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Kazutoshi Shindo Ryoko NakamuraIkuko Chinda Yasuo OhnishiSueharu Horinouchi Haruko TakahashiKazuo Iguchi Shigeaki HarayamaKensuke Furukawa Norihiko Misawa 《Tetrahedron》2003,59(11):1895-1900
The bphA1(2072)A2A3A4 gene cluster codes for a shuffled biphenyl dioxygenase holoenzyme with broad substrate specificity. These bphA1(2072)A2A3A4 genes were expressed in the actinomycetes Streptomyces lividans using a thiostrepton-inducible promoter PtipA. Biotransformation experiments of various aromatics including carboxylic acid or amine in their molecular structure, such as 1-naphthoic acid, 2-(1-naphthyl)acetic acid, diphenylamine, and 1-benzyl-4-piperidone, were performed using the recombinant S. lividans cells. These ionized aromatics were converted to the corresponding 1,2-dihydrodiol, mono- or tri-hydroxy forms in 48 h. The structure of the converted products was determined by their EI-MS, 1H- and 13C NMR analysis, and several products were found to be novel compounds. 相似文献
23.
Perovskite-type barium lithium fluoride (BaLiF3) was synthesized by pyrolysis of metal trifluoroacetates. The reaction temperature necessary for producing a single-phase material was found to be 600°C, which was lower than that for a conventional solid-state reaction or a melting method. Eu-doped BaLiF3 was also prepared and characterized to examine the suitability of trifluoroacetates for precursors in synthesizing homogeneous complex metal fluoride materials. It was demonstrated that trivalent Eu3+, which was used as acetate for a starting material, was reduced to divalent Eu2+ in the pyrolysis process of BaLiF3, as indicated by a broad blue emission due to an allowed 4f65d→4f7 transition at 408 nm with a ultraviolet excitation at 254 nm. The concentration quenching of the blue emission occurred at 5 at% of Eu in BaLiF3, indicating that Eu was homogeneously dispersed in the BaLiF3 host lattice. Mechanisms of the formation and reduction process of BaLiF3 were discussed based on pertinent chemical reactions. 相似文献
24.
Pavel Smirnov Hisanobu Wakita Masaharu Nomura Toshio Yamaguchi 《Journal of solution chemistry》2004,33(6-7):903-922
The structure and complex formation of concentrated aqueous gallium(III) bromide (GaBr3) solutions have been investigated over a temperature range 80–333 K by Raman spectroscopy, X-ray absorption fine structure (XAFS), and X-ray diffraction. The Raman spectra obtained at various [Br?]/[Ga3+] molar ratios and temperatures have shown that complex formation between Ga3+ and Br? occurs as a predominant species, with [GaBr4]? at [Ga3+] as high as 1~2 M (M = mol?dm ?3) and [Br?]/[Ga3+] ratios > ~2, and that cooling of the solutions favors the formation of the aqua Ga3+. The intermediate species were not seen in the Raman spectra. The XAFS data have revealed that the aqua complex has a sixfold coordination as [Ga(H2O)6]3+ with a Ga3+–H2O distance of (1.96 ± 0.02) Å, whereas the [GaBr4]? complex has a Ga3+–Br? distance of (2.33± 0.02) Å, and that vitrification of the aqueous GaBr3 solution at liquid nitrogen temperature shifts the equilibrium toward the aqua complex. The X-ray diffraction data at different subzero temperatures have shown a tendency of decreasing Ga3+–Br? and increasing Ga3+–H2O interactions with lowering temperature, confirming the preference of aqua Ga3+ in the supercooled liquid state as well as in the glassy state. The Ga3+–H2O distance of ~1.8 Å for the tetrahedral coordination was found in a 2.01 M gallium(III) bromide solution with a [Br?]/[Ga3+] ratio of 3.7 and gradually increased to a value of 1.92 Å for octahedral geometry with decreasing temperature, suggesting that equilibrium shifts from [GaBr4]? to [Ga(H2O)6]3+ through intermediate species, [GaBr n ](3?n)+ (n = 2 and 3). The Ga3+–Br? and Br?–Br? distances within [GaBr4]? with an almost tetrahedral symmetry are (2.35± 0.02) and (3.82± 0.03) Å, respectively. The Ga3+ has the second hydration shell at (4.03± 0.03) Å and the hydration of Br? is characterized with a Br?–H2O distance of (3.35± 0.02) Å at all temperatures investigated. 相似文献
25.
Evaluation of homogeneity of binary blends of poly(3-hydroxybutyrate) and poly(L-lactic acid) studied by near infrared chemical imaging (NIRCI). 总被引:1,自引:0,他引:1
Tsuyoshi Furukawa Harumi Sato Hideyuki Shinzawa Isao Noda Shukichi Ochiai 《Analytical sciences》2007,23(7):871-876
The homogeneity of blends of poly((R)-3-hydroxybutyrate) (PHB) and poly(L-lactic acid) (PLLA) was evaluated by the near infrared chemical imaging (NIRCI) technique. NIRCI can nondestructively investigate a sample over a wide field of view within a few minutes to acquire a large number of spatially resolved NIR spectral data. NIRCI may be combined with multivariate analysis not only for qualitative analysis but also for statistically based quantitative analysis. The score images derived from the partial least squares regression (PLSR) analysis directly show that PHB/PLLA blends are highly homogeneous. The standard deviations (STD) of the histograms, indicating the distribution of the score values, show small values for the blends. These results qualitatively and quantitatively show the high level of homogeneity of PHB/PLLA blends. The predictions of the spatially averaged concentrations of the blend components obtained from PLSR results show values similar to the actual contents for the blends. The small errors of the predictions are also explained by STD values. 相似文献
26.
[reaction: see text] Regioselectivity of the oxidative coupling of 5,10,15-triarylporphyrin metal complexes with DDQ-Sc(OTf)(3) was dependent on the central metal and meso-aryl substituent. Oxo-quinoidal porphyrin was obtained from Ni(II) porphyrin under the same conditions. 相似文献
27.
Eiichi Kobayashi Shojiro Kaita Sadahito Aoshima Junji Furukawa 《Journal of polymer science. Part A, Polymer chemistry》1995,33(13):2175-2182
Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)3: R = CH3, CH2Cl, CHCl2, CCl3, and CF3], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)3—(i—Bu)3Al—Et2AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)3: CF3 > CCl3 > CHCl2 > CH2Cl ~ CH3. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI3)3- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ~ 14.5 mol %) by 13C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)2 and Co(acac)3-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc. 相似文献
28.
Reinosuke Hayakawa Toshio Nishi Kunio Arisawa Yasaku Wada 《Journal of Polymer Science.Polymer Physics》1967,5(1):165-177
Thermal expansion and dielectric relaxation of polyacrylonitrile were measured in the temperature range from ?75 to 152°C. at frequencies from 30 cps to 3 Mc./sec. The thermal expansion curve and the temperature dependence of logarithmic relaxation time both show an inflection at 85°C. An x-ray study by Bohn reveals that this inflection comes from the thermal expansion of the paracrystalline phase of this polymer, and consequently the transition at 85°C. and the associated relaxation are ascribed to molecular motion in the paracrystalline phase. The relaxation strength increases with increasing temperature above this point. The transition is caused by freezing of the bending vibration of chains whereas the relaxation results from rotational vibration. The length of segments in this phase is roughly estimated to be ca. 100 A. by comparing the observed relaxation strength with the theory developed on the basis of the above considerations. 相似文献
29.
Chiral beta-amino esters are synthesized in one-pot from three components, amines, aldehydes, and ethyl bromoacetate, under the rhodium-catalyzed Reformatsky-type reaction condition, where complete diastereoselection is achieved in the nucleophilic addition step of ethyl bromoacetate to the imines prepared in 相似文献
30.
Formation of silver nanoparticles has been developed based on a template technique. Amphiphilic star-block copolymers employed as single molecule template, utilizing the coordination of Ag+ ions with carboxyl groups in the core of the star-block copolymer. Silver nanoparticles have been prepared by the addition of chemical reductant, e.g., NaBH4. The solution of the resultant nanosphere composites showed yellow due to the surface plasmon resonance. These composites were soluble in organic solvents, because hydrophobic corona of the star-block copolymer protected the fabricated silver nanoparticles from aggregation. 相似文献