Catalytic intermolecular Pauson-Khand-type reaction: strong directing effect of pyridylsilyl and pyrimidylsilyl groups and isolation of Ru complexes relevant to catalytic reaction

Some circumstantial evidence for the directing effect of the 2-pyridylsilyl group in the Ru-catalyzed intermolecular Pauson-Khand-type reaction (PKR) of alkenyl(2-pyridyl)silane, alkyne, and carbon monoxide has been provided. Most importantly, we have succeeded in isolating several monometallic Ru complexes relevant to the catalytic reaction: Ru(vinylsilane)(CO)(3) complexes and ruthenacyclopentene. While the stoichimetric reaction of the Ru(vinylsilane)(CO)(3) complex with an alkyne led to the formation of the corresponding cyclopentenone (PKR product) at 100 degrees C, the ruthenacyclopentene intermediate was quantitatively produced at 50 degrees C. This complex was also converted to a cyclopentenone upon heating at 100 degrees C. Moreover, it was also found that the Ru(vinylsilane)(CO)(3) complex and ruthenacyclopentene serve as catalysts in intermolecular PKR.     

A simplified measurement of hydrated crystal densities of low melting points (low transition points) by solidifications of aqueous solutions

A volume change method for measuring crystal densities is described. It allows the densities of unstable hydrated crystals at room temperature to be determined, by measurements of volume changes during the solidification of aqueous solutions. NaCl x 2H2O, KCl, MgSO4 x 12H2O and K2HPO4 x 6H2O were measured by the method and their densities (SE) are 1.61+/-0.02, 1.99+/-0.05, 1.45+/-0.01 and 1.75+/-0.02 g ml(-1) respectively. Data of NaCl x 2H2O and KCl are in good agreement with the previously reported values.     

NaI闪烁探测器测量感生放射性及其蒙特卡罗模拟

描述了如何使用蒙特卡罗方法评估产生在加速器屏蔽混凝土中的感生放射性. 使用EGS4程序模拟了NaI闪烁探测器测量屏蔽混凝土块表面剂量率时, 对于半径和厚度的响应. 结果发现,在屏蔽混凝土块半径和厚度分别达到40cm和30cm时, 表面剂量率达到饱和. 研究了东京大学SF回旋加速器北墙位置8和位置9的表面剂量率, 并和使用NaI闪烁探测器的测量结果进行了对比, 发现模拟和实验结果符合很好. 并且, 获得了表面剂量和表面感生放射性之间的转换系数, 对于⁶⁰Co转换系数为0.90(Bq·g^－1)·(μSv·h^－1)^－1, 对于¹⁵²Eu转换系数为1.26(Bq·g^－1)·(μSv·h^－1)^－1. 这样, 就可以通过NaI闪烁探测器表面剂量的测量结果简单评估加速器设备屏蔽混凝土中的感生放射性.     

Noise-Limitations of Coherence Imaging Based on Wavefront Folding Interferometry

Noise-limitations of the coherence imaging system based on the wavefront folding interferometer are studied. The signal-to-noise ratio SNR in two kinds of noise-limiting cases, the photon-noise-limit and the detector-noise-limit, is derived and are compared with the experimental results. The experimental demonstration is conducted using a wavefront folding interferometer and a single slit that provides the light source. An ensemble of ten sets of data are measured under the same conditions and the statistics of the retrieved images are computed from them. It is verified that the experimental results generally agree with the theoretical expectations.     

Structural characterization of hierarchically porous alumina aerogel and xerogel monoliths

Detailed nanostructures have been investigated for hierarchically porous alumina aerogels and xerogels prepared from ionic precursors via sol–gel reaction. Starting from AlCl₃·6H₂O and poly(ethylene oxide) (PEO) dissolved in a H₂O/EtOH mixed solvent, monolithic wet gels were synthesized using propylene oxide (PO) as a gelation initiator. Hierarchically porous alumina xerogels and aerogels were obtained after evaporative drying and supercritical drying, respectively. Macroporous structures are formed as a result of phase separation, while interstices between the secondary particles in the micrometer-sized gel skeletons work as mesoporous structures. Alumina xerogels exhibit considerable shrinkage during the evaporative drying process, resulting in relatively small mesopores (from 5.4 to 6.2 nm) regardless of the starting composition. For shrinkage-free alumina aerogels, on the other hand, the median mesopore size changes from 13.9 to 33.1 nm depending on the starting composition; the increases in PEO content and H₂O/EtOH volume ratio both contribute to producing smaller mesopores. Small-angle X-ray scattering (SAXS) analysis reveals that variation of median mesopore size can be ascribed to the change in agglomeration state of primary particles. As PEO content and H₂O/EtOH ratio increase, secondary particles become small, which results in relatively small mesopores. The results indicate that the agglomeration state of alumina primary particles is influenced by the presence of weakly interacting phase separation inducers such as PEO.     

Electronic structures of newly designed two-dimensional high-spin organic polymers

Practical two-dimensional high-spin organic polymers are newly designed and the electronic structures are examined on the basis of the ab initio two-dimensional unrestricted Hartree–Fock crystal orbital (UHF-CO) method. The present polymers can be oxidized up to six electrons per unit cell, and it is predicted that the three-electron and six-electron oxidations per unit cell lead to the high-spin organic polymers having superdegenerate band structures originating from the characteristic non-bonding crystal orbital patterns.     

Facile synthesis, crystal structures, and high-spin cationic states of all-para-brominated oligo(N-phenyl-m-aniline)s.

Syntheses of both the dimer (3) and the trimer (4) of all-para-brominated poly(N-phenyl-m-aniline)s (2c) were achieved in a one-pot procedure from the parent nonbrominated oligomers and benzyltrimethylammonium tribromide [(BTMA)Br(3)]. An X-ray crystallographic analysis revealed that 4 has a U-shaped structure, suggesting that 2c easily adopts helical structures. Furthermore, the redox properties were investigated by the UV-vis and EPR measurements. It was confirmed that the both 3 and 4 can be oxidized into the dications 3(2+) and 4(2+) with triplet spin-multiplicity.     

Coarse Metal Powder-Assisted pulsed CO2 Laser-induced Breakdown Spectroscopy for the Direct Determination of Heavy Metals in Soil

A novel method of laser-induced plasma spectroscopy utilizing a pulsed transversely excited atmospheric CO₂ laser has been developed for the high-sensitivity determination of heavy metals in soil. A coarse metal powder was used to trap the soil and to assist with plasma generation. When the CO₂ laser (10.6?µm, 1.5?J, 200?ns) was irradiated on the metal and soil powder, a high-temperature and long-lifetime luminous plasma was induced. Fine particles of soil were dissociated and were excited in the plasma region. The method was used for the rapid determination of Cr, Pb, and Hg in loam. The limits of detection for Cr, Pb, and Hg were approximately 0.8, 15, and 0.7?mg/kg, respectively.     

Air-stable, room-temperature emissive disilenes with π-extended aromatic groups

π-Conjugated disilenes with 2-naphthyl or 2-fluorenyl groups on the silicon atoms have been synthesized as air-stable emissive red solids using the bulky 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl (Eind) groups. The strong π-π* absorptions and distinct emission at room temperature, both in solution and in the solid state, have been observed due to the substantial contribution of the 3p(π)*(Si-Si)-2p(π)*(carbon π-electron system) conjugation.