Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Status of heavy element research using a gas-filled recoil separator at RIKEN

A gas-filled type of recoil separator for heavy element research was installed at an experimental hall of RIKEN Linear Accelerator facility to realize getting higher intensity of primary beam and long beam time. Performance of the separator was studied using target recoils and various nuclear reactions. The results show the high performance of the separator for heave element research. As an application of the GARIS, production and identification of an isotope of the 110th element ²⁷¹[110] have been performed using the ²⁰⁸Pb(⁶⁴Ni,1n)²⁷¹[110] reaction. Three decay chains coincide well both in decay times and energies with the ones reported by the group of SHIP experiment at GSI, Germany. Our results provide a confirmation of the synthesis of an isotope ²⁷¹[110] of element 110.     

Color Zone Map in Peripheral Vision at Various Illuminance Levels

We measured the entire region of mesopic and photopic vision to determine the color zone covering the visual field with unique red, yellow, green, and blue hue components. Eight kinds of test stimuli in the natural color system (NCS) color notation system were used. These stimuli were presented at horizontal and vertical meridians, and at meridians inclined at 45° angles. The illuminance level was set at six levels: 0.01 lx-1000 lx. The evaluation method measured chromatic, white, and black components as well as the hue component of the stimuli. Results show that the color zone of the retina extended further into the periphery with increasing illuminance; the response of opponent colors y-b was shown to be greater than that of the opponent colors r-g.     

A new luciferase reporter gene assay for the detection of androgenic and antiandrogenic effects based on a human prostate specific antigen promoter and PC3/AR human prostate cancer cells.

We developed a new mammalian cell-based luciferase reporter gene assay for androgenic and antiandrogenic activities of chemicals and environmental samples. Environmental samples usually have a complex matrix that may contain the constituents acting as androgen receptor (AR) agonists, AR antagonists or aryl hydrocarbon receptor (AhR) agonists. AhR agonists are known to elicit the antiandrogenic effect through cross-talk between AR and AhR signal transduction pathways. In this study, PC3/AR human prostate carcinoma cells were transiently transfected with a prostate-specific antigen (PSA) promoter-driven luciferase expression plasmid. The cells were treated with a test compound or an environmental sample for 24 h at 37 degrees C and then measured for luciferase activity. The luciferase activity was induced by dihydrotestosterone (DHT) in a concentration-dependent manner in a concentration range from 10 fM to 1 nM. R1881, a synthetic androgen receptor agonist, induced luciferase activity and its inductive effects was additive to that of DHT. The luciferase activity was not induced by cortisol, a glucocorticoid, progesterone, a progestin, and 17beta-estradiol, an estrogen in a concentration range of up to 1 microM. DHT-induced luciferase activity was reduced by bicalutamide and cyproterone acetate, AR antagonists, and also by benzo[a]pyrene, an aryl hydrocarbon receptor agonist, through AhR-mediated pathways. All of these findings indicate that the present assay system correctly responds to AR agonists, AR antagonists and AhR agonist and, therefore, it is a powerful tool for the sensitive and selective screening of chemicals and environmental samples for their androgenic and antiandrogenic activities. We developed the first assay system, in which the expression of luciferase was driven by the promoter of a prostate-specific antigen gene, a typical human androgen-regulated gene.     

Large-volume injection electrothermal AAS combined with tungsten-treated pyrolytic graphite furnace: determination of cadmium in tap, snow and river water samples with phosphate modifier.

A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples.     

Phase Conjugation in Saturable Absorbing Dye Films by Degenerate Four-Wave Mixing and Holographic Processes Using Nanosecond Pulse and CW Lasers

We report on the simultaneous generation of phase-conjugate signals by degenerate four-wave mixing (DFWM) and holographic processes using a nanosecond pulse and a CW lasers in polyvinyl alcohol (PVA) films doped with four kinds of saturable absorbing dyes. For the pulse laser, of the four kinds of dye-doped PVA films, the erythrosine B-doped PVA and uranine doped-PVA films generate PC signals only by the DFWM process, while the other dye-doped PVA films generate PC signals simultaneously by not only the DFWM process but also the holographic process. Especially, the safranin T-doped PVA film generates strong PC signals by the holographic process. In contrast, all of the dye-doped PVA films generate the two types of PC signals for the CW laser. The fading of dye molecules is found to result in the generation of the holographic component of PC signals which governs the temporal behavior of the total PC signals.     

Anisotropic giant magnetoresistance originating from the π-d interaction in a molecule

We synthesized TPP[Fe^III(Pc)(CN)₂]₂, PTMA_x[Fe^III(Pc)(CN)₂]·y(MeCN), and PXX [Fe^III(Pc)(CN)₂], a new series of charge-transfer salts containing the axially-substituted phthalocyanine (Pc), [Fe^III(Pc)(CN)₂]⁻. In this molecular unit, the π conduction electron derived from the Pc-ring coexists with the d electron which is a potential source of a local magnetic moment. Therefore various phenomena associated with the interplay between local magnetic moments and conduction electrons are expected. We observed the giant negative magnetoresistance (GNMR) in all the three salts. The GNMR is highly anisotropic for the magnetic-field direction, and reflects the g-tensor anisotropy of the local magnetic moment in the [Fe^III(Pc)(CN)₂]⁻ unit. This indicates that the GNMR in these salts originates from the strong π-d interaction in the [Fe^III(Pc)(CN)₂]⁻ unit.