Isotopic evidence in tree rings for historical changes in atmospheric sulfur sources

Little is understood about the usefulness of sulfur isotopic ratios (sigma 34S) in tree rings because the sulfur content in rings is generally insufficient for analysis using conventional methods. We present sigma 34S values of the water-soluble and the organically bound sulfur fractions in rings of coniferous trees grown in Japan, analyzed using a large-volume oxygen bomb. Comparing the sigma 34S values of the organically bound fraction in tree rings with past atmospheric sulfur concentrations and with those of their sources, we find clear evidence that the sigma 34S values of the organically bound fraction in the rings are dependent upon the values of the atmospheric sulfur sources. The evidence suggests that the sigma 34S values in tree rings are a useful chronological proxy for evaluating possible causes of past atmospheric sulfur pollution.     

Characterization of Acetylxylan Esterase from White-Rot Fungus Irpex lacteus

The carbohydrate esterase family 1 (CE1) in CAZy contains acetylxylan esterases (AXEs) and feruloyl esterases (FAEs). Here we cloned a gene coding for an AXE belonging to CE1 from Irpex lacteus (IlAXE1). IlAXE1 was heterologously expressed in Pichia pastoris, and the recombinant enzyme was purified and characterized. IlAXE1 hydrolyzed p-nitrophenyl acetate, α-naphthyl acetate and 4-methylumbelliferyl acetate, however, it did not show any activity on ethyl ferulate and methyl p-coumarate. We also examined the activity on partially acetylated and feruloylated xylan extracted from corncob by hydrothermal reaction. Similarly, ferulic and p-coumaric acids were not liberated, and acetic acid was only detected in the reaction mixture. The results indicated that IlAXE1 is an acetylxylan esterase actually reacted to acetyl xylan. However, since IlAXE1 was unable to completely release acetic acid esterifying xylopyranosyl residues, it is assumed that acetyl groups exhibiting resistance to deacetylation by IlAXE1 are present in corn cob xylan.     

Salt damage to brick kiln walls in Japan: spatial and seasonal variation of efflorescence and moisture content

To clarify the mechanism of salt fretting of a brick building, monthly observations were made over one year at a two-storey brick kiln in central Japan. Products of weathering that had fallen were collected and weighed; salts were identified using XRD and the moisture content of the brick was measured at its surface using a portable infrared optical moisture meter. Gypsum (CaSO₄·2H₂O) was found at the bottom of the first floor wall in the warm and humid season. Thenardite (Na₂SO₄) is dominant on the first floor wall; it is abundant in the cold and dry season but sparse in the warm and humid season. Magnesium sulphate is dominant on the second floor wall; epsomite (MgSO₄·7H₂O) was observed in the dry-to-wet season and hexahydrite (MgSO₄·6H₂O) in the wet-to-dry season. Seasonal changes in salt abundance result from the temperature dependence of the solubilities and equilibrium relative humidities (ERH) of each salt. The amount of brick decay material due to salt weathering is much greater from the second floor wall than from the first floor wall and is greater from spring to the end of summer. These seasonal and spatial variations of the rate of brick decay can be explained by a combination of factors: (1) the types of salt, (2) efflorescence or sub-florescence and (3) salt deliquescence.     

Effect of ultrafine grain refinement on hydrogen embrittlement of metastable austenitic stainless steel

Micro-tensile tests were performed on high-pressure-torsion-processed specimens of type 304 steel with grain sizes in the range of 0.1–0.5 μm to clarify the effect of ultrafine grain refinement on the hydrogen embrittlement (HE) of metastable austenitic steel. The ultrafine-grained (UFG) specimens with average grain sizes < ～0.4 μm exhibited a limited uniform elongation followed by a steady-stress regime in the stress–strain curves, which was attributed to a martensitic transformation. A high yield stress and a moderate elongation to failure were attained for the UFG specimens with an average grain size of ～0.5 μm in the uncharged state. Hall–Petch relationships well hold between the yield stress and the average grain size for each uncharged and hydrogen-charged specimen. Hydrogen charging increased the friction stress by 40% but did not change the Hall–Petch coefficient. Hydrogen-induced ductility loss was mitigated by ultrafine grain refinement. Ductility loss due to hydrogen charging manifested in the local deformation after a martensitic transformation. This indicates that hydrogen does not significantly affect the martensitic transformation, but shortens the subsequent local deformation process.     

基于4次线性微分方程的雷电冲击试验波形分析

当冲击试验电压高时,冲击试验电压的波形叠加过冲和振荡。这是由于冲击试验回路的残余电感、被试设备的大杂散电容或二者共同作用产生的。文章用4次微分方程式对振荡冲击试验的等值回路进行了分析,结果表明,波形可分为非振荡波头、振荡波头、非极性反转波尾、非振荡的极性反转波尾和振荡极性反转波尾5个部分。非振荡的极性反转波尾和振荡极性反转波尾的产生原理是不同的。波形的高频分量定义为振荡波形,非振荡波形是不含振荡波形成份的波形。文章的研究结果是后者的产生原因和等值电阻、等值电感的关系以及4次方程的根有关。文章给出了它们之间的关系。     

Excitons in organic-inorganic hybrid compounds (CnH2n + 1NH3)2PbBr4 (n = 4, 5, 7 and 12)

Thin films of microcrystalline (C_nH_2n + 1NH₃)₂PbBr₄ (n = 4, 5, 7 and 12) have been prepared by a modified spin-coating method, and the effect of the number of carbon atoms of the alkyl chain length (n) on optical properties has been investigated. Absorption spectra reveal that (C_nH_2n + 1NH₃)₂PbBr₄ films show stable excitons with a binding energy of a few hundred meV. The excitonic structure of (C_nH_2n + 1NH₃)₂PbBr₄ varies with the number of carbon atoms. The lowest-energy exciton splits into a few fine-structure levels at low temperature. (C_nH_2n + 1NH₃)₂PbBr₄ films (n = 5, 7 and 12) show not only singlet excitons but also triplet excitons at low temperature, while (C₄H₉NH₃)₂PbBr₄ films show only singlet excitons. The intersystem crossing from excited singlet state to triplet state plays an important role in the relaxation process of excitons.     

Leaching test of gamma-emitting Cs,Ru, Zr,and U from neutron-irradiated UO2/ZrO2 solid solutions in non-filtered surface seawater

The leaching behaviors of gamma-ray radionuclides, Cs-137, Ru-103, and Zr-95, produced by neutron irradiation of UO₂/ZrO₂ solid solutions, in real surface seawater were investigated under atmospheric conditions. The fraction of radionuclide inventory leached in the seawater was in the order of Cs > Ru (～U) ? Zr, indicating that the fraction was significantly affected by the chemical state of the radionuclides. However, the amount of soluble nuclides was proportional to that of uranium regardless of whether the solid solutions were prepared under an oxidative or reductive environment. A tiny fraction of Ru was filtered out by a 3 kDa nominal molecular weight cut-off filter after the 160 d leaching test, suggesting a different behavior from its ionic form, but Cs and U did not form a colloid-like species in seawater.     

Cross-coupling reaction of alkyl halides with grignard reagents catalyzed by Ni, Pd, or Cu complexes with pi-carbon ligand(s)

Transition metal-catalyzed cross-coupling reactions of organic halides and pseudo-halides containing a C-X bond (X = I, Br, Cl, OTf, OTs, etc.) with organometallic reagents are among the most important transformations for carbon-carbon bond formation between a variety of sp, sp(2), and sp(3)-hybridized carbon atoms. In particular, researchers have widely employed Ni- and Pd-catalyzed cross-coupling to synthesize complex organic structures from readily available components. The catalytic cycle of this process comprises oxidative addition, transmetalation, and reductive elimination steps. In these reactions, various organometallic reagents could bear a variety of R groups (alkyl, vinyl, aryl, or allyl), but the coupling partner has been primarily limited to sp and sp(2) carbon compounds: alkynes, alkenes, and arenes. With alkyl coupling partners, these reactions typically run into two problems within the catalytic cycle. First, oxidative addition of alkyl halides to a metal catalyst is generally less efficient than that of aryl or alkenyl compounds. Second, the alkylmetal intermediates formed tend to undergo intramolecular beta-hydrogen elimination. In this Account, we describe our efforts to overcome these problems for Ni and Pd chemistry. We have developed new catalytic systems that do not involve M(0) species but proceed via an anionic complex as the key intermediate. For example, we developed a unique cross-coupling reaction of alkyl halides with organomagnesium or organozinc reagents catalyzed by using a 1,3-butadiene as the additive. This reaction follows a new catalytic pathway: the Ni or Pd catalyst reacts first with R-MgX to form an anionic complex, which then reacts with alkyl halides. Bis-dienes were also effective additives for the Ni-catalyzed cross-coupling reaction of organozinc reagents with alkyl halides. This catalytic system tolerates a wide variety of functional groups, including nitriles, ketones, amides, and esters. In addition, we have extended the utility of Cu-catalyzed cross-coupling reactions. With 1-phenylpropyne as an additive, Cu-catalyzed reactions of alkyl chlorides, fluorides, and mesylates with Grignard reagents proceed efficiently. These new catalytic reactions use pi-carbon ligands such as pi-allyl units or alkynes instead of heteroatom ligands such as phosphines or amines. Overall, these reactions provide new methodology for introducing alkyl moieties into organic molecules.     

Study of molecular behavior in oxidation of insulating oil using terahertz spectroscopy

The stock of aged power equipment is increasing and it is important to clarify the characteristics of deteriorated insulating oil. This paper describes a basic study of molecular behavior in the oxidation of insulating oil by terahertz spectroscopy. The oxidation of insulating oil was modeled by using various compositions of dodecane and 2‐octanol. The terahertz measurements indicated that signi?cant absorption related to hydroxyl groups (‐OH) occurred between 6 and 7 THz. The absorption band was also observed in accelerated aging alkylbenzene, which is used in power equipment as insulating oil and is sensitive to hydrogen bonds. © 2013 Wiley Periodicals, Inc. Electr Eng Jpn, 183(1): 9–15, 2013; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.22335