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101.
Determination of chemical form of antimony in contaminated soil around a smelter using X-ray absorption fine structure. 总被引:1,自引:0,他引:1
Masaki Takaoka Satoshi Fukutani Takashi Yamamoto Masato Horiuchi Naoya Satta Nobuo Takeda Kazuyuki Oshita Minoru Yoneda Shinsuke Morisawa Tsunehiro Tanaka 《Analytical sciences》2005,21(7):769-773
Only limited information is available about the behavior of antimony (Sb) in contaminated soils. However, understanding the behavior of Sb in contaminated soils is important, because the toxicity or solubility of this element depends on its chemical state. In this study, we investigated the levels of Sb and the chemical forms of Sb in the soil around a smelter using X-ray absorption fine structure (XAFS) spectra. The highest Sb concentration in the contaminated soil was 2900 mg/kg dry soil. According to Sb-K edge X-ray absorption near edge (XANE) spectra, the Sb in the soil was in the form of Sb(V) compounds. The similarity of extended XAFS (EXAFS) spectra suggests that Sb speciation was independent of the sampling site, which indicates that Sb or Sb2O3 emitted from the smelter was converted into Sb(V) compounds in the soil. 相似文献
102.
Reactions of enynes with three or two ester groups (1-4) in the presence of halogen-ligand Lewis acids gave cyclized products with halide incorporation (5-8) with high generality. The cyclization process was also analyzed in a theoretical study. Facile isomerization and dehydrohalogenation of five-membered products 5 and 8 by Al(2)O(3) or Et(3)N were also observed; this process introduces conjugated moieties into the products. 相似文献
103.
The reaction of the ortho-alkynylarylimines 1 with allyltributylstannane and allyl chloride in the presence of allylpalladium chloride dimer (5 mol %) and Cu(OAc)2 (20 mol %) in CH3CN at 50 °C gave the 1,4-diallyl-1,2-dihydroisoquinolines 2 in good yields. Most probably, the reaction proceeds through tandem bis-allylation of the imine-alkyne functional groups with bis-π-allylpalladium. 相似文献
104.
Characterization of clarithromycin polymorph was performed by solid-state cross polarization and magic angle spinning (CP/MAS) 13C-NMR spectroscopy. Two polymorphs, form II and form I, of clarithromycins indicated characteristic resonances of C1 carbonyl carbon at 176.2 and 175.2 ppm, respectively. Since each peak of C1 carbon was well separated in the spectrum of the two polymorphs, we performed quantitative analysis of the polymorphic fraction from the peak area of these peaks. The peak area of form I was found to linearly increase with an increase of its content, with a correlation coefficient of above 0.99. Solid-state NMR was found to be a useful technique to determine the characteristics of the polymorphic forms. 相似文献
105.
Nakamura I Mizushima Y Gridnev ID Yamamoto Y 《Journal of the American Chemical Society》2005,127(27):9844-9847
A new catalytic cyclization of o-alkynylbenzaldehyde acetals 1 to the functionalized indenes 2 was found to be strictly controlled by the number of triphenylphosphine ligands on the Pd catalyst. Only complexes with three available coordination sites on Pd catalyze this reaction. Mechanistic study suggests that pi-coordination of Pd to the benzene ring is a key step controlled by the number of vacant coordination sites. 相似文献
106.
Fumiyuki Ozawa Takashi Ito Yoshiyuki Nakamura Akio Yamamoto 《Journal of organometallic chemistry》1979,168(3):375-391
New palladium(0) complexes with a variety of coordinated olefins [Pd(olefin)(PMePh2)2] (II) (olefin = styrene, ethyl methacrylate, methyl methacrylate, methyl acrylate, methacrylonitrile, and dimethyl maleate), were prepared by the reactions of [PdEt2(PMePh2)2] (I) with corresponding olefins in toluene. These complexes were characterized by means of elemental analysis, IR and 1H NMR spectroscopy and the chemical reactions. The dissociation of the coordinated olefin from complex II in solution was confirmed by spectroscopic studies of [Pd(mma)(PMePh2)2] (mma = methyl methacrylate). From the variable temperature NMR study, kinetic parameters for the dissociation process were determined as Ea = 7 kcal/mol, and ΔS3 (293 K) = -30 cal/deg · mol. Some new hydrido complexes, [Pd(H)ClL2] (IV) (L = PMePh2, PEtPh2 and PEt2Ph), were prepared by the reactions of [Pd(olefin)L2] with dry HCl. 相似文献
107.
The molecular mechanism for 5-bromo-2'-deoxyuridine (BrdU) photosensitization was studied in thymine-requiring wild-type and uracil-DNA glycosylase (UDG)-deficient ung mutant cells of Escherichia coli K-12. Wild-type cells were more sensitive to BrdU photosensitiLation than ung mutant cells. IJV induced the identica/ numbers of alkaline sucrose single-strand breaks (SSB) in 5-bromouracil-DNA (BrU-DNA) of both the wild type and ung mutant. The ung mutant cells repaired SSB almost completely, whereas the wild-type cells with UDG produced more adverse SSB by 90 min after UV. Neutral agarose gel electrophoresis of minipreps indicated that UV induced (1) more smears of host BrU-DNA possibly by more double-strand breaks (DSB) and (2) a greater decline of pBR322 Form I BrU-DNA in the wild-type cells than the ung cells. These results indicated a greater induction of SSB by apyrimidinic (AP) endonucleases in wild-type cells. The ung/ wild ratios (=1.7–1.9) for cellular and plasmid BrdU sensitizations aftcr growth in 50% BrdU were similar. The extents of UDG-dependent and UDG-independent sensitizations in wild-type cells were ∼40 and ∼60%, respectively. The xth nfo double mutant defective in both exonuclcase III and endonucleasc IV was more sensitive to BrdU photosensitization than the wild type, indicating that an excess of AP sites remaining after uracil excision in the xth nfo mutant causes a greater BrdU photosensitization than SSB by AP endonucleases in wild-type cells. Conversely, the xth rfo ung triple mutant was more resistant to BrdU photosensitization than the xth nfo double mutant, so that UV-induced uracil residues in the BrU-DNA are tolerated and do not appear to be directly responsible for BrdU photosensitization. 相似文献
108.
Improved synthesis of four stereoisomeric chiral 1,3-dimethyl-1,2,3,4-tetrahydroisoquinolines (1a, b, ent-1a, b) was achieved via the super acid-induced cyclization of chiral N-[1-methyl-2-(phenylsulfinyl)ethyl]-N-(1-phenylethyl)formamides (4a, b, ent-4a, b) using the Pummerer-type cyclization reaction as a key step. The cyclization leading to the isoquinoline ring proceeded in a quantitative manner when trifluoromethane sulfonic acid (TFSA) was used as the super acid, although Friedel-Crafts-type alkylation of 4-phenylsulfanyl TIQ derivatives (5) with benzene used as the solvent accompanied cyclization to yield the 4-phenyl-TIQs (7). The byproduct (7) was exclusively formed when a large excess amount of TFSA was used. 相似文献
109.
Masao Matsuoka Tsuyoshi Matsuda June Tamaki Yoshifumi Yamamoto Chiaki Iwakura 《Research on Chemical Intermediates》2006,32(5):389-402
Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based
material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification
of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty
was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM
observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy
with a composition of Zr0.9Ti0.1Ni1.1Co0.1Mn0.5V0.2Cr0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing
mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic
stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and
diffusion path length of hydrogen. 相似文献
110.
A series of complexes, [M(bpy)(SAr)2] (M = platinum(II) or palladium(II), bpy = 2,2'-bipyridine, SAr = 2- or 4-(acylamino)benzenethiolate, or 2-(alkylcarbamoyl)benzenethiolate), were synthesized and characterized on the basis of 1H NMR, IR, and electrochemical properties. The structures of [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) and [Pt(bpy)(S-2-t-BuNHCOC6H4)2] (3) were determined by X-ray analysis. The complexes have intramolecular NH...S hydrogen bonds between the amide NH group and the sulfur atom. A weak NH...S hydrogen bond in these complexes and [Pd(bpy)(S-2-Ph3CCONHC6H4)2] (4) is detected from the 1H NMR spectra and the IR spectra in chloroform and in the solid state. [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) exhibits a remarkably high-energy-shifted lowest-energy band in UV-visible spectra and has a positively shifted oxidation potential. The blue-shift of 42 nm and the positive shift of +0.24 V, as compared to those of [Pt(bpy)(SC6H5)2), are due to the effect of the NH...S hydrogen bond. 相似文献