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.     

Copolymerization of Carbon Dioxide and Epoxide: Functionality of the Copolymer

Carbon dioxide and epoxide copolymerize in the presence of some organometallic catalyst systems under moderate conditions to give aliphatic polycarbonates of high molecular weight. Some metalloporphyrins of aluminum and zinc were found to act as novel catalysts for the polymerization of epoxide and for the copolymerization of carbon dioxide and epoxide, though not alternating. The polymers are characterized by the narrow molecular weight distribution and the unusual stereoregularity. Starting from the copolymerization of carbon dioxide and trimethylsilyl glycidyl ether with diethylzinc-water catalyst system, a readily degradable polycarbonate having hydroxyl group was obtained.     

From Living to “Immortal” Polymerization

Aluminum porphyrin is an excellent initiator for the living polymerizations of a wide variety of monomers such as epoxide, β-lactone, δ-lactone, ε-lactone, and lactide, and also for the alternating copolymerization of epoxide and cyclic acid anhydride or carbon dioxide, to give polymers and copolymers with narrow molecular weight distribution. Aluminum porphyrin was recently found to initiate also the living polymerization of methacrylic ester. In the polymerizations of epoxides and lactones initiated with aluminum porphyrin in the presence of an appropriate protic compound, polymers with narrow molecular weight can be obtained with the number of the polymer molecules more than those of the initiator. This fact demonstrates the “immortal” nature of the polymerization due to unusual reactivities of aluminum prophyrin.     

Index Abstracts

Abstract

Calorimetric titrations have been performed in anhydrous acetonitrile at 25°C to give the complex stability constants (K _s) and the thermodynamic parameters (ΔGΔ, ΔHΔ and ΔSΔ) for the complexation of light lanthanoid(III) nitrates (La-Gd) with N-benzylaza-21-crown-7 3. Data analyses, assuming 1:1 stoichiometry, were successfully applied to all light lanthanoid-azacrown ether combinations employed. Using the present and previous data on 15- to 21- membered N-benzylazacrown ethers 1–3, the effect of ring size upon complexation behavior was discussed comparatively and globally from the thermodynamic point of view. The complexation behaviors are analyzed in terms of the size-fit concept, N-substituent coordination numbers, and lanthanoid's surface charge density. Thermodynamically the complexation of light lanthanoids with azacrown ethers is enthalpy-driven, while the cation selectivity is generally entropy-driven in acetonitrile.     

A novel derivatization reagent possessing a bromoquinolinium structure for biological carboxylic acids in HPLC‐ESI‐MS/MS

A novel bromoquinolinium reagent, i.e. 1‐(3‐aminopropyl)‐3‐bromoquinolinium bromide (APBQ), was synthesized for the analysis of carboxylic acids. A simple and practical precolumn derivatization procedure using the APBQ in RP chromatography and MS (HPLC‐MS) has been developed using bile acids and free fatty acids, as the representative carboxylic acids in biological samples. The APBQ efficiently reacted with carboxylic acids at 60°C for 60 min in the presence of N,N‐dicyclohexylcarbodiimide and pyridine as the activation reagents. Because the APBQ possesses a bromine atom in the structure, the identification of a series of carboxylic acids was easily achieved due to the characteristic bromine isotope pattern in the mass spectra. The APBQ also has a quaternary amine structure, thus the positively charged derivatives are predominate for the highly sensitive detection of carboxylic acids. The APBQ was successfully applied to the selective determination of biological carboxylic acids in human plasma. The bile acids (chenodeoxycholic acid and deoxycholic acid) and several saturated (stearic acid and palmitic acid) and unsaturated free fatty acids (oleic acid and linoleic acid) were reasonably determined by HPLC‐MS under the proposed procedure. Based on the results of analyses of human plasma and saliva, the proposed procedure using APBQ seems to be applicable for the qualitative and quantitative analyses of a series of carboxylic acids in biological samples.     

Synthesis of Novel Spiro[indol-2,2′-pyrroles] Using Isocyanide-Based Multicomponent Reaction

An efficient and facile method for the synthesis of novel spiro[indole-2,2′-pyrroles] from N-methyl-3-isatin imines, t-butyl isocyanide, and dialkyl acetylenedicarboxylate has been achieved by [3 + 2] cyclo addition reaction. All the products were purified by column chromatography as yellow solids and confirmed with ¹H NMR, ¹³C NMR, fast atom bombardment, mass, and infrared. Compound 11 was further confirmed with x-ray analysis.     

Convenient Method for Dehalogenation of Aryl Halides

Reductive dehalogenation of aryl halides was achieved using hydrogen and a palladium catalyst. By using deuterium gas, the deuterated arenes were readily prepared.     

Novel synthesis of zerumbone-pendant derivatives and their biological activity

Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through S_N2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC₅₀ against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC₅₀: 0.24 μM).     

Investigation of radon and thoron concentrations in a landmark skyscraper in Tokyo

The temporal variation of the radon concentration, and the radon and thoron concentrations every 3 months for a year were measured using two types of devices in a landmark skyscraper, the Tokyo Metropolitan Government Daiichi Building. In the measurement of temporal variation of the radon concentration using a pulse type ionization chamber, the average radon concentration was 21 ± 13 Bq m^?3 (2–68 Bq m^?3). The measured indoor radon concentration had a strong relationship with the operation of the mechanical ventilation system and the activities of the office workers. The radon concentration also increased together with temperature. Other environmental parameters, such as air pressure and relative humidity, were not related to the radon concentration. In the long-term measurements using a passive radon and thoron discriminative monitor, no seasonal variation was observed. The annual average concentrations of radon and thoron were 16 ± 8 and 16 ± 7 Bq m^?3, respectively. There was also no relationship between the two concentrations. The annual average effective dose for office workers in this skyscraper was estimated to be 0.08 mSv y^?1 for 2000 working hours per year. When considering the indoor radon exposure received from their residential dwellings using the annual mean radon concentration indoors in Japan (15.5 Bq m^?3), the annual average effective dose was estimated to be 0.37 mSv y^?1. This value was 31 % of the worldwide average annual effective dose.