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41.
Makoto OzawaTakaaki Taguchi Takayuki ItohYutaka Ebizuka Kevin I Booker-MilburnG.Richard Stephenson Koji Ichinose 《Tetrahedron》2003,59(44):8793-8798
A novel shunt product was isolated from a disruptant of the actVI-ORFA gene involved in the biosynthesis of actinorhodin (ACT) in Streptomyces coelicolor A3(2). Its structure was elucidated as 1,4-naphthoquinone-8-hydroxy-3-[3(S)-acetoxy-butyric acid], (S)-NHAB, based on NMR, MS, and CD spectroscopic data as well as a single crystal X-ray crystallographic analysis. The formation of (S)-NHAB involves a retro-Claisen type C-C bond cleavage of an ACT biosynthetic intermediate. Feeding experiments with [1-13C] and [2-13C] acetates indicated its biosynthetic origin as a single octaketide chain. The relevant gene product, Act-ORFA, which is a functionally unknown protein, is proposed to play a regulatory role related to the multi-enzymatic steps to ACT production, based on the metabolic profile of its disruptant and the wide distribution of actVI-ORFA homologues in the gene clusters for Streptomyces aromatic polyketides. 相似文献
42.
[structure: see text] A convergent total synthesis of cis-solamin and its diastereomer was accomplished using VO(acac)2-catalyzed diastereoselective epoxidation followed by cyclization of bis-homoallylic alcohol as the key step. By comparison of the optical rotation of two possible diastereomers, it is suggested that the absolute configuration of natural cis-solamin is 1a. 相似文献
43.
Hitoshi Tanaka Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1977,15(11):2613-2621
Photodegradation behavior of atactic and isotactic polymers of tert-butyl vinyl ketone (t-BVK) and its copolymers with styrene and α-methylstyrene was studied in dioxane as a solvent at room temperature. The quantum yield of main-chain scission of atactic poly(t-BVK) was found to be larger than that of isotactic poly(t-BVK) and atactic poly(methyl vinyl ketone). From the Stern-Volmer plots on the quenching study of atactic poly(t-BVK) with naphthalene and 2,5-dimethyl-2,4-hexadiene, it was found that 60–70% of its photochemical reaction underwent main-chain scission from the triplet state. It was also found that the increase in t-BVK contents of both copolymers accelerated the photodegradation, and the copolymer with styrene was more photodegradable than that with α-methylstyrene. These results seemed to suggest that the main-chain scission of these vinyl ketone polymers and copolymers proceeded through a Norrish type II photoelimination mechanism. 相似文献
44.
Akikazu Matsumoto Katsuhiko Fukushima Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1991,29(12):1697-1706
Radical polymerization of N,N,N′,N′-tetraalkylfumaramides (TRFAm) bearing methyl, ethyl, n-propyl, isopropyl, and isobutyl groups as N-substituents (TMFAm, TEFAm, TnPFAm, TIPFAm, and TIBFAm, respectively) was investigated. In the polymerization of TEFAm initiated with 1,1′-azobiscyclohexane-1-carbonitrile (ACN) in benzene, the polymerization rate (Rp) was expressed as follows: Rp = k [ACN]0.28 [TEFAm]1.26, and the overall activation energy was 102.1 kJ/mol. The introduction of a bulky alkyl group into N-substituent of TRFAm decreased the Rp in the following order: TMFAm > TEFAm > TnPFAm > TIBFAm > TIPFAm ~ 0. The relative reactivities of these monomers were also investigated in radical copolymerization with styrene (St) and methyl methacrylate (MMA). In copolymerization of TRFAm (M2) with St (M1), monomer reactivity ratios were determined to be r1 = 1.07 and r2 = 0.20 for St–TMFAm, and r1 = 1.88 and r2 = 0.11 for St–TEFAm, from which Q2 and e2 values were estimated to be 0.35 and 0.44 for TMFAm, and 0.19 and 0.47 for TEFAm, respectively. The other TRFAm were also copolymerized with St, but copolymerization with MMA gave polymers containing a small amount of TRFAm units. The polymer from TRFAm consists of a less-flexible poly(N,N-dialkylaminocarbonylmethylene) structure. The solubility and thermal property of the polymers were also investigated. 相似文献
45.
A new chelating radical ligand 4ImNNH (2-(4-imidazolyl)-4,4,5,5-tetramethylimidazolin-1-oxyl 3-oxide) was prepared, and complexation with divalent transition metal salts gave complexes, [M(4ImNNH)(2)X(2)], which showed intermolecular ferromagnetic interaction in high probability (7 out of 10 paramagnetic compounds investigated here). The nitrate complexes (X = NO(3); M = Mn (1), Co (2), Ni (3), Cu (4)) crystallize isomorphously in monoclinic space group P2(1)/a. The equatorial positions are occupied with two 4ImNNH chelates and the nitrate oxygen atoms are located at the axial positions. Magnetic measurements revealed that the intramolecular exchange couplings in 1, 2, and 4 were antiferromagnetic, while that in 3 was ferromagnetic with 2J/k(B) = +85 K, where the spin Hamiltonian is defined as H = -2J(S(1).S(2) + S(2).S(3)) based on the molecular structures determined as the linear radical-metal-radical triads. The intramolecular ferromagnetic interaction in 3 is interpreted in terms of orthogonality between the radical pi and metal dsigma orbitals. Compounds 1-3 exhibited intermolecular ferromagnetic interaction ascribable to a two-dimensional hydrogen bond network parallel to the crystallographic ab plane. Complex 3 became an antiferromagnet below 3.4 K and exhibited a metamagnetic transition on applying a magnetic field of 5.5 kOe at 1.8 K. The complexes prepared from metal halides, [M(4ImNNH)(2)X(2)] (X = Cl, Br; M = Mn, Co, Ni, Cu), showed intramolecular antiferromagnetic interactions, which are successfully analyzed based on the radical-metal-radical system. The crystal structures determined here on 1-4, [Mn(4ImNNH)(2)Cl(2)], and [Cu(4ImNNH)(2)Br(2)] always have intermolecular hydrogen bonds of H(imidazole).X(axial ligand)-M, where X = NO(3), Cl, Br. This interaction seems to play an important role in molecular packing and presumably also in magnetic coupling. 相似文献
46.
A simple oxide classification has been proposed on the basis of correlation between electronic polarizabilities of the ions and their binding energies determined by XPS. Three groups of oxides have been considered taking into account the values obtained on refractive-index- or energy-gap-based oxide ion polarizability, cation polarizability, optical basicity, O 1s binding energy, metal (or nonmetal) binding energy, and Yamashita-Kurosawa's interaction parameter of the oxides. The group of semicovalent predominantly acidic oxides includes BeO, B2O3, P2O5, SiO2, Al2O3, GeO2, and Ga2O3 with low oxide ion polarizability, high O 1s binding energy, low cation polarizability, high metal (or nonmetal) outermost binding energy, comparatively low optical basicity, and strong interionic interaction, leading to the formation of strong covalent bonds. Some main group oxides so-called ionic or basic such as CaO, In2O3, SnO2, and TeO2 and most transition metal oxides show relatively high oxide ion polarizability, O 1s binding energy in a very narrow medium range, high cation polarizability, and low metal (or nonmetal) binding energy. Their optical basicity varies in a narrow range and it is close to that of CaO. The group of very ionic or very basic oxides includes CdO, SrO, and BaO as well as PbO, Sb2O3, and Bi2O3, which possess very high oxide ion polarizability, low O 1s binding energy, very high cation polarizability, and very low metal (or nonmetal) binding energy. Their optical basicity is higher than that of CaO and the interionic interaction is very weak, giving rise to the formation of very ionic chemical bonds. 相似文献
47.
Hiroshi Takeuchi Makoto Nakagawa Takayuki Saito Toru Egawa Kiyoshi Tanaka Shigehiro Konaka Toshiyuki Mitsuhashi 《International journal of quantum chemistry》1994,52(6):1339-1348
The energy spectra of free water molecules were measured at scattering angles 2θ ranging from 10.5° to 75.7°, using an angle-dispersive-type diffractometer and synchrotron radiation as an X-ray source. A silicon (111) monochrometer was used to obtain incident X-rays with the wavelengths of (1.543/n) Å (n = 1,3,4,5). Observed inelastic scattering peaks are clearly separated from eleastic ones at s values [s = (4π/λ) sin Å] larger than 8 Å?1. The increase of the separation with an increasing s value was consistent with the classical theory of the Compton shift. The total (elastic plus inelastic) intensities were obtained over a range of s = 0.74–5.0 Å?1. Experimental difference intensities Δσee and Δσne were obtained separately by combining the X-ray and high-energy electron scattering data. The experimental results are in reasonable agreement with the theoretical intensities calculated from SCF and CI molecular wave functions with a basis set of double-zeta plus polarization functions. © 1994 John Wiley & Sons, Inc. 相似文献
48.
Takayuki Otsu Bunichiro Yamada Shigeru Sugiyama Shigeki Mori 《Journal of polymer science. Part A, Polymer chemistry》1980,18(7):2197-2207
Radical polymerization and copolymerization of some o-alkylphenyl methacrylates were carried out and the effect of the ortho-substituents on the ability to homopolymerize, on the monomer reactivities, and on the ceiling temperatures of the monomers was studied. The effect of the substituent on tacticities and thermal stabilities of the polymers formed was also discussed. The ability to honiopolymerize and the monomer reactivity were considerably decreased by the introduction of the o-substituent. 2,6-Di-tert-butylphenyl methacrylate formed no methanol-insoluble polymer at 60°C. On the basis of the tacticity determined it was noted that the o-substituted phenyl methacrylates preferred syndiotactic addition in the propagation reaction less than did phenyl methacrylate or methyl methacrylate. The polymers formed from the o-substituted monomers were thermally less stable than poly(phenyl methacrylate), and, consistent with this finding, ceiling temperatures of the o-substituted phenyl methacrylates seemed to be lower than that of phenyl methacrylate. The effects observed were characteristic of the o-substituents conformationally close to the carbon-carbon double bond of the monomer or the carbon carrying the unpaired electron of the polymer radical. 相似文献
49.
Aqueous Titanate Sols from Ti Alkoxide-α-Hydroxycarboxylic Acid System and Preparation of Titania Films from the Sols 总被引:1,自引:0,他引:1
Ohya Tomokazu Ito Masamichi Yamada Keiko Ban Takayuki Ohya Yutaka Takahashi Yasutaka 《Journal of Sol-Gel Science and Technology》2004,30(2):71-81
Aqueous titanate sols were prepared by reactions of titanium tetraisopropoxide (TIP) with -hydroxycarboxylic acids in water. IR and Raman spectra, and elemental analyses of the precipitates obtained from the sols revealed that the carboxylates were chelated to titanium but the Ti species were polymerized to form a cluster that had a colloidal nature. Spin-coating of titania (TiO2) thin films from these sols was also examined. Interestingly, it was found that (004) preferentially oriented anatase films with refractive index of 2.54 were obtained from TIP-lactic acid-NH3 (1:1:1, molar ratio) aqueous sol. This crystallographic orientation was characteristic of the TIP-lactic acid-NH3 (1:1:1) system, and was not affected by the kinds of substrates used and the heating rate of the film. TEM observation indicated that small anatase grains had already formed at 200°C. Therefore, the crystallographic orientation might depend strongly on the structure of the chemical species of the precursor solutions. 相似文献
50.
Motokawa R Annaka M Nakahira T Koizumi S 《Colloids and surfaces. B, Biointerfaces》2004,38(3-4):213-219
By employing small-angle neutron scattering (SANS), we investigated the microstructures of, poly(N-isopropylacrylamide) (PNIPA)-block-poly(ethylene glycol) (PEG) (NE) in deuterated water D2O, as related to macroscopic behaviors of fluidity, turbidity and synerisis. SANS revealed following results: (i) microphase separation occurs at around above 17 °C in a temperature range of transparent sol below 30 °C. In the microdomain appeared in the transparent sol state, both block chains of PNIPA and PEG are swollen by water; (ii) for the NE solution of polymer concentration Wp > 3.5% (w/v), corresponding to opaque gel above 30 °C, a percolated structure, i.e., network-like domain is formed by NE as a result of macrophase separation due to dehydration of the PNIPA chains. As the temperature increases toward 40 °C, the network domain is squeezed along a direction parallel to the NE interface, which leads to increase of the interfacial thickness given by swollen PEG chains and to the macroscopic synerisis behavior. 相似文献