- ions. The Cl- ions were readily exchangeable for various anions (NO3-, SO4(2-), dodecylsulfonate, etc.) at ambient temperature. Photoluminescence studies showed that the compounds display typical RE3+ emission. With rare-earth-based host layers and tunable interlayer guests, the new compounds may be of interest for optoelectronic, magnetic, catalytic, and biomedical materials.     

Selective photocatalytic oxidation of alcohols to aldehydes in water by TiO2 partially coated with WO3

Semiconductor TiO₂ particles loaded with WO₃ (WO₃/TiO₂), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO₃/TiO₂ catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO₂. In particular, a catalyst loading 7.6 wt % WO₃ led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO₂ surface of the catalyst, which is active for oxidation, is partially coated by the WO₃ layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO₂ surface. This suppresses subsequent decomposition of the aldehyde on the TiO₂ surface and results in high aldehyde selectivity. The WO₃/TiO₂ catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity.