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11.
A new synthesis of (±), (+)- and (-)-lineatin (3,3,7-trimethyl-2, 9-dioxatricyclo [3.3.1.04,7] nonane, ) was achieved. The stereochemistry of (+)-lineatin was established as 1, 4, 5, 7 by an X-ray crystallographic analysis of an intermediate . 相似文献
12.
Ueda J Takeshita K Matsumoto S Yazaki K Kawaguchi M Ozawa T 《Photochemistry and photobiology》2003,77(2):165-170
The reaction of singlet oxygen (1O2) generated by ultraviolet-A (UVA)-visible light (lambda > 330 nm) irradiation of air-saturated solutions of hematoporphyrin with phenolic compounds in the presence of a spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), gave an electron spin resonance (ESR) spectrum characteristic of the DMPO-hydroxyl radical spin adduct (DMPO-*OH). In contrast, the ESR signal of 5,5-dimethyl-2-pyrrolidone-N-oxyl, an oxidative product of DMPO, was observed in the absence of phenolic compounds. The ESR signal of DMPO-*OH decreased in the presence of either a *OH scavenger or a quencher of *O2 and under anaerobic conditions, whereas it increased depending on the concentration of DMPO. These results indicate both 1O2- and DMPO-mediated formation of free *OH during the reaction. When DMPO was replaced with 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO), no DEPMPO adduct of oxygen radical species was obtained. This suggests that 1O2, as an oxidizing agent, reacts little with DEPMPO, in which a strong electron-withdrawing phosphoryl group increases the oxidation potential of DEPMPO compared with DMPO. A linear correlation between the amounts of DMPO-*OH generated and the oxidation potentials of phenolic compounds was observed, suggesting that the electron-donating properties of phenolic compounds contribute to the appearance of *OH. These observations indicate that 1O2 reacts first with DMPO, and the resulting DMPO-1O2 intermediate is immediately decomposed/reduced to give *OH. Phenolic compounds would participate in this reaction as electron donors but would not contribute to the direct conversion of 1O2 to *OH. Furthermore, DEPMPO did not cause the spin-trapping agent-mediated generation of *OH like DMPO did. 相似文献
13.
Ono K Yoshida A Saito N Fujishima T Honzawa S Suhara Y Kishimoto S Sugiura T Waku K Takayama H Kittaka A 《The Journal of organic chemistry》2003,68(19):7407-7415
Six novel 2-substituted analogues of 1alpha,25-dihydroxy-19-norvitamin D(3), 6a,b-8a,b, were efficiently synthesized utilizing (-)-quinic acid as the A-ring precursor. The C2-modified A-rings were prepared as 4-alkylated (3R,5R)-3,5-dihydroxycyclohexanones 12-15 from (-)-quinic acid based on radical allylation at the C4 position of methyl (-)-quinicate. The new type of the CD-ring coupling partner 23 was synthesized from 25-hydroxy Grundmann's ketone 19 to apply to the modified Julia olefination to construct a diene unit between the A-ring and the CD-ring. The coupling yields, including a deprotection step, were 47-62%. After the separation of the diastereomers based on C2 stereochemistry, the structure (2alpha or 2beta) was determined by (1)H NMR experiments and compared to DeLuca's 2-methyl- and 2-ethyl-1alpha,25-dihydroxy-19-norvitamin D(3). Thus, the synthesized 2alpha-(3-hydroxypropyl)-1alpha,25-dihydroxy-19-norvitamin D(3) (8a) showed almost the same potency in binding to the bovine thymus vitamin D receptor (VDR) as the natural hormone 1, while its beta-isomer 8b had only a 3% affinity. Both 2alpha-allyl- and 2alpha-propyl-1alpha,25-dihydroxy-19-norvitamin D(3) (6a and 7a) and their 2beta-analogues (6b and 7b) possessed a weak affinity for the VDR. The strong VDR ligand 8a was ca. 36-fold more potent in induction of HL-60 cell differentiation than 1, and interestingly, even the weaker ligand 8b showed a 6.7-fold higher potency in the cell differentiation activity than that of 1. 相似文献
14.
Hideki Moriishi Osamu Kikuchi Keizo Suzuki Gilles Klopman 《Theoretical chemistry accounts》1984,64(5):319-338
Reaction potential maps (RPM) have been introduced as a new tool for the study of molecular reactivity. The equipotential energy maps, which are created on given planes around a molecule, define reaction contours towards specific counter-reagent models and are evaluated by perturbation theory. Since the calculated interaction energy involves electrostatic, polarization, exchange, and charge transfer energies, the RPM's can be used to predict site selectivity in a variety of chemical reactions. We found that the calculated RPM's of the SCN– anion explained well the experimental observations that it reacts at the S atom with soft electrophiles and at the N atom with hard electrophiles. The difference in reactivity between SCN– and OCN– was clearly shown by the RPM's of these anions. The ambident nucleophilic nature of the NO
2
–
and the CH2CHO– anions was also well represented by their RPM's. 相似文献
15.
16.
Weerasak Chomkitichai Hathaithip Ninsonti Akira Baba Sukon Phanichphant Kazunari Shinbo Keizo Kato Futao Kaneko 《Surface and interface analysis : SIA》2014,46(9):607-612
We demonstrate the multiple plasmonic effect on the photocurrent properties of photoanodes containing Ag or Au nanoparticles (NPs) loaded onto titanium dioxide film (Ag–TiO2 or Au–TiO2) on Au grating surfaces. Ag–TiO2 or Au–TiO2 nanocomposite particles are prepared by a flame spray pyrolysis route. The structures and morphologies of the prepared products are characterized by high‐resolution transmission electron microscopy. The Ag–TiO2 or Au–TiO2 composite NPs are deposited by spin coating onto the Au grating surfaces. The photoanode electrode is a layered structure of blu‐ray disc‐recordable grating substrate/Au/Ag (or Au)–TiO2/dye/electrolyte/indium‐tin oxide. The plasmonic effect is induced when Ag or Au NPs are located within the propagating surface plasmon (SP) field on the Au grating surface. The short‐circuit photocurrent is increased by exciting the grating‐coupled propagating SP on the Au gratings and is further enhanced by positioning the Ag or Au NPs within the grating‐coupled SP field. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
17.
Masao Sumita Hibeki Abe Hiroyuki Kayaki Keizo Miyasaka 《Journal of Macromolecular Science: Physics》2013,52(1-2):171-184
The electrical conductivities of carbon-black-filled low-density polyethylene (LDPE), poly(methyl methacrylate) (PMMA), and poly(vinyl chloride)-vinyl acetate (PVC/ VAc) copolymer were measured as functions of carbon content and melt viscosity of the matrix at the temperatures at which the composites were prepared. Sharp breaks in the relationship between the carbon filler content and the conductivity of composites were observed in all specimens at some content of the carbon filler. The conductivity jumps as much as 10 orders of magnitude at the break point. This phenomenon has been known as the “percolation threshold”. The critical carbon content corresponding to the break point 相似文献
18.
Matsumoto T Kominami T Ueda K Sugimoto T Tada T Noguchi S Yoshino H Murata K Shiro M Negishi E Toyota N Endo S Takahashi K 《Inorganic chemistry》2002,41(18):4763-4769
The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1. 相似文献
19.
Hirokazu Tanaka Keizo Yoshida Yoshikuni Itoh Hiroshi Imanaka 《Tetrahedron letters》1981,22(35):3421-3422
The structure elucidation and synthesis of WS-1228 A, produced by , were described. 相似文献
20.
Tsuneo Uematsu 《Zeitschrift fur Physik C Particles and Fields》1985,29(1):143-146
We discuss a component formalism ofN=1 supergravity theories in 2 and 3 spacetime dimensions. Starting from gauge theories of the superconformal group, we derive the tensor calculus for conformal and Poincaré supergravity theories. A supersymmetric extension of the non-trivial analog of Einstein's equation for 2 dimensions is given in terms of the scalar curvature multiplet. 相似文献