Reaction of a diaryldigermyne with ethylene

Reaction of the stable digermyne BbtGeGeBbt (Bbt = 2,6-[CH(SiMe₃)₂]₂-4-[C(SiMe₃)₃]-C₆H₂) with ethylene initially afforded the corresponding 1,2-digermacyclobutene. Depending on the reaction conditions applied, further reaction of this 1,2-digermacyclobutene with ethylene furnished two different reaction products: a 1,4-digermabicyclo[2.2.0]hexane or a bis(germiranyl)ethane. Combined experimental and theoretical results suggested that the 1,4-digermabicyclo[2.2.0]hexane and the bis(germiranyl)ethane are the thermodynamic and kinetic reaction products, respectively. A reaction mechanism in agreement with these results was proposed.     

Spatial AC Josephson effect

Investigating the current threshold in the mixed state of superconductors basing on the Ginzburg-Landau theory, we find that the threshold is determined by a mechanism analogous to the Josephson effect. An experimental evidence of this phenomenon is presented.     

An efficient synthesis of the anti-asthmatic agent T-440: a selective N-alkylation of 2-pyridone

6,7-Diethoxy-1-[1-(2-methoxyethyl)-2-oxo-1,2-dihydropyridin- 4-yl]naphthalene-2,3-dimethanol [T-440, (1)] is a potential anti-asthmatic agent based on selective phosphodiesterase 4 inhibition. It was necessary for the further evaluation of 1 to develop an efficient synthetic route for 1, especially the construction of the 1-(2-methoxyethyl)-2-pyridone moiety. We examined an N-selective alkylation of pyridone derivative (2) in basic media. 2-Methoxyethylation of 2 with 2-methoxyethyl iodide utilizing LiH as the base gave predominantly an N-alkyl pyridone derivative (3a) in 82% yield (N/O-alkylation=92/8), which is compatible with an ab initio calculation of transition-state structures for the methylation of 2-pyridone. Single crystallization of a crude mixture of 3a and 4a furnished pure 3a, which is a key synthetic intermediate of 1.     

Liquid chromatography-mass spectrometry for simultaneous analyses of iminodipeptides containing an N-terminal or a C-terminal proline

Simultaneous analyses of synthetic iminodipeptides containing an N-terminal proline or a C-terminal proline have been demonstrated using liquid chromatography-mass spectrometry with an atmospheric pressure ionization interface system. The separation of iminodipeptides was carried out on a reversed-phase high-performance liquid chromatographic column using 0.1% aqueous trifluoroacetic acid-methanol (75:25, v/v, pH 2.0) as mobile phase. Very intense protonated molecular ions [M + H]+ of various synthetic iminodipeptides, Pro-Gly, Gly-Pro, Pro-Ala, Ala-Pro, Pro-Val, Val-Pro, Pro-Leu and Leu-Pro, were observed. Pro-Gly (Pro-X) and Gly-Pro (X-Pro) have the same protonated molecular ion (m/z 173), but the peaks of these compounds on the mass chromatograms were clearly distinguished by the differences of the retention times and mass spectra. The synthetic iminodipeptides containing an N-terminal proline added to urine samples from a patient with prolidase deficiency were also distinguished from iminodipeptides containing a C-terminal proline in urine samples from a patient with prolidase deficiency by scanning the [M + H]+ ion of each iminodipeptide. We established the method to measure simultaneously the various iminodipeptides containing an N-terminal or a C-terminal proline in biological samples.     

Inclusive production ofK s 0 , K s 0 K s 0 andK *±(892) in\bar pp interactions at 3.0, 3.5, 4.0 and 4.5 GeV/c

InclusiveK _s ⁰ andK _s ⁰ K _s ⁰ production in \(\bar pp\) interactions at 3.0, 3.5, 4.0 and 4.5 GeV/c are studied. Cross sections ofK _s ⁰ , K _s ⁰ K _s ⁰ andK ^*±(892) are presented for each incident momentum. The production ofK _s ⁰ andK ^*±(892) through annihilation process is investigated. It is found that the annihilation process is dominant but decreases with incident momentum. The annihilation process is compared withe ⁺ e ^? interactions. Remarkable similarity between them is found in the \({{x_0 = 2E(K_s^0 )} \mathord{\left/ {\vphantom {{x_0 = 2E(K_s^0 )} {\sqrt s }}} \right. \kern-0em} {\sqrt s }}\) distribution. Events with two detectedK _s ⁰ 's are analyzed. The result shows theK _s ⁰ K _s ⁰ pairs are produced in the central region of c.m. system and there is a clearS ^* signal in theK _s ⁰ K _s ⁰ effective mass distribution.     

A layered tungstic acid H2W2O7 x nH2O with a double-octahedral sheet structure: conversion process from an aurivillius phase Bi2W2O9 and structural characterization

The conversion process of an Aurivillius phase, Bi(2)W(2)O(9), into a layered tungstic acid by hydrochloric acid treatment has been investigated, and resultant H(2)W(2)O(7) x nH(2)O has been fully characterized. The c parameter of Bi(2)W(2)O(9) [2.37063(5) nm] decreases to 2.21(1) nm in an acid-treated product dried at ambient temperature. The a and b parameters of Bi(2)W(2)O(9) [a = 0.54377(1) nm and b = 0.54166(1) nm] also decrease slightly to a = 0.524(1) nm and b = 0.513(1) nm in the acid-treated product dried at ambient temperature, indicating structural changes in the ReO(3)-like slabs in Bi(2)W(2)O(9) upon acid treatment. Drying at 120 degrees C leads to a further decrease in the c parameter [1.86(1) nm] with no notable change in the a and b parameters [a = 0.5249(2) nm and b = 0.513(2) nm]. The formation of an expandable layered structure is demonstrated by the successful intercalation of n-octylamine [interlayer distance 2.597(9) nm] and n-dodecylamine [interlayer distance 3.56(2) nm]. The compositions of the acid-treated products are determined to be H(2)W(2)O(7) x nH(2)O typically with n = 0.58 for the air-dried product and n = 0 for the product dried at 120 degrees C. As a consequence, the composition of the layer is H(2)W(2)O(7), and the decrease in the c parameter upon drying is ascribable to the loss of interlayer water. Scanning electron microscopy reveals no morphological change during acid treatment, which strongly suggests a selective leaching of the bismuth oxide sheets as a reaction mechanism. High-resolution transmission electron microscopy (HREM) observation of the acid-treated product shows consistency with a structural model for H(2)W(2)O(7), derived from Bi(2)W(2)O(9) through removal of the bismuth oxide sheets and contraction along the c axis. HREM observation also reveals that the WO(6) octahedra arrangement changes slightly with acid treatment. A one-dimensional electron density map projected on the c axis for the product dried at 120 degrees C, H(2)W(2)O(7), shows good consistency with that calculated for the structural model.     

Pyrolytic conversion of an Al?Si?N?C precursor prepared via hydrosilylation between [Me(H)SiNH]4 and [HAlN(allyl)]m[HAlN(ethyl)]n

An iminoalane‐silazane polymer (ISP), an Al? Si? N? C precursor, has been synthesized via Pt‐catalyzed hydrosilylation between poly(allyl iminoalane‐co‐ethyl iminoalane) {[HAlN(allyl)]_m[HAlN (ethyl)]_n, AE‐alane} and 1,3,5,7‐tetrahydro‐1,3,5,7‐tetramethylcyclotetrasilazane {[Me(H)SiNH]₄, TCS}. The IR and ¹H NMR spectra of ISP indicate that the relative amounts of the allyl groups decrease slightly in comparison with those of AE‐alane, suggesting that hydrosilylation occurs partially. TG analysis up to 900 °C reveals that the ceramic yield of ISP is 83.1 mass%. It is suggested that the high ceramic yield can be ascribed to cross‐linking reactions occurring during pyrolysis. Possible reactions during pyrolysis are hydrosilylation, polymerization of the C?C bonds in the allyl groups and dehydrocoupling among the SiH groups, NH groups and AlH groups in ISP. The pyrolyzed residue at 1700 °C contains crystalline AlN, 2H‐SiC, β‐SiC and β‐Si₃N₄ and amorphous carbon, as revealed by solid‐state nuclear magnetic resonance (NMR) spectroscopy, Raman spectroscopy and X‐ray diffraction (XRD) analysis. Copyright © 2006 John Wiley & Sons, Ltd.     

First enantioselective synthesis of (-)- and (+)-virgatusin, tetra-substituted tetrahydrofuran lignan

The first highly enantioselective syntheses of tetra-substituted tetrahydrofuran lignan, (-)- and (+)-virgatusin, were achieved. Hemiacetal was stereoselectively obtained from Evans's syn-aldol product as a single isomer. This hemiacetal was converted to (-)-virgatusin via hydrogenolysis. (+)-Virgatusin was also synthesized through the same process. The enantiomeric excess of the both enantiomers was determined as more than 99% ee.     

Analysis of trace actinide elements in soil organic matter: Optimization of sample processing to improve chemical separation of U and Pu

Chemical separation yield of actinide elements from soil samples containing high amounts of organic matters was often low as compared to that for samples containing low organic matters. We compared chemical yield of uranium and plutonium from organic-rich Japanese soil and humic acid samples which were subjected to three different pretreatment procedures ((1) pulverization only, (2) dry-ashing at 510 °C after pulverization, and (3) 680 kGy gamma-ray irradiation after pulverization) prior to acid digestion. Separation of U and Pu was performed by U-TEVA resin and AG1-X8 anion exchange resin, respectively. For organic samples, pretreatment procedures governed the yield of actinide elements significantly. Chemical separation yield of U was low (6±1%) for Aldrich humic acid sample after dry-ashing at 510 °C. For such samples, gamma-ray irradiation improved the yield of U to 35±22%. Recovery of Pu was lower for some organic soil samples which were dry-ashed at 510 °C (27±2%) as compared to those which were not dry-ashed (62±10%).