Improvement of spatial homogeneity in GdBCO/IBAD-MgO coated conductor

Recent process optimization allows improving homogeneity and a significant increase of J_c in GdBa₂Cu₃O_7-δ deposited on ion-beam assisted deposited MgO template (GdBCO/IBAD-MgO). We applied low-temperature laser scanning microscopy and laser scanning thermo-electric microscopy (LSTEM) to investigate local dissipation and defects simultaneously in recent GdBCO/IBAD-MgO coated conductor. By using high-resolution LSTEM, we could detect current blocking obstacles which are responsible for the large scale local dissipation. Data on the present GdBCO/IBAD-MgO coated conductors point out a significant reduction of current blocking obstacles compared to the previous process. We have shown the improvement of spatial homogeneity in the recent GdBCO/IBAD-MgO coated conductors. Current blocking obstacles are much less densely distributed as compared to previous YBCO/IBAD-GZO coated conductor. Obstacles larger than several micrometer significantly increase local dissipation whereas smaller defects do not influence it noticeably. 2D map of the phase delay component of the thermoelectric voltage lock-in signal is effective to analyze current blocking obstacles having action upon local dissipation.     

Polymerization of Vinyl and Diene Monomers in Canal Complexes

In recent years the so-called biomimetic chemistry has received much attention. Studies of the preparation and design of functional polymers which can serve as polymeric enzyme and nucleic acid models appear to be a particularly rapidly expanding areas of research. These polymers and their aggregates should require highly specific sites or, in other words, atmospheres around them, in order to facilitate a series of selective reactions under conditions similar to those of biochemical environments. In this connection, molecular design of certain three-dimensional, highly organized spaces which consist of various sorts of molecular aggregates and can incorporate definite molecules in a specified way within their space are of interest for performing controlled organic and polymer synthetic reactions.     

Synthesis of Sulfonylurea Derivatives Used as Oral Antidiabetics by the Selenium-Assisted Carbonylation Using Carbon Monoxide with Sulfur

Sulfonylurea derivatives including useful antidiabetics (Tolbutamide, Chlorpropamide) were synthesized in good yields from benzene-sulfonamides with thiocarbamates in the presence of DBU. Thiocarbamates were prepared by the selenium-assisted carbonylation of primary amines with carbon monoxide, sulfur, and methyl iodide under mild conditions.     

One-Step Dialkoxylation of Aromatic Diamines with Trialkyl Phosphate

Alkylesters of orthophosphoric acids have been used for alkylation of phenols¹, anilines², and nitrogen heterocyclic compounds.³ However, no example is reported on their use as an alkoxylating agent for aromatic amines. We have found that alkyl phosphates can act as alkoxylating agents for aromatic diamines in the presence of H₂O or aqueous H₃PO₄. We now report the one-step dialkoxylation of aromatic diamines such as diaminoanthracene and -naphthalene by trialkyl phosphates.     

Induced production of novel prenyldepside and coumarins in endophytic fungi Pestalotiopsis acaciae

Concomitant supplementation of a histone deacetylase inhibitor, suberoylanilide hydroxamic acid, and a DNA methyltransferase inhibitor, 5-azacytidine, to the culture medium of a plant endophytic fungus, Pestalotiopsis acaciae, dramatically altered its metabolic profiles. As a result, three novel aromatic compounds, 2′-hydroxy-6′-hydroxymethyl-4′-methylphenyl-2,6-dihydroxy-3-(2-isopentenyl)benzoate (1), 4,6-dihydroxy-7-hydroxymethyl-3-methylcoumarin (2) and 4,6-dihydroxy-3,7-dimethylcoumarin (3), were isolated, along with five known polyketides, endocrocin (4), pestalotiollide B (5), pestalotiopyrone G (6), scirpyrone A (7) and 7-hydroxy-2-(2-hydroxypropyl)-5-methylchromone (8).     

Nuclear field shift effect in isotope fractionation of thallium

Environmental transport of Tl is affected by redox reaction between Tl(I) and Tl(III) and ligand exchange reactions of them. In order to deepen the knowledge of Tl chemistry, we investigated fractionation of Tl stable isotopes (²⁰³Tl and ²⁰⁵Tl) in a chemical exchange system. Tl isotopes were fractionated in a liquid–liquid extraction system, in which aqueous and organic phases are hydrochloric acid solution and dichloroethane including a crown ether, respectively. After purification by ion-exchange chemistry, the isotope ratio of ²⁰⁵Tl/²⁰³Tl in equilibrated aqueous phase was measured precisely by multiple-collector–inductively-coupled-plasma–mass-spectrometry. A large isotope fractionation >1 ‰ was found. Electronic structures of possible Tl species (hydrated Tl⁺, Tl³⁺, and Tl chlorides) were calculated by ab initio methods, and the isotope fractionation factor was theoretically obtained. The isotope fractionation via intramolecular vibrations was calculated to be much smaller than the experimental result. The isotope fractionation via isotopic change in nuclear volume, named the nuclear field shift effect, was calculated to be >1 ‰ in Tl(I)–Tl(III) redox systems and/or ligand exchange systems of Tl(III). The nuclear field shift effect was found to be the major origin of Tl isotope fractionation.     

Hydrogen-bonded liquid crystals built from hydrogen-bonding donors and acceptors. Infrared study on the stability of the hydrogen bond between carboxylic acid and pyridyl moieties

Abstract

The stability of a hydrogen-bonded complex built through inter-molecular hydrogen bonding between carboxylic acid and pyridine fragments has been examined using infrared spectroscopy. Infrared spectra as a function of temperature have been recorded for the 1:1 complex of 4-hexyloxybenzoic acid and trans-4-propoxy-4′-stilbazole from the crystalline state to the isotropic state. A dependence of the stability of the hydrogen bond on molecular orientation is observed clearly in the infrared spectra. The spectra also suggest that the hydrogen bond is an unionized type with a double minimum potential energy.     

Photochromic chiral liquid crystalline systems containing spiro-oxazine with a chiral substituent I. Synthesis and characterization of compounds

Photochromic acrylates containing both biphenylene and spiro-oxazine moieties with a chiral substituent and the related polymers were prepared and yielded photochromic chiral liquid crystalline systems. The photochromic acrylates containing both an undecamethylene group and a (2S, 3S)-2-chloro-3-methylpentanoyloxy group (A11SOP) or a (-)-menthoxyacetoxy group (A11SOM) gave a supercooled mesophase; the latter reflected right-handed visible light (blue colour) at room temperature. On the other hand, the photochromic acrylate containing both the (R)-(-)-2-methylpropylene and (2S, 3S)-2-chloro-3-methylpentanoyloxy groups (A3SOP) showed no mesophase. The related homopolymers, PA11SOP and PA11SOM, did not exhibit mesophases because of steric hindrance between the side groups of the polymers. However, only PA11SOM exhibited shear-induced birefringence under 100-104°C. Several copolymers consisting of the nematogenic monomer, 4-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzonitrile (A6CN), and A11SOP or A11SOM possessed a smectic phase due to reduction of the steric hindrance between the potentially smectogenic A11SOP or A11SOM moieties.     

Selective hydrogen peroxide oxidation of sulfides to sulfoxides or sulfones with MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions

Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0–1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions.