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61.
Mizukami Fujio Maeda Kazuyuki Toba Makoto Sano Tsuneji Niwa Shu-ich Miyazaki Mitsuharu Kojima Kunihiko 《Journal of Sol-Gel Science and Technology》1997,8(1-3):101-106
The preparation of mullite by the sol-gel method using organic polydentate ligands and the effect of the raw materials and
organic polydentate ligands on the formation of mullite were investigated. Two series of samples were prepared using tetraethoxyorthosilicate
(TEOS) and aluminum nitrate nonahydrate, or dibutoxyethylacetoacetatoaluminum (Al(OBu)2(AcAcEt)) as the silica and alumina sources, respectively, and using ethylene glycol (EG), 1,3-propanediol (PD), 1,3-butanediol
(BD), 2-methyl-2, 4-pentanediol (MPD), diethlene glycol monoethyl ether (DEME) and ethoxyethanol as the ligands. When the
alumina source was aluminum nitrate nonahydrate, mullite was apt to appear in the order of EG>PD>MPD. When Al(OBu)2(AcAcEt) was the alumina source, the tendency toward the appearance of mullite crystalline phase was EG>BD>DEME>MPD. Between
the two alumina sources, aluminum nitrate nonahydrate gave mullite much easier than Al(OBu)2(AcAcEt). These relationships were discussed from the viewpoints of the coordination ability of the ligands and the miscibility
between the silica and alumina. 相似文献
62.
Masaki Kashiwara Takahiro Kawai Toshio Oshima 《Communications in Mathematical Physics》1978,60(2):97-130
We use the holonomic character of Feynman integrals to describe their singularity structure explicitly in some simple cases. The results in §1 show that under moderate conditions Feynman amplitudes can be locally expressed essentially in terms of Legendre functions near the points where two positive- Landau-Nakanishi surfaces meet. Related topics such as hierarchical principle in perturbation theory are also discussed in terms of holonomic systems involved. In §4 we use the concrete expressions for Feynman amplitudes obtained in §1 to discuss the validity of Sato's conjecture.Supported in part by NSF MCS 75-2333Supported in part by NSF GP 36269 相似文献
63.
Mitsuru Sano 《先进技术聚合物》1995,6(3):178-184
The redox behavior in acetone solution of (1,5-dithiacyclooctane 1-oxide)bis(pentaammineruthenium(II)) has been characterized, where the concept of “molecular hysteresis” is presented. Detailed thermodynamics for the complex are studied, in which intramolecular electron transfer rates for Ru3+OS/Ru2+→Ru2+SO/Ru3+ were determined as 0.12 sec?1 and 0.055 sec?1. The molecular hysteresis consists of two important factors: isomerizations for the sulfoxideruthenium complexes and the slow intramolecular electron transfer in the complex; both are examined. Isomerization rates for Ru3+S→O and Ru2+O→S determined range from 0.4 to 5000 sec?1 and from 0.7 to 16 sec?1, respectively, for [Ru(NH3)5(sulfoxide)]2+/3+. A mechanism for the slow electron transfer in the complex is also presented. Features of molecular hysteresis are discussed. 相似文献
64.
Abe I Oguro S Utsumi Y Sano Y Noguchi H 《Journal of the American Chemical Society》2005,127(36):12709-12716
The chalcone synthase (CHS) superfamily of type III polyketide synthases (PKSs) produces a variety of plant secondary metabolites with remarkable structural diversity and biological activities (e.g., chalcones, stilbenes, benzophenones, acrydones, phloroglucinols, resorcinols, pyrones, and chromones). Here we describe an octaketide-producing novel plant-specific type III PKS from aloe (Aloe arborescens) sharing 50-60% amino acid sequence identity with other plant CHS-superfamily enzymes. A recombinant enzyme expressed in Escherichia coli catalyzed seven successive decarboxylative condensations of malonyl-CoA to yield aromatic octaketides SEK4 and SEK4b, the longest polyketides known to be synthesized by the structurally simple type III PKS. Surprisingly, site-directed mutagenesis revealed that a single residue Gly207 (corresponding to the CHS's active site Thr197) determines the polyketide chain length and product specificity. Small-to-large substitutions (G207A, G207T, G207M, G207L, G207F, and G207W) resulted in loss of the octaketide-forming activity and concomitant formation of shorter chain length polyketides (from triketide to heptaketide) including a pentaketide chromone, 2,7-dihydroxy-5-methylchromone, and a hexaketide pyrone, 6-(2,4-dihydroxy-6-methylphenyl)-4-hydroxy-2-pyrone, depending on the size of the side chain. Notably, the functional diversity of the type III PKS was shown to evolve from simple steric modulation of the chemically inert single residue lining the active-site cavity accompanied by conservation of the Cys-His-Asn catalytic triad. This provided novel strategies for the engineered biosynthesis of pharmaceutically important plant polyketides. 相似文献
65.
The spectrum of magnetic resonance is typically affected by a modulated structure in an incommensurate phase, resulting in the broadened spectrum characterized by ‘edge singularities’. We demonstrate that the modulated structure in the crystal where molecular motion exists is responsible for the narrowing of the spectrum in the fast motional region by means of the simulation of 2H NMR spectrum of [Mg(H2O)6][SiF6]. The program developed by combining the theories of phase solitons in the incommensurate phase and motional change of 2H NMR spectrum was used for the simulation. We obtained a good agreement between the theoretical 2H NMR spectrum and experimental one for [Mg(H2O)6][SiF6]. 相似文献
66.
Masami Sawada Yasuo Okumura Hitoshi Yamada Yoshio Takai Shigetoshi Takahashi Takahiro Kaneda Keiji Hirose Soichi Misumi 《Journal of mass spectrometry : JMS》1993,28(12):1525-1528
Using fast atom bombardment (FAB) mass spectrometry (MS), cross-chiral relationships were confirmed for the first time for the diasteromeric host-guest complexations between the chiral crown ether host (1) and the chiral organic ammonium ion guest (2) on the basis of the relative peak intensities (RPI). Both host–guest combinations (R, R, R, R) – 1, (R) – 2 and (S, S, S, S) – 1, (S) – 2 obviously provided larger RPI values than the combination of both (R, R, R, R) – 1, (S) – 2 and (S, S, S, S) – 1, (R) – 2 by a factor of 1.6 as an averaged value: 1.87 (n = 4)/1.16 (n = 4) = 1.6. These results are consistent with the expected stabilities of the host-guest complexations by CPK model examinations. Successfully observed cross-chiral examinations strongly suggest a potentially useful FABMS/RPI methodology for rapidly searching newly designed and synthesized crown ether-like host compounds with a higher degree of enantioselectivity. 相似文献
67.
T Kawakita T Kuroita M Yasumoto M Sano K Inaba T Fukuda T Tahara 《Chemical & pharmaceutical bulletin》1992,40(3):624-630
A series of 3,4-dihydro-3-oxo-1,4-benzoxazine-8-carboxamide derivatives was synthesized and evaluated for serotonin-3 (5-HT3) receptor antagonistic activity assessed by their ability to antagonize the von Bezold-Jarish (BJ) effect in rats. Derivatives bearing 1-azabicyclo[2.2.2]oct-3-yl moiety as a basic function attached to the carboxamide at position 8 showed more potent antagonistic activity than those bearing the other three basic moieties. Structure-activity relationships of this series showed that methyl and chloro groups were more effective as substituents at positions 4 and 6, respectively. The representative compound 15 (Y-25130) in this series showed potent antagonistic activity on the BJ effect (ED50 = 1.3 micrograms/kg i.v.), high affinity for 5-HT3 receptor (Ki = 2.9 nM) and complete protection against cisplatin-induced emesis in dogs at a dose of 0.1 mg/kg i.v. 相似文献
68.
A series of iminodiacetic acid (IDA)-linked polyamides (DpPyPyPy-IDA-PyPyPyDp) were prepared and constitute polyamides joined head-to-head by a functionalizable five-atom linker. It was found that the IDA linker exerts a unique influence over the DNA binding conformation differing from both the beta-alanine (extended) or gamma-aminobutyric acid (hairpin) linkers, resulting in cooperative parallel side-by-side 2:1 binding in an extended conformation most likely with a staggered versus stacked alignment. A generalized variant of a fluorescent intercalator displacement (FID) assay conducted on a series of hairpin deoxyoligonucleotides containing a systematically varied A/T-rich binding-site size was used to distinguish between the binding modes of the IDA-linked polyamides. 相似文献
69.
Y. Watanabe M. Nakada K. Endo H. Nakahara H. Sano 《Journal of Radioanalytical and Nuclear Chemistry》1989,136(4):257-266
KX-ray-gated emission Mössbauer spectra of57Co-labelled CoF2 and CoF2.2H2O were measured at room temperature, using the coincidence technique. A difference was found in the relative intensity of57Fe(II)/57Fe(III) between the X-ray-gated and non-gated emission spectra. The results are explained in terms of local radiolytic effects of water of crystallization and the chemical effects associated with the de-excitation processes caused by EC-decay. 相似文献
70.
Electrochemically driven clathration/declathration of ferrocene and its derivatives by a nanometer-sized coordination cage 总被引:1,自引:0,他引:1
The electrochemical, NMR, and crystallographic studies clearly indicate that the clathration and declathration of ferrocene and its derivatives in a self-assmbled Pd(II)-linked nanometer-sized cage can be controlled by the oxidation state of the guest. Namely, the guests are clathrated when they are reduced but declathrated when they are oxidized. The process is rapid on the NMR time scale but slow on the CV time scale. 相似文献