Room-Temperature,Metal-Free,and One-Pot Preparation of 2H-Indazoles through a Mills Reaction and Cyclization Sequence

The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence.     

Long-wavelength light emission from InAs quantum dots covered by GaAsSb grown on GaAs substrates

We fabricated InAs quantum dots (QDs) with a GaAsSb strain-reducing layer (SRL) on a GaAs(0 0 1) substrate. The wavelength of emission from InAs QD is shown to be controllable by changing the composition and thickness of the SRL. An increase in photoluminescence intensity with increasing compositions of Sb and thickness of the GaAsSb SRL is also seen. The efficiency of radiative recombination was improved under both conditions because the InAs/GaAsSb/GaAs hetero-interface band structure more effectively suppressed carrier escape from the InAs QDs.     

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.     

Ultrahigh‐molecular‐weight‐polyethylene‐fiber surface treatment by electron‐beam‐irradiation‐induced graft polymerization and its effect on adhesion in a styrene–butadiene rubber matrix

Aiming to develop a high‐performance fiber‐reinforced rubber from styrene–butadiene rubber (SBR), we applied a special technique using electron‐beam (EB)‐irradiation‐induced graft polymerization to ultrahigh‐molecular‐weight‐polyethylene (UHMWPE) fibers. The molecular interaction between the grafted UHMWPE fibers and an SBR matrix was studied through the evaluation of the adhesive behavior of the fibers in the SBR matrix. Although UHMWPE was chemically inert, two monomers, styrene and N‐vinyl formamide (NVF), were examined for graft polymerization onto the UHMWPE fiber surface. Styrene was not effective, but NVF was graft‐polymerized onto the UHMWPE fibers with this special method. A methanol/water mixture and dioxane were used as solvents for NVF, and the effects of the solvents on the grafting percentage of NVF were also examined. The methanol/water mixture was more effective. A grafting percentage of 16.4% was the highest obtained. This improved the adhesive force threefold with respect to that of untreated UHMWPE fibers. These results demonstrated that EB irradiation enabled graft polymerization to occur even on the inert surface of UHMWPE fibers. However, the mechanical properties of the fibers could be compromised according to the dose of EB irradiation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2595–2603, 2004     

Improved detectability with a polymer-based trapping device in rapid HPLC analysis for ultra-low levels of bisphenol A (BPA) in environmental samples.

A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system.     

Linear and Nonlinear Optical Properties Of Racemic (±)2-(α-Methylbenzylamino)-5-Nitropyridine Single Crystals

Linear and nonlinear optical properties of racemic (±)2-(α-methylbenzylamino)-5-nitropyridine ((±)MBANP) single crystals have been comprehensively investigated and compared with those of the enantiomorph (–)2-(α-methylbenzylamino)-5-nitropyridine ((–)MBANP) crystals. (±)MBANP crystal exhibits very high chemical and physical stability, but relatively small nonlinear optical coefficients (d₃₁ = 6.8 pm/V, d₃₂ = 4.7 pm/V, d₃₃ = 0.84 pm/V). A comparison between the nonlinear optical coefficients of (±)MBANP and (–)MBANP demonstrates the validity of the oriented-gas model in molecular crystals that neglects all the contributions from intermolecular interaction.     

Numerical reconstruction of an infrared wavefront utilizing an optical phase modulation device

We utilize nitroanisole, that absorbs infrared (IR) radiation as heat, as an optical modulation device based on a thermal process. The nitroanisole exhibits a thermal lens effect, i.e. a temperature dependent refractive index. Hence, the nitroanisole can induce phase modulation to visible light, in direct response to intensity of the incident IR radiation. The proposed method can be used to obtain the phase modulation distribution that corresponds to the IR intensity distribution, i.e. the IR hologram itself, on the nitroanisole by examining the phase map of visible light that is modulated upon passing through the nitroanisole. The IR wavefront can be reconstructed by calculating extracted IR holograms through the Fresnel transform. It is verified that both the amplitude and the phase of the IR wavefront can be reconstructed accurately by proposed method.     

Design of a widely tunable laser with a chirped ladder filter

We theoretically investigated a digitally tunable laser with a chirped ladder filter and a ring resonator to obtain a wide wavelength tuning range covering the whole C- or L- band. The clear relation between the tuning range and laser structure, especially the ladder filter, is described analytically. The introduction of a chirped structure into a ladder filter is effective in achieving both wide tunability and a stable lasing mode. A numerical simulation based on multimode rate equations shows that a tuning range of over 40 nm and a mode suppression ratio over 40 dB can be achieved by introducing a chirped ladder filter.     

Different acute effects of oral and intratracheal administration of disodium arsenate and gallium arsenide on heme synthesis in rats

The acute influences of arsenic compounds on the metabolism of porphyrins and heme in various organs of rats after oral or intratracheal administration of disodium arsenate (Na₂HAsO₄) and gallium arsenide (GaAs) were examined and compared. For the oral administration experiments, 21 or 84 mg of Na₂HAsO₄, or 2 or 4 g of GaAs, per cm³ saline per kg body weight of each animal was administered to Jcl: Wistar male rats and the organs were removed after exsanguination from the vein of the right axilla under anesthesia with ether, 16 h after administration. In the case of intratracheal administration, rats given 8.2 or 16.4 mg of Na₂HAsO₄, or 0.2 or 0.4 g GaAs per cm³ saline per kg body weight were examined under the same experimental conditions as for the administration route. Increase in the body weight of rats was suppressed after intratracheal administration of the two arsenic compounds. In these rats the hematocrit value increased significantly. These changes were not shown by the orally administered rats. Elevation in δ-aminolevulinate synthase (ALA-S, EC 2.3.1.37) activity in erythroblasts by Na₂HAsO₄ was much higher after intratracheal administration than after oral administration. Suppression in the activities of δ-aminolevulinate dehydratase (ALA-D, EC 4.2.1.24) and porphobilinogen deaminase (PBG-D, EC 4.3.1.8) in peripheral erythrocytes by Na₂HAsO₄ and GaAs were stronger by intratracheal administration than by the oral route. Influences of GaAs on the activity of PBG-D in rat liver were shown to be more effective by oral administration than by the intratracheal route. Oral administration of Na₂HAsO₄ and GaAs had a stronger suppression effect on the activities of ALA-D and PBG-D in rat kidney. It seems from these results that the different extents of the influence of arsenic compounds might depend on the routes of intake.