Geographical distribution of plutonium derived from the atomic bomb in the eastern area of Nagasaki

In order to know the distribution of plutonium derived from the Nagasaki atomic bomb, soil samples were measured to determine the ²⁴⁰Pu/²³⁹Pu isotope ratio of and concentrations of ^239+240Pu and ¹³⁷Cs. The ^239+240Pu concentrations in soils, except for Nishiyama area, were close to the average concentration of soil collected in Japan. In soils collected at the Nishiyama area and at the eastern area of Nagasaki Prefecture and at part of northern area in Kumamoto Prefecture, the ²⁴⁰Pu/²³⁹Pu ratios were lower than the global fallout values. This suggests that plutonium from the atomic bomb was deposited in the eastern area from the hypocenter reaching up to 100 km eastwards.     

Determination of cyclosporin A in the serum of kidney transplant patients by rapid-flow fractionation and normal-phase high-performance liquid chromatography

High-performance liquid chromatography was used to determine cyclosporin A (CsA) concentrations in the serum of kidney transplant patients by rapid-flow fractionation (RFF) followed by silica gel normal-phase high-performance liquid chromatography (HPLC). The extraction of CsA from serum was achieved by RFF using a short diatomaceous earth column eluted with diethyl ether-n-hexane (50:50, v/v). The recovery was more than 80% at concentrations of 50-150 micrograms/l. The concentration of this compound was determined by HPLC using a conventional silica gel column with 3.3 M ammonia solution-ethanol-n-hexane (0.31:10.69:89, v/v) as eluent. Concentration calibration was made on the basis of the peak-height ratio of CsA to CsD as the internal standard. The coefficient of variation of this assay was less than 6.5% and the results were used for the therapeutic drug monitoring of CsA administered to kidney transplant patients. Measurements of the CsA concentrations in 160 serum specimens were also made by conventional radioimmunoassay (RIA) using commercial kits. The data obtained by RIA were on average 2.5 times those obtained by HPLC. Higher values in RIA were observed characteristically with patients with severe disfunction resulting from CsA hepatotoxicity. From the results, it appeared that HPLC rather than RIA provides more precise and reliable values for the concentration of this drug.     

Spin-dependent electron momentum densities in Co2FeGa studied by Compton scattering

The spin density of Heusler alloy Co₂FeGa, has been studied using the Compton scattering technique with 274 keV circularly polarized synchrotron radiation in the high energy inelastic scattering beamline (BL08W), at SPring-8, Japan. The magnetic Compton profiles along the two principal directions [1 1 0] and [1 1 1] were measured. The spin profiles shows a good agreement with our FLAPW-GGA results, where the theoretical results were based on the ferromagnetic ground state. The 3d spin moment at the Co and the Fe site was found to be in excellent agreement with the earlier reported neutron diffraction measurements.     

Polycyclic N‐Heterocyclic Compounds,Part 72: Reaction of N‐([1]Benzofuro (or Benzothieno)[3,2‐d]pyrimidin‐4‐yl)formamidine and N‐(Pyrido[2,3‐d]pyrimidin‐4‐yl)formamidine Derivatives with Hydroxylamine Hydrochloride

The reactions of N‐([1]benzofuro[3,2‐d]pyrimidin‐4‐yl)formamidines with hydroxylamine hydrochloride gave rearranged cyclization products via ring cleavage of the pyrimidine component accompanied by a ring closure of the 1,2,4‐oxadiazole to give N‐[2‐([1,2,4]oxadiazol‐5‐yl)[1]benzofuran‐3‐yl)formamide oximes. N‐([1]Benzothieno[3,2‐d]pyrimidin‐4‐yl)formamidines and N‐(pyrido[2,3‐d]pyrimidin‐4‐yl)formamidines with hydroxylamine hydrochloride gave similar results.     

Crystalline‐Sponge‐Based Structural Analysis of Crude Natural Product Extracts

Characterization of complex natural product mixtures to the absolute structural level of their components often requires significant amounts of starting materials and lengthy purification process, followed by arduous structure elucidation efforts. The crystalline sponge (CS) method has demonstrated utility in the absolute structure elucidation of isolated organic compounds at miniscule quantities compared to conventional methods. In this work, we developed a new CS‐based workflow that greatly expedites the in‐depth structural analysis of crude natural product extracts. Using a crude extract of the red alga Laurencia pacifica, we showed that CS affinity screening prior to compound isolation enables prioritization of analytes present in the extract, and we subsequently resolved the molecular structures of six sesquiterpenes with stereochemical clarity from around 10 mg crude extract. This study demonstrates a new chemotyping workflow that can greatly accelerate natural product discovery from complex samples.     

Reductive coupling of N-methoxycarbonyl lactams with benzophenone and 9-fluorenone by low-valent titanium

The reductive coupling of N-methoxycarbonyl lactams with benzophenone by Zn-TiCl₄ in THF gave cross-coupled products as cyclic α-diphenylidene-N-methoxycarbonylamines and ring-opening α,α-diphenyl-α-hydroxy-ω-(N-methoxycarbonyl)amino ketones selectively depending on the reduction conditions. The reductive coupling of N-methoxycarbonyl lactams with 9-fluorenone by Zn-TiCl₄ gave cyclic α-(9H-fluoren-9-ylidene)-N-methoxycarbonylamines preferentially irrespective to the conditions.     

Syntheses and properties of dumbbell‐shaped POSS derivatives linked by luminescent π‐conjugated units

Dumbbell‐shaped isobutyl‐substituted 1,2‐bis(4‐vinylphenyl)acetylene‐linked POSS (DA1), 9,10‐bis(4‐vinylphenyl)ethynyl)anthracene‐linked POSS (DA2), and 5,5″‐bis((4‐vinyl)phenyl)ethynyl)‐2,2′:5′2″‐terthiophene‐linked POSS (DA3), and corresponding model compounds were synthesized by cross metathesis and Sonogashira reaction, and their film formability, and thermal and optical properties were examined. The dumbbell structures of the obtained compounds were confirmed by ¹H‐, ¹³C‐, and ²⁹Si‐NMR and MALDI‐TOF‐MS analysis. The dumbbell‐shaped POSS compounds gave optically transparent films. All the model compounds, however, formed opaque films. All the films were emissive under UV irradiation. The dumbbell structures minimize longer wavelength shifts and improve emission efficiency of the luminescent π‐conjugated linker units in their solid states compared with the model compounds. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.